Novel compound, conjugated polymer and production method therefor, composition for film formation, organic thin film, and organic semiconductor element

Abstract

Provided are: a novel conjugated polymer having both high carrier mobility and high solubility; a method for producing the polymer; a composition for film formation which includes the polymer; an organic thin film including the polymer; an organic semiconductor element containing the polymer; and an organic thin film transistor element. A compound according to the present disclosure is represented by general formula (1). (In the formula, R1, R2, R3, and R4 each independently represent a C1-C50 alkyl group or a C11-C50 branched alkenyl group, the alkyl or alkenyl group optionally containing -O-, -CO-, or -COO-, and at least one of R1, R2, R3, and R4 represents a branched alkyl group having two or more branches having 11-50 carbon atoms or a branched alkenyl group having one or more branches having 11-50 carbon atoms; R5 and R6 each independently represent a hydrogen atom, a fluorine atom, or a C1-C50 alkyl group; J1 and J2 each independently represent a chalcogen atom; and M1 and M2 each independently represent a hydrogen atom, a halogen atom, or one group selected from the group consisting of boron-containing groups and tin-containing groups.)

Description

Novel compounds, conjugated polymers and methods for producing the same, film-forming compositions, organic thin films, and organic semiconductor devices.

[0001] The present invention relates to a novel compound having an indenofluorenochalcogenadiazole skeleton, a conjugated polymer containing the skeleton as a structural unit, a method for producing the same, and a film-forming composition, an organic thin film, and an organic semiconductor device.

[0002] Conjugated organic compounds are well known as organic semiconductors used in organic thin-film solar cells, organic thin-film transistors, organic ELs, and the like. Conjugated organic compounds have characteristics 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] In particular, there are many examples of developing donor-acceptor (D-A) type polymers aimed at increasing intermolecular interactions or expanding the absorption region due to electrostatic interactions. Patent document 2 describes a D-A type polymer. Non-patent document 1 describes a D-A type polymer having a naphthobisthiadiazole skeleton. Non-patent document 2 describes a D-A type polymer having an anthravisthiadiazole skeleton. Patent document 3 describes a D-A type polymer having a bis(thienocyclopenta)benzothiadiazole skeleton.

[0004] Japanese Patent Publication No. 2017-59668 WO2023 / 210569 Japanese Patent Publication No. 2012-503045

[0005] Journal of the American Chemical Society, Vol. 134, pp. 3498–3507, 2012. Macromolecules, Vol. 51, pp. 5473–5484, 2018.

[0006] Conjugated polymers used as materials for organic semiconductors require properties such as high carrier mobility and high solubility, but conventional conjugated polymers do not possess both of these characteristics. The D-A type polymer described in Patent Document 2 has high carrier mobility, but further improvement in solubility is needed from the viewpoint of improving film formation.

[0007] Accordingly, an object of the present invention is to provide a novel conjugated polymer having both high carrier mobility and high solubility, a method for producing the polymer, a film-forming composition containing the polymer, an organic thin film containing the polymer, an organic semiconductor device containing the polymer, and an organic thin film transistor device.

[0008] In order to solve the above problems, the present inventors have conducted intensive studies and found that a conjugated polymer containing a specific structural unit exhibits relatively high carrier mobility while having high solubility. The conjugated polymer containing a specific structural unit and the monomer that provides the polymer are novel substances. Also, there are no reported examples of the solubility and carrier mobility of the polymer. Furthermore, the present inventors have also found that an organic thin film can be easily formed using a film-forming composition containing the polymer, and that an organic thin film transistor device produced using the organic thin film can be stably driven, thereby completing the present invention.

[0009] That is, the present invention is constituted by the following summary.

[0010] [1] A compound represented by the following general formula (1). (wherein R １ , R ２ , R ３ and R ４ each independently represent an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, the alkyl or alkenyl group may contain -O-, -CO- or -COO-, and at least one of R １ , R ２ , R ３ and R ４ represents a branched alkyl group having 11 to 50 carbon atoms and having two or more branches, or a branched alkenyl group having 11 to 50 carbon atoms and having one or more branches. R ５ and R ６ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 50 carbon atoms. J １ and J ２ each independently represent a chalcogen atom. M １ and M ２Each of these independently represents a single group selected from the group consisting of hydrogen atoms, halogen atoms, boron-containing groups, and tin-containing groups.

[0011] [3] A structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom.) A conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0012] [5] A compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom.) A compound represented by the following general formula (TT-B) or (T2-B) is reacted in the presence of a transition metal catalyst and a base. (In the formula, M ３－Ｂ and M ４－Ｂ Each of these independently represents a boron-containing group.) The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This has the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0013] [7] A compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom.) A compound represented by the following general formula (TT-Sn) or (T2-Sn) is reacted in the presence of a transition metal catalyst. (wherein M ３－Ｓｎ and M ４－Ｓｎ each independently represent a tin-containing group.) A structural unit represented by the following general formula (2), and (wherein R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ and J ２ have the same meanings as defined above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (3) or general formula (4).

[0014] [9] A compound represented by the following general formula (1a), (wherein R １ , R ２ , R ３ and R ４ each independently represent an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO- or -COO-, and R １ , R ２ , R ３ and R ４ at least one of which represents a branched alkyl group having 11 to 50 carbon atoms and two or more branches, or a branched alkenyl group having 11 to 50 carbon atoms and one or more branches. R ５ and R ６ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 50 carbon atoms. J １ and J ２ each independently represent a chalcogen atom. M １－ｈａｌ and M ２－ｈａｌ each independently represent a halogen atom.) reacting thieno[3,2-b]thiophene or 2,2'-bithiophene in the presence of a transition metal catalyst, a base and an organic acid, a divalent structural unit represented by the following general formula (2), (wherein R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J１ and J ２ represent the same meaning as described above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (3) or general formula (4).

[0015]

[11] A film-forming composition comprising the conjugated polymer according to [3].

[0016]

[12] An organic thin film comprising the conjugated polymer according to [3].

[0017]

[13] An organic semiconductor device comprising the conjugated polymer according to [3].

[0018]

[14] An organic thin film transistor device comprising the conjugated polymer according to [3].

[0019] The conjugated polymer according to an embodiment of the present invention is an organic semiconductor having both high carrier mobility and high solubility, and can efficiently drive an organic thin film transistor device having the conjugated polymer as an active layer.

[0020] It is a diagram showing the structure according to the cross-sectional shape of an organic thin film transistor device.

[0021] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and various modifications can be made within the described scope, and embodiments obtained by appropriately combining technical means respectively disclosed in different embodiments are also included in the technical scope of the present invention. In this specification, unless otherwise specified, "P to Q" representing a numerical range means "not less than P and not more than Q".

[0022] [Compound] The compound according to an embodiment of the present invention (sometimes referred to as "the compound of the present embodiment" in this specification) is a compound represented by general formula (1) (hereinafter sometimes simply referred to as compound (1)).

[0023] (In the formula, R １ , R ２ , R ３ and R ４Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １ and M ２ Each of these independently represents a single group selected from the group consisting of hydrogen atoms, halogen atoms, boron-containing groups, and tin-containing groups.

[0024] In 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 may be linear, branched, or cyclic, and may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentrichocontyl, dotrichocontyl, tritrichocontyl, tetratrichocontyl, pentacosyl, hexatrichocontyl, tetracontyl, hentetracontyl, dotetracontyl Examples include linear alkyl groups such as pentyl group, tritetracontyl group, tetratetracontyl group, and pentacontyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl 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, 4-tetradecylicosyl group, and 12-butyloctadecyl group; and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group.

[0025] In general formula (1), R １ , R ２ , R ３ and R ４As the C1-C50 alkyl group represented by , C1-C34 alkyl groups are preferred in that the solubility of the compound of this embodiment is high, C1-C20 alkyl groups are more preferred, and methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, or 12-butyloctadecyl group are even more preferred, and decyl group or hexadecyl group are particularly preferred.

[0026] In general formula (1), R １ , R ２ , R ３ and R ４ At least one of them represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. From the viewpoint of solubility, R １ , R ２ , R ３ and R ４ Preferably, two to four of these groups are independently branched alkyl groups having two or more branches with 11 to 50 carbon atoms, or branched alkenyl groups having one or more branches with 11 to 50 carbon atoms. More preferably, three or four of these groups are present, and most preferably, all four are present.

[0027] Examples of the branched alkyl group include 3,7-dimethyl-2-dodecyl group, 3,7,11-trimethyltridecyl group, 3-ethyl-7,11-dimethylpentadecyl group, 2,6-diethyl-10-methylheptadecyl group, 3,7,11-trimethyldodecyl group, 3,7,11-trimethyleicosyl group, 2,6,10,14-tetramethyldocosane group, 2,5,8,11,14-pentamethyltriacontyl group, 3,7,11,15-tetramethylhexadecyl group, 3-ethyl-7,11,15-trimethyloctadecyl group, and 3,7,11,15,1 9-pentamethyleicosyl group, 2,6-diisopropyl-10,14-dimethylheptadecyl group, 3,7-dimethyl-11-isobutylnonadecyl group, 2,5,8-trimethyl-3-ethylhexadecyl group, 3-propyl-7,11,15-trimethylpentacosyl group, 3,7,11-triisopropylheptadecyl group, 2,6-dibutyl-10-methylheptadecyl group, 3,7-diethyl-11,15-dimethylnonadecyl group, 2,6,10,14,18-pentamethyltricosyl group, 3-isopropyl-7,11,15-tetramethyleicosyl group , 2-ethyl-6,10,14-trimethyldocosyl group, 3,7,11,15-tetramethyl-9-hexadecyl group, 3,7-dimethyl-2-tetradecyl group, 3,7,11-trimethyl-5-heptadecyl group, 2,6-diethyl-10,14-dimethylnonadecyl group, 3-ethyl-7,11,15,19-tetramethyleicosyl group, 2,6,10,14-tetramethyl-8-icosyl group, 3,7,11-trimethyl-4-dodecyl group, 2,5,8,11,14,18-hexamethyl-triacontyl group, 3,7,11,15,19,23-hexameth 2,6-diethyl-10,14,18-trimethylheptadecyl group, 3,7,11,15,19-hexamethyl-eicosyl group, 2,5,8-trimethyl-3-ethylpentadecyl group, 2,6,10,14,18,22-hexamethyldocosyl group, 3,7-diisopropyl-11,15-dimethyloctadecyl group, 3,7,11-triisopropyl-5-hexadecyl group, 2,6,10,14,18-pentamethylpentadecyl group, 3,7,1115,19,23-Hexamethyltricosyl group, 3-Ethyl-7,11,15-Trimethylheptadecyl group, 2,6,10,14,18,22,26-Heptamethylheptadecyl group, 3,7,11,15,19,23,27-Heptamethyleicosyl group, 2,5,8,11,14-Pentamethylnonadecyl group, 3-Isopropyl-7,11,15,19-Tetramethyloctadecyl group, 2,6-Diisopropyl-10,14,18,22-Tetramethyltriacontyl group, 3,7,11-Triethyl-15 Examples include methylhexadecyl group, 2,6,10,14-tetraethyldocosyl group, 3-propyl-7,11,15,19,23-pentamethyltricosyl group, and 2,6,10,14,18,22,26,30-octamethyleicosyl group, with 3,7-dimethyloctyl group, 3,7,11-trimethyldodecyl group, 3,7,11,15-tetramethylhexadecyl group, and 3,7,11,15,19-pentamethyleicosyl group being preferred, and 3,7,11,15-tetramethylhexadecyl group being particularly preferred.

[0028] Examples of the branched alkenyl group include 2-ethyl-1-hexenyl group, 2-ethyl-2-hexenyl group, 2-ethyl-3-hexenyl group, 2-ethyl-4-hexenyl group, 2-ethyl-5-hexenyl group, 3,7-dimethyl-1-octenyl group, 3,7-dimethyl-2-octenyl group, 3,7-dimethyl-3-octenyl group, 3,7-dimethyl-4-octenyl group, 3,7-dimethyl-5-octenyl group, 3,7-dimethyl-6-octenyl group, 3,7-dimethyl-7-octenyl group, 2-hexyl-1-decenyl group, and 2-hexyl-2- Decenyl group, 2-hexyl-3-decenyl group, 2-hexyl-4-decenyl group, 2-hexyl-5-decenyl group, 2-hexyl-6-decenyl group, 2-hexyl-7-decenyl group, 2-hexyl-8-decenyl group, 2-hexyl-9-decenyl group, 2-decyl-1-tetradecenyl group, 2-decyl-2-tetradecenyl group, 2-decyl-3-tetradecenyl group, 2-decyl-4-tetradecenyl group, 2-decyl-5-tetradecenyl group, 2-decyl-6-tetradecenyl group, 2-decyl-7-tetradecenyl group, 2-decyl-8-tetradecenyl Group, 2-decyl-9-tetradecenyl group, 2-decyl-10-tetradecenyl group, 2-decyl-11-tetradecenyl group, 2-decyl-12-tetradecenyl group, 2-decyl-13-tetradecenyl group, 2-dodecyl-1-tetradecenyl group, 2-dodecyl-2-tetradecenyl group, 2-dodecyl-3-tetradecenyl group, 2-dodecyl-4-tetradecenyl group, 2-dodecyl-5-tetradecenyl group, 2-dodecyl-6-tetradecenyl group, 2-dodecyl-7-tetradecenyl group, 2-dodecyl-8-tetradecenyl group, 2-dodecyl-9-tetradecenyl group Tradecenyl group, 2-dodecyl-10-tetradecenyl group, 2-dodecyl-11-tetradecenyl group, 2-dodecyl-12-tetradecenyl group, 2-dodecyl-13-tetradecenyl group, 2-dodecyl-1-hexadecenyl group, 2-dodecyl-2-hexadecenyl group, 2-dodecyl-3-hexadecenyl group, 2-dodecyl-4-hexadecenyl group, 2-dodecyl-5-hexadecenyl group, 2-dodecyl-6-hexadecenyl group, 2-dodecyl-7-hexadecenyl group, 2-dodecyl-8-hexadecenyl group, 2-dodecyl-9-hexadecenyl group,2-dodecyl-10-hexadecenyl group, 2-dodecyl-11-hexadecenyl group, 2-dodecyl-12-hexadecenyl group, 2-dodecyl-13-hexadecenyl group, 2-dodecyl-14-hexadecenyl group, 2-dodecyl-15-hexadecenyl group, 2-tetradecyl-1-hexadecenyl group, 2-tetradecyl-2-hexadecenyl Nyl group, 2-tetradecyl-3-hexadecenyl group, 2-tetradecyl-4-hexadecenyl group, 2-tetradecyl-5-hexadecenyl group, 2-tetradecyl-6-hexadecenyl group, 2-tetradecyl-7-hexadecenyl group, 2-tetradecyl-8-hexadecenyl group, 2-tetradecyl-9-hexadecenyl group, 2-tetradecyl Examples include the 2-10-hexadecenyl group, 2-tetradecyl-11-hexadecenyl group, 2-tetradecyl-12-hexadecenyl group, 2-tetradecyl-13-hexadecenyl group, 2-tetradecyl-14-hexadecenyl group, 2-tetradecyl-15-hexadecenyl group, 3,7-dimethyl-2-octenyl group, 3,7,11-trimethyl-2-dodecenyl group, and 3,7,11,15-tetramethyl-2-hexadecenyl group, with 3,7-dimethyl-2-octenyl group, 3,7,11-trimethyl-2-dodecenyl group, and 3,7,11,15-tetramethyl-2-hexadecenyl group being preferred, and 3,7,11,15-tetramethyl-2-hexadecenyl group being particularly preferred.

[0029] In general formula (1), R １ , R ２ , R ３ and R ４ The 3,7,11-trimethyldodecyl group and the 3,7,11,15-tetramethylhexadecyl group are particularly preferred.

[0030] The alkyl or alkenyl group may contain -O-, -CO-, or -COO-, and examples of groups containing -O-, -CO-, or -COO- include 5-(2-ethylhexyloxy)pentyl group, 5-(2-butyloctyloxy)pentyl group, 5-(2-hexyldecyloxy)pentyl group, 5-(2-octyldodecyloxy)pentyl group, 6-(2-ethylhexyloxy)hexyl group, 6-(2-butyloctyloxy)hexyl group, 6-(2-hexyldecyloxy)hexyl group, and 6-(2-octyldodecyloxy)hexyl group. , 7-(2-ethylhexyloxy)heptyl group, 7-(2-butyloctyloxy)heptyl group, 7-(2-hexyldecyloxy)heptyl group, 7-(2-octyldodecyloxy)heptyl group, 8-(2-ethylhexyloxy)octyl group, 8-(2-butyloctyloxy)octyl group, 8-(2-hexyldecyloxy)octyl group, 8-(2-octyldodecyloxy)octyl group, 9-(2-ethylhexyloxy)nonyl group, 9-(2-butyloctyloxy)nonyl group, 9-(2-hexyldecyloxy)nonyl group, 9-( 2-octyldodecyloxy)nonyl group, 10-(2-ethylhexyloxy)decyl group, 10-(2-butyloctyloxy)decyl group, 10-(2-hexyldecyloxy)decyl group, 10-(2-octyldodecyloxy)decyl group, 11-(2-ethylhexyloxy)undecyl group, 11-(2-butyloctyloxy)undecyl group, 11-(2-hexyldecyloxy)undecyl group, 11-(2-octyldodecyloxy)undecyl group, 4-[(2-ethylhexyl)carbonyl]butyl group, 4-[(2-butyloctyl) Carbonyl]butyl group, 4-[(2-hexyldecyl)carbonyl]butyl group, 4-[(2-octyldodecyl)carbonyl]butyl group, 5-[(2-ethylhexyl)carbonyl]pentyl group, 5-[(2-butyloctyl)carbonyl]pentyl group, 5-[(2-hexyldecyl)carbonyl]pentyl group, 5-[(2-octyldodecyl)carbonyl]pentyl group, 6-[(2-ethylhexyl)carbonyl]hexyl group, 6-[(2-butyloctyl)carbonyl]hexyl group, 6-[(2-hexyldecyl)carbonyl]hexyl group,6-[(2-octyldodecyl)carbonyl]hexyl group, 7-[(2-ethylhexyl)carbonyl]heptyl group, 7-[(2-butyloctyl)carbonyl]heptyl group, 7-[(2-hexyldecyl)carbonyl]heptyl group, 7-[(2-octyldodecyl)carbonyl]heptyl group, 8-[(2-ethylhexyl)carbonyl]octyl group, 8-[(2-butyloctyl)carbonyl]octyl group, 8-[(2-hexyldecyl)carbonyl]octyl group, 8-[(2-octyldodecyl)carbonyl]octyl group, 9-[(2-ethylhexyl [(2-butyloctyl)carbonyl]nonyl group, 9-[(2-butyloctyl)carbonyl]nonyl group, 9-[(2-hexyldecyl)carbonyl]nonyl group, 9-[(2-octyldodecyl)carbonyl]nonyl group, 10-[(2-ethylhexyl)carbonyl]decyl group, 10-[(2-butyloctyl)carbonyl]decyl group, 10-[(2-hexyldecyl)carbonyl]decyl group, 10-[(2-octyldodecyl)carbonyl]decyl group, 4-[(2-ethylhexyl)oxycarbonyl]butyl group, 4-[(2-butyloctyl)oxycarbonyl]butyl Group, 4-[(2-hexyldecyl)oxycarbonyl]butyl group, 4-[(2-octyldodecyl)oxycarbonyl]butyl group, 5-[(2-ethylhexyl)oxycarbonyl]pentyl group, 5-[(2-butyloctyl)oxycarbonyl]pentyl group, 5-[(2-hexyldecyl)oxycarbonyl]pentyl group, 5-[(2-octyldodecyl)oxycarbonyl]pentyl group, 6-[(2-ethylhexyl)oxycarbonyl]hexyl group, 6-[(2-butyloctyl)oxycarbonyl]hexyl group, 6-[(2-hexyldecyl) [oxycarbonyl]hexyl group, 6-[(2-octyldodecyl)oxycarbonyl]hexyl group, 7-[(2-ethylhexyl)oxycarbonyl]heptyl group, 7-[(2-butyloctyl)oxycarbonyl]heptyl group, 7-[(2-hexyldecyl)oxycarbonyl]heptyl group, 7-[(2-octyldodecyl)oxycarbonyl]heptyl group, 8-[(2-ethylhexyl)oxycarbonyl]octyl group, 8-[(2-butyloctyl)oxycarbonyl]octyl group, 8-[(2-hexyldecyl)oxycarbonyl]octyl group,8-[(2-octyldodecyl)oxycarbonyl]octyl group, 9-[(2-ethylhexyl)oxycarbonyl]nonyl group, 9-[(2-butyloctyl)oxycarbonyl]nonyl group, 9-[(2-hexyldecyl)oxycarbonyl]nonyl group, 9-[(2-octyldodecyl)oxycarbonyl]nonyl group, 10-[(2-ethylhexyl)oxycarbonyl]decyl group, 10-[(2-butyloctyl)oxycarbonyl [bonyl]decyl group, 10-[(2-hexyldecyl)oxycarbonyl]decyl group, 10-[(2-octyldodecyl)oxycarbonyl]decyl group, 3,7-dimethyl-2-methoxydodecyl group, 3,7,11-trimethyl-2-ethoxytridecyl group, 2-(3,7,11,15-tetramethylhexadecyloxy)ethyl group, 3,7,11-trimethyl-15-methoxyhexadecyl group, 3,7,11,15,19-penta Methyl-2-methoxyeicosyl group, 2,6,10,14-tetramethyl-18-ethoxidecosyl group, 3,7,11-trimethyl-15-isopropoxyhexadecyl group, 3,7,11-trimethyl-2-methoxy-4-dodecenyl group, 3,7-dimethyl-10-oxododecyl group, 3,7,11,15-tetramethyl-2-oxohexadecyl group, 2,6,10,14-tetramethyl-18-oxodocosyl group, 3,7,11 Examples include the trimethyl-2-oxo-4-dodecenyl group, methoxycarbonyl-3,7,11-trimethyldodecyl group, ethoxycarbonyl-3,7,11,15-tetramethylhexadecyl group, 2-methoxycarbonyl-3,7,11-trimethyltridecyl group, 3-ethoxycarbonyl-7,11-dimethylpentadecyl group, and 2-(3,7,11,15-tetramethylhexadecyloxycarbonyl)ethyl group.

[0031] In general formula (1), R １ , R ２ , R ３ and R ４ The 3,7,11-trimethyldodecyl group and the 3,7,11,15-tetramethylhexadecyl group are particularly preferred.

[0032] In general formula (1), R ５ and R ６In terms of increasing the carrier mobility of the conjugated polymer using the compound of this embodiment, hydrogen atoms, fluorine atoms, or C1-C34 alkyl groups are preferred, hydrogen atoms, fluorine atoms, or C1-C20 alkyl groups are more preferred, and hydrogen atoms, fluorine atoms, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, eicosyl groups, 2-ethylhexyl groups, 3,7-dimethyloctyl groups, 2-hexyloctyl groups, 2-hexyldecyl groups, or 2-octyldodecyl groups are even more preferred. Among these, in terms of increasing the carrier mobility, ５ and R ６ It is especially preferable that it be a hydrogen atom.

[0033] In general formula (1), the above J １ and J ２ As the chalcogen atom represented by , 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 it increases the solubility of the compound in this embodiment.

[0034] In general formula (1), the M １ and M ２ Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms.

[0035] In general formula (1), the M １ and M ２ Examples of boron-containing groups represented by this formula include dihydroboryl groups and dialkoxyboryl groups.

[0036] In general formula (1), the M １ and M ２ Examples of tin-containing groups represented by this symbol include trialkylstany groups, dialkylarylstany groups, alkyldiarylstany groups, and triarylstany groups.

[0037] In general formula (1), the M １ and M ２In this embodiment, the compounds are preferably monomers with good reactivity, and therefore hydrogen atoms, bromine atoms, iodine atoms, boron-containing groups, or tin-containing groups are preferred, hydrogen atoms, bromine atoms, iodine atoms, dihydroboryl groups, dialkoxyboryl groups, or trialkylstanyl groups are more preferred, and bromine atoms are even more preferred.

[0038] Examples of compounds used in this embodiment include the following compounds, but the present invention is not limited to these.

[0039] In the compound of this embodiment, M １ M ２ The following is an example of the case where C is a hydrogen atom. In the formula, C ｎ H ２ｎ＋１ represents a branched alkyl group. n represents a natural number between 11 and 50, which may be the same or different.

[0040]

[0041] In the compound of this embodiment, M １ M ２ The following are examples of the case where is a halogen atom. In the formula, a to i may be the same or different, and represent natural numbers from 1 to 50. Examples of specific compounds included in these are also shown below.

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] In the compound of this embodiment, M １ M ２ As an example of the case where is a boron-containing group, M １ M ２ The following are examples of cases involving boron-containing groups.

[0067]

[0068] In the compound of this embodiment, M １ M ２ As an example of the case where it is a tin-containing group, M １ M ２ The following are examples of cases involving tin-containing groups.

[0069]

[0070] In the above formulas, preferably formulas (1-1-7) to (1-1-9), formulas (1-1-13) to (1-1-15), formulas (2-1-7) to (2-1-9), formulas (2-1-13) to (2-1-15), formulas (3-1-7) to (3-1-9), formulas (3-1-13) to (3-1-15), formulas (1-1-7f) to (1-1-9f), formulas (1-1-13f) to (1-1-15f), formulas (2-1-7f) to (2-1-9f), formulas (2-1-13f) to (2-1-15f) ), formulas (3-1-7f) to (3-1-9f), formulas (3-1-13f) to (3-1-15f), formulas (3-2-1f) to (3-2-6f), and particularly preferably formulas (1-1-7) to (1-1-9), formulas (1-1-13) to (1-1-15), formulas (1-1-1f) to (1-1-3f), formulas (1-1-7f) to (1-1-9f), formulas (1-1-13f) to (1-1-15f), and even more preferably formulas (1-1-7) and (1-1-13).

[0071] [Method for Producing the Compound] Next, the method for producing the compound of this embodiment will be described. The method for producing the compound of this embodiment is as shown in the following manufacturing steps (a), (b), and (c).

[0072] <Manufacturing Process (a)> Manufacturing process (a) involves generating an anion species corresponding to the compound represented by general formula (int-1) using a base such as an organometallic reagent, and reacting it with an alkyl halide to produce the compound of general formula (1) [M １ = M ２ This is a process for producing a compound represented by [the case of a hydrogen atom] (hereinafter referred to as "general formula (1)A").

[0073] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This has the same meaning as above.)

[0074] Examples of compounds represented by the general formula (int-1) include the following compounds, but the present invention is not limited to these. Specific examples of compounds included in these are also shown below.

[0075]

[0076] The compound represented by general formula (int-1) used in manufacturing process (a) is not limited in its method of acquisition, but can also be produced by appropriately combining known organic synthesis reactions. Commercially available products may also be used.

[0077] The base is not particularly limited as long as it generates an anionic species without decomposing the compound represented by the general formula (int-1). Specifically, this includes metal hydrides such as lithium hydride, sodium hydride, and potassium hydride; metal alkoxides such as lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide; organic bases such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), and 1,4-diazabicyclo[2.2.2]octane (DABCO); metallic magnesium reagents (Grignard reagents) such as 1,1-dimethylpropylmagnesium chloride, sec-butylmagnesium chloride, tert-butylmagnesium chloride, isopropylmagnesium chloride, and isopropylmagnesium bromide; lithium diisopropylamide (LDA), lithium Examples of metal amides include dicyclohexylamide, lithium 2,2,6,6-tetramethylpiperidinyl, and 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex; silazides such as lithium bis(trimethylsilyl)amide (also known as lithium hexamethyldisilazide), sodium bis(trimethylsilyl)amide (also known as sodium hexamethyldisilazide), and potassium bis(trimethylsilyl)amide (also known as potassium hexamethyldisilazide); and it is preferable to use sodium hydride, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, or 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex in terms of good reaction yield, with sodium hydride, sodium tert-butoxide, or potassium tert-butoxide being more preferable.

[0078] There are no particular restrictions on the amount of base used, but in terms of good reaction yield, 2.0 to 10.0 molar equivalents per molar equivalent of the compound represented by general formula (int-1) is preferred, and 2.0 to 6.0 molar equivalents is more preferred.

[0079] Examples of alkyl halides include chloroalkanes such as chloromethane, chloroethane, 1-chloropropane, 1-chlorobutane, 1-chloropentane, 1-chlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, 1-chloroundecane, 1-chlorododecane, 1-chlorotridecane, 1-chlorotetradecane, 1-chloropentadecane, 1-chlorohexadecane, 1-chloroheptadecane, 1-chlorooctadecane, 1-chlorononadecane, and 1-chloroeicosane; bromomethane, bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, and 1-bromotetate Bromoalkanes such as tracecane, 1-bromopentadecane, 1-bromohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-bromononadecane, 1-bromoeicosane; iodomethane, iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane, 1-iododecane, 1-io Examples of iodoalkanes include doundecane, 1-iodododecane, 1-iodotridecane, 1-iodotetradecane, 1-iodopentadecane, 1-iodohexadecane, 1-iodoheptadecane, 1-iodooctadecane, 1-iodononadecane, and 1-iodoeicosane; bromoalkanes or iodoalkanes are preferred, and iodoalkanes are more preferred, due to their good reaction yield.

[0080] There are no particular restrictions on the amount of alkyl halide used, but in terms of good reaction yield, 2.0 to 12.0 molar equivalents per molar equivalent of the compound represented by general formula (int-1) is preferred, and 2.0 to 8.0 molar equivalents is more preferred.

[0081] Manufacturing step (a) can be carried out in a solvent. There are no particular restrictions on the solvents that can be used, as long as they do not inhibit the reaction. These 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; and N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP). Examples of solvents include amide solvents such as ); 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 o-dichlorobenzene (DCB); fluorine solvents such as bis(2,2,2-trifluoroethyl)=N,N-diisopropylphosphoramidate (PF-37) and phosphoric acid=tris(2,2,2-trifluoroethyl) (TFEP); nitromethane; water; and these may be mixed and used in any ratio. Of these, aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred in terms of good reaction yield, ether solvents are more preferred, and THF is even more preferred.

[0082] There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL / mg, more preferably in the range of 0.001 to 10 mL / mg, and even more preferably in the range of 0.005 to 1.0 mL / mg, relative to the weight of the compound used (the compound represented by general formula (int-1)).

[0083] The manufacturing process (a) is preferably carried out under an inert gas atmosphere such as argon or nitrogen gas, as this results in a good reaction yield.

[0084] The manufacturing process (a) can be carried out at a temperature appropriately selected from -80°C to 100°C, and is preferably carried out at a temperature appropriately selected from -50°C to 50°C, and more preferably at a temperature appropriately selected from -30°C to 30°C, as this yields a good reaction yield.

[0085] The reaction time varies depending on the compound used (a compound represented by the general formula (int-1)), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, and more preferably 1 to 48 hours.

[0086] The compound represented by general formula (1)A is obtained by conventional processing after the completion of manufacturing step (a). If necessary, it may be purified using general methods used by those skilled in the art for the purification of organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, and Soxhlet extraction.

[0087] Examples of compounds represented by general formula (1)A obtained in manufacturing process (a) include the following compounds, but the present invention is not limited to these. In the formula, C ｎ H ２ｎ＋１ represents a branched alkyl group, and n represents a natural number between 11 and 50, which may be the same or different.

[0088]

[0089] <Manufacturing Process (b)> Manufacturing process (b) involves reacting a halogenating agent with a compound represented by general formula (1)A to produce the compound of this embodiment, general formula (1)[M １ M ２This is a process for producing compounds represented by the following formulas: [in the case of halogen atoms] (hereinafter referred to as "general formula (1)B").

[0090] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ J ２ M １－ｈａｌ and M ２－ｈａｌ (This has the same meaning as above.)

[0091] The halogenating agents include iodine, hydroiodic acid, N-iodosuccinimide, trimethylsilyliodide, N-iodophthalimide, tetramethylammonium dichloroiodate, benzyltrimethylammonium dichloroiodate, N-iodosaccharin, bis(pyridine)iodonium tetrafluoroborate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, 1-chloro-2-iodoethane, pyridineiodin monolith, and 1,3-diiodo-5,5-dimethylhydan Iodinating agents such as toin, N,N-dimethyl-N-(methylsulfanylmethylene)ammonium iodide, and carbon tetraiodide; bromine, hydrobromic acid, N-bromosuccinimide, 1,2-dibromo-1,1,2,2-tetrachloroethane, trimethylsilyl bromide, N-bromophthalimide, tetrabutylammonium tribromide, N-bromosaccharin, bis(2,4,6-trimethylpyridine)bromonium hexafluorophosphate, pyridinium bromide perbromide, and 4-dimethylaminopyridinium bromide. Perbromide, N-bromoacetamide, bromodimethylsulfonium bromide, 1-butyl-3-methylimidazolium tribromide, boron tribromide, phosphorus tribromide, trimethylphenylammonium tribromide, 1,3-dibromo-5,5-dimethylhydantoin, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, dibromoisocyanuric acid, 1,8-diazabicyclo[5.4.0]-7-undecene hydrobromic acid, benzyltrimethylammonium tribromide, bromotrichloromethane, carbon tetrabromide Examples of brominating agents include oxalyl chloride, methoxyacetyl chloride, methanesulfonyl chloride, N-chlorosuccinimide, N-chlorophthalimide, trimethylsilyl chloride, 1,3-dichloro-5,5-dimethylhydantoin, thionyl chloride, benzyltrimethylammonium tetrachloroiodate, phosphorus trichloride, phosphorus pentachloride, cyanuric acid chloride, N-chlorosaccharin, trichloromethanesulfonyl chloride, trichlorocyanuric acid, etc., and these may be mixed in any ratio. Brominating agents are preferred in terms of good reaction yield, and bromine or hydrogen bromide is even more preferred.

[0092] There are no particular restrictions on the amount of halogenating agent used, but in terms of good reaction yield, 2.0 to 20 molar equivalents per molar equivalent of the compound represented by general formula (1)A is preferred, and 2.0 to 10 molar equivalents is more preferred.

[0093] Manufacturing step (b) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and the solvents exemplified in manufacturing step (a) can be used as examples. Halogen solvents, acidic solvents and mixed solvents thereof are preferred in terms of good reaction yield, and chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, o-DCB, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, acetic acid and mixed solvents thereof are more preferred, and a mixture of chloroform, hydrobromic acid and acetic acid solution is particularly preferred.

[0094] There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL / mg, more preferably in the range of 0.001 to 10 mL / mg, and even more preferably in the range of 0.005 to 1.0 mL / mg, relative to the weight of the compound used (general formula (1)A).

[0095] The manufacturing process (b) is preferably carried out under an inert gas atmosphere such as argon or nitrogen gas, as this results in a good reaction yield.

[0096] The manufacturing process (b) can be carried out at a temperature appropriately selected from 0°C to 180°C, and is preferably carried out at a temperature appropriately selected from 20°C to 160°C, and more preferably at a temperature appropriately selected from 20°C to 140°C, in order to obtain a good reaction yield.

[0097] The reaction time varies depending on the compound used (general formula (1)A), the solvent, and the reaction temperature, but is preferably 0.1 to 24 hours, and more preferably 1 to 12 hours.

[0098] The compound represented by general formula (1)B is obtained by conventional processing after the completion of manufacturing step (b). If necessary, it may be purified using general methods used by those skilled in the art for the purification of organic compounds, such as washing, precipitation, filtration, dialysis, recrystallization, column chromatography, preparative HPLC, and Soxhlet extraction.

[0099] As compounds represented by general formula (1)B obtained in manufacturing process (b), formulas (G1-1) to (G1-9), formulas (G2-1) to (G2-9), formulas (G3-1) to (G3-9), formulas (1-1-7) to (1-1-18), formulas (1-2-1) to (1-2-8), formulas (2-1-7) to (2-1-18), formulas (2-2-1) to (2-2-6), formulas (3-1-7) to (3-1-18), formulas (3-2-1) to (3-2-6), formulas (G1-1f) to (G1 Examples of compounds represented by formulas (G2-9f), (G2-1f) to (G2-9f), (G3-1f) to (G3-9f), (1-1-7f) to (1-1-18f), (1-2-1f) to (1-2-6f), (2-1-7f) to (2-1-18f), (2-2-1f) to (2-2-6f), (3-1-7f) to (3-1-18f), (3-2-1f) to (3-2-8f) can be given, but the present invention is not limited to these.

[0100] <Manufacturing Process (c)> Manufacturing process (c) involves reacting a compound represented by general formula (1)B with a boron compound or a tin compound to produce the compound of this embodiment, general formula (1) [M １ M ２ This is a process for producing a compound represented by [the case where each group consists of a boron-containing group and a tin-containing group] (hereinafter referred to as "general formula (1)C").

[0101]

[0102] The boron compounds that can be used in the manufacturing process (c) are not particularly limited, and examples include compounds (Brea-1) to (Brea-9).

[0103]

[0104] In particular, (Brea-1), (Brea-2), (Brea-3), (Brea-4), (Brea-5), or (Brea-6) are preferred due to their good reaction yield, with (Brea-5) being more preferred.

[0105] There are no particular restrictions on the amount of boron compound used, but in terms of good reaction yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents, and more preferably in the range of 2 to 8 molar equivalents, per 1 molar equivalent of compound (1)B.

[0106] The tin compounds that can be used are not particularly limited, and examples include compounds (Snrea-1) to (Snrea-3). It is preferable to use (Snrea-1) because it has a good reaction yield. Here, as the tin compound, tin compounds in which the Me (methyl group) and n-Bu (n-butyl group) bonded to Sn in (Snrea-1) to (Snrea-3) are Et (ethyl group), nPr (n-propyl group), or Ph (phenyl group) can also be used.

[0107]

[0108] There are no particular restrictions on the amount of tin compound used, but in terms of good reaction yield, it is preferable that the amount is in the range of 1 to 10 molar equivalents, more preferably in the range of 2 to 8 molar equivalents, and even more preferably in the range of 2 to 5 molar equivalents, per 1 molar equivalent of compound (1)B.

[0109] The manufacturing method (c) can be carried out in the presence of a base. Examples of bases that can be used include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium hexamethyldisilazide, lithium tetramethylpiperidide, lithium diisopropylamide, and 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex. Alkyllithium is preferred in terms of good reaction yield, methyllithium, n-butyllithium, sec-butyllithium, or tert-butyllithium are more preferred, and n-butyllithium is even more preferred.

[0110] There are no restrictions on the amount of base used, but in terms of yield, 1 to 10 molar equivalents per 1 molar equivalent of compound (1)B is preferred, more preferably in the range of 2 to 5 molar equivalents, and even more preferably in the range of 2 to 3 molar equivalents.

[0111] Manufacturing step (c) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and the solvents exemplified in manufacturing step (a) can be used as examples. Aliphatic hydrocarbon solvents, ether solvents, aromatic hydrocarbon solvents, mixed solvents of aliphatic hydrocarbon solvents and ether solvents, or mixed solvents of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred in terms of good reaction yield, ether solvents are more preferred, and THF is even more preferred.

[0112] There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL / mg relative to the weight of compound (1)B used, more preferably in the range of 0.001 to 10 mL / mg, even more preferably in the range of 0.005 to 1.0 mL / mg, and especially preferably in the range of 0.01 to 1.0 mL / mg.

[0113] The manufacturing process (c) is preferably carried out under an inert gas atmosphere such as argon or nitrogen gas, as this results in a better yield.

[0114] There are no restrictions on the reaction temperature at which manufacturing step (c) is carried out, but it is preferable to carry it out in the range of -78°C to 100°C, and more preferably in the range of -78°C to 30°C, for good yield.

[0115] The reaction time varies depending on the type of compound (1)B, the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours, even more preferably 1 to 48 hours, and particularly preferably 1 to 24 hours.

[0116] The compound represented by general formula (1)C is obtained by normal processing after the completion of manufacturing step (c). If necessary, it may be purified by recrystallization, precipitation, filtration, dialysis, column chromatography, preparative HPLC, Soxhlet extraction, etc.

[0117] As a compound represented by general formula (1)C obtained in manufacturing process (c), M １ M ２ The following boron-containing groups or tin-containing groups can be listed.

[0118]

[0119]

[0120] [Conjugated Polymer] A conjugated polymer according to one embodiment of the present invention (which may also be referred to as "the conjugated polymer of this embodiment" in this specification) comprises a structural unit represented by general formula (2) and a structural unit represented by general formula (3) or general formula (4).

[0121] (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom.

[0122]

[0123] In general formula (2), R １ , R ２ , R ３ , R ４ , R ５ and R ６The alkyl group having 1 to 50 carbon atoms represented by may be linear, branched, or cyclic, and may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentrichocontyl, dotrichocontyl, tritrichocontyl, tetratrichocontyl, pentacosyl, hexatrichocontyl, tetracontyl, hentetracontyl, dotetracontyl Examples include linear alkyl groups such as pentyl group, tritetracontyl group, tetratetracontyl group, and pentacontyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl 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, 4-tetradecylicosyl group, and 12-butyloctadecyl group; and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group.

[0124] In general formula (2), R １ , R ２ , R ３ and R ４As the C1-C50 alkyl group represented by , C1-C34 alkyl groups are preferred in that the solubility of the compound of this embodiment is high, C1-C20 alkyl groups are more preferred, and methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, or 12-butyloctadecyl group are even more preferred, and decyl group or hexadecyl group are particularly preferred.

[0125] In general formula (2), R １ , R ２ , R ３ and R ４ At least one of them represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. From the viewpoint of solubility, R １ , R ２ , R ３ and R ４ Preferably, two to four of these are independently branched alkyl groups having two or more branches with 11 to 50 carbon atoms, or branched alkenyl groups having one or more branches with 11 to 50 carbon atoms. More preferably, three or four of these are these groups, and most preferably, all four are.

[0126] Examples of the branched alkyl group include 3,7-dimethyl-2-dodecyl group, 3,7,11-trimethyltridecyl group, 3-ethyl-7,11-dimethylpentadecyl group, 2,6-diethyl-10-methylheptadecyl group, 3,7,11-trimethyldodecyl group, 3,7,11-trimethyleicosyl group, 2,6,10,14-tetramethyldocosane group, 2,5,8,11,14-pentamethyltriacontyl group, 3,7,11,15-tetramethylhexadecyl group, 3-ethyl-7,11,15-trimethyloctadecyl group, and 3,7,11,15,1 9-pentamethyleicosyl group, 2,6-diisopropyl-10,14-dimethylheptadecyl group, 3,7-dimethyl-11-isobutylnonadecyl group, 2,5,8-trimethyl-3-ethylhexadecyl group, 3-propyl-7,11,15-trimethylpentacosyl group, 3,7,11-triisopropylheptadecyl group, 2,6-dibutyl-10-methylheptadecyl group, 3,7-diethyl-11,15-dimethylnonadecyl group, 2,6,10,14,18-pentamethyltricosyl group, 3-isopropyl-7,11,15-tetramethyleicosyl group , 2-ethyl-6,10,14-trimethyldocosyl group, 3,7,11,15-tetramethyl-9-hexadecyl group, 3,7-dimethyl-2-tetradecyl group, 3,7,11-trimethyl-5-heptadecyl group, 2,6-diethyl-10,14-dimethylnonadecyl group, 3-ethyl-7,11,15,19-tetramethyleicosyl group, 2,6,10,14-tetramethyl-8-icosyl group, 3,7,11-trimethyl-4-dodecyl group, 2,5,8,11,14,18-hexamethyl-triacontyl group, 3,7,11,15,19,23-hexameth 2,6-diethyl-10,14,18-trimethylheptadecyl group, 3,7,11,15,19-hexamethyl-eicosyl group, 2,5,8-trimethyl-3-ethylpentadecyl group, 2,6,10,14,18,22-hexamethyldocosyl group, 3,7-diisopropyl-11,15-dimethyloctadecyl group, 3,7,11-triisopropyl-5-hexadecyl group, 2,6,10,14,18-pentamethylpentadecyl group, 3,7,1115,19,23-Hexamethyltricosyl group, 3-Ethyl-7,11,15-Trimethylheptadecyl group, 2,6,10,14,18,22,26-Heptamethylheptadecyl group, 3,7,11,15,19,23,27-Heptamethyleicosyl group, 2,5,8,11,14-Pentamethylnonadecyl group, 3-Isopropyl-7,11,15,19-Tetramethyloctadecyl group, 2,6-Diisopropyl-10,14,18,22-Tetramethyltriacontyl group, 3,7,11-Triethyl-15 Examples include methylhexadecyl group, 2,6,10,14-tetraethyldocosyl group, 3-propyl-7,11,15,19,23-pentamethyltricosyl group, and 2,6,10,14,18,22,26,30-octamethyleicosyl group, with 3,7-dimethyloctyl group, 3,7,11-trimethyldodecyl group, 3,7,11,15-tetramethylhexadecyl group, and 3,7,11,15,19-pentamethyleicosyl group being preferred, and 3,7,11,15-tetramethylhexadecyl group being particularly preferred.

[0127] Examples of the branched alkenyl group include 2-ethyl-1-hexenyl group, 2-ethyl-2-hexenyl group, 2-ethyl-3-hexenyl group, 2-ethyl-4-hexenyl group, 2-ethyl-5-hexenyl group, 3,7-dimethyl-1-octenyl group, 3,7-dimethyl-2-octenyl group, 3,7-dimethyl-3-octenyl group, 3,7-dimethyl-4-octenyl group, 3,7-dimethyl-5-octenyl group, 3,7-dimethyl-6-octenyl group, 3,7-dimethyl-7-octenyl group, 2-hexyl-1-decenyl group, and 2-hexyl-2- Decenyl group, 2-hexyl-3-decenyl group, 2-hexyl-4-decenyl group, 2-hexyl-5-decenyl group, 2-hexyl-6-decenyl group, 2-hexyl-7-decenyl group, 2-hexyl-8-decenyl group, 2-hexyl-9-decenyl group, 2-decyl-1-tetradecenyl group, 2-decyl-2-tetradecenyl group, 2-decyl-3-tetradecenyl group, 2-decyl-4-tetradecenyl group, 2-decyl-5-tetradecenyl group, 2-decyl-6-tetradecenyl group, 2-decyl-7-tetradecenyl group, 2-decyl-8-tetradecenyl Group, 2-decyl-9-tetradecenyl group, 2-decyl-10-tetradecenyl group, 2-decyl-11-tetradecenyl group, 2-decyl-12-tetradecenyl group, 2-decyl-13-tetradecenyl group, 2-dodecyl-1-tetradecenyl group, 2-dodecyl-2-tetradecenyl group, 2-dodecyl-3-tetradecenyl group, 2-dodecyl-4-tetradecenyl group, 2-dodecyl-5-tetradecenyl group, 2-dodecyl-6-tetradecenyl group, 2-dodecyl-7-tetradecenyl group, 2-dodecyl-8-tetradecenyl group, 2-dodecyl-9-tetradecenyl group Tradecenyl group, 2-dodecyl-10-tetradecenyl group, 2-dodecyl-11-tetradecenyl group, 2-dodecyl-12-tetradecenyl group, 2-dodecyl-13-tetradecenyl group, 2-dodecyl-1-hexadecenyl group, 2-dodecyl-2-hexadecenyl group, 2-dodecyl-3-hexadecenyl group, 2-dodecyl-4-hexadecenyl group, 2-dodecyl-5-hexadecenyl group, 2-dodecyl-6-hexadecenyl group, 2-dodecyl-7-hexadecenyl group, 2-dodecyl-8-hexadecenyl group, 2-dodecyl-9-hexadecenyl group,2-dodecyl-10-hexadecenyl group, 2-dodecyl-11-hexadecenyl group, 2-dodecyl-12-hexadecenyl group, 2-dodecyl-13-hexadecenyl group, 2-dodecyl-14-hexadecenyl group, 2-dodecyl-15-hexadecenyl group, 2-tetradecyl-1-hexadecenyl group, 2-tetradecyl-2-hexadecenyl Nyl group, 2-tetradecyl-3-hexadecenyl group, 2-tetradecyl-4-hexadecenyl group, 2-tetradecyl-5-hexadecenyl group, 2-tetradecyl-6-hexadecenyl group, 2-tetradecyl-7-hexadecenyl group, 2-tetradecyl-8-hexadecenyl group, 2-tetradecyl-9-hexadecenyl group, 2-tetradecyl Examples include the 2-10-hexadecenyl group, 2-tetradecyl-11-hexadecenyl group, 2-tetradecyl-12-hexadecenyl group, 2-tetradecyl-13-hexadecenyl group, 2-tetradecyl-14-hexadecenyl group, 2-tetradecyl-15-hexadecenyl group, 3,7-dimethyl-2-octenyl group, 3,7,11-trimethyl-2-dodecenyl group, and 3,7,11,15-tetramethyl-2-hexadecenyl group, with 3,7-dimethyl-2-octenyl group, 3,7,11-trimethyl-2-dodecenyl group, and 3,7,11,15-tetramethyl-2-hexadecenyl group being preferred, and 3,7,11,15-tetramethyl-2-hexadecenyl group being particularly preferred.

[0128] The alkyl or alkenyl group may contain -O-, -CO-, or -COO-, and examples of groups containing -O-, -CO-, or -COO- include 5-(2-ethylhexyloxy)pentyl group, 5-(2-butyloctyloxy)pentyl group, 5-(2-hexyldecyloxy)pentyl group, 5-(2-octyldodecyloxy)pentyl group, 6-(2-ethylhexyloxy)hexyl group, 6-(2-butyloctyloxy)hexyl group, 6-(2-hexyldecyloxy)hexyl group, and 6-(2-octyldodecyloxy)hexyl group. , 7-(2-ethylhexyloxy)heptyl group, 7-(2-butyloctyloxy)heptyl group, 7-(2-hexyldecyloxy)heptyl group, 7-(2-octyldodecyloxy)heptyl group, 8-(2-ethylhexyloxy)octyl group, 8-(2-butyloctyloxy)octyl group, 8-(2-hexyldecyloxy)octyl group, 8-(2-octyldodecyloxy)octyl group, 9-(2-ethylhexyloxy)nonyl group, 9-(2-butyloctyloxy)nonyl group, 9-(2-hexyldecyloxy)nonyl group, 9-( 2-octyldodecyloxy)nonyl group, 10-(2-ethylhexyloxy)decyl group, 10-(2-butyloctyloxy)decyl group, 10-(2-hexyldecyloxy)decyl group, 10-(2-octyldodecyloxy)decyl group, 11-(2-ethylhexyloxy)undecyl group, 11-(2-butyloctyloxy)undecyl group, 11-(2-hexyldecyloxy)undecyl group, 11-(2-octyldodecyloxy)undecyl group, 4-[(2-ethylhexyl)carbonyl]butyl group, 4-[(2-butyloctyl) Carbonyl]butyl group, 4-[(2-hexyldecyl)carbonyl]butyl group, 4-[(2-octyldodecyl)carbonyl]butyl group, 5-[(2-ethylhexyl)carbonyl]pentyl group, 5-[(2-butyloctyl)carbonyl]pentyl group, 5-[(2-hexyldecyl)carbonyl]pentyl group, 5-[(2-octyldodecyl)carbonyl]pentyl group, 6-[(2-ethylhexyl)carbonyl]hexyl group, 6-[(2-butyloctyl)carbonyl]hexyl group, 6-[(2-hexyldecyl)carbonyl]hexyl group,6-[(2-octyldodecyl)carbonyl]hexyl group, 7-[(2-ethylhexyl)carbonyl]heptyl group, 7-[(2-butyloctyl)carbonyl]heptyl group, 7-[(2-hexyldecyl)carbonyl]heptyl group, 7-[(2-octyldodecyl)carbonyl]heptyl group, 8-[(2-ethylhexyl)carbonyl]octyl group, 8-[(2-butyloctyl)carbonyl]octyl group, 8-[(2-hexyldecyl)carbonyl]octyl group, 8-[(2-octyldodecyl)carbonyl]octyl group, 9-[(2-ethylhexyl [(2-butyloctyl)carbonyl]nonyl group, 9-[(2-butyloctyl)carbonyl]nonyl group, 9-[(2-hexyldecyl)carbonyl]nonyl group, 9-[(2-octyldodecyl)carbonyl]nonyl group, 10-[(2-ethylhexyl)carbonyl]decyl group, 10-[(2-butyloctyl)carbonyl]decyl group, 10-[(2-hexyldecyl)carbonyl]decyl group, 10-[(2-octyldodecyl)carbonyl]decyl group, 4-[(2-ethylhexyl)oxycarbonyl]butyl group, 4-[(2-butyloctyl)oxycarbonyl]butyl Group, 4-[(2-hexyldecyl)oxycarbonyl]butyl group, 4-[(2-octyldodecyl)oxycarbonyl]butyl group, 5-[(2-ethylhexyl)oxycarbonyl]pentyl group, 5-[(2-butyloctyl)oxycarbonyl]pentyl group, 5-[(2-hexyldecyl)oxycarbonyl]pentyl group, 5-[(2-octyldodecyl)oxycarbonyl]pentyl group, 6-[(2-ethylhexyl)oxycarbonyl]hexyl group, 6-[(2-butyloctyl)oxycarbonyl]hexyl group, 6-[(2-hexyldecyl) [oxycarbonyl]hexyl group, 6-[(2-octyldodecyl)oxycarbonyl]hexyl group, 7-[(2-ethylhexyl)oxycarbonyl]heptyl group, 7-[(2-butyloctyl)oxycarbonyl]heptyl group, 7-[(2-hexyldecyl)oxycarbonyl]heptyl group, 7-[(2-octyldodecyl)oxycarbonyl]heptyl group, 8-[(2-ethylhexyl)oxycarbonyl]octyl group, 8-[(2-butyloctyl)oxycarbonyl]octyl group, 8-[(2-hexyldecyl)oxycarbonyl]octyl group,8-[(2-octyldodecyl)oxycarbonyl]octyl group, 9-[(2-ethylhexyl)oxycarbonyl]nonyl group, 9-[(2-butyloctyl)oxycarbonyl]nonyl group, 9-[(2-hexyldecyl)oxycarbonyl]nonyl group, 9-[(2-octyldodecyl)oxycarbonyl]nonyl group, 10-[(2-ethylhexyl)oxycarbonyl]decyl group, 10-[(2-butyloctyl)oxycarbonyl [bonyl]decyl group, 10-[(2-hexyldecyl)oxycarbonyl]decyl group, 10-[(2-octyldodecyl)oxycarbonyl]decyl group, 3,7-dimethyl-2-methoxydodecyl group, 3,7,11-trimethyl-2-ethoxytridecyl group, 2-(3,7,11,15-tetramethylhexadecyloxy)ethyl group, 3,7,11-trimethyl-15-methoxyhexadecyl group, 3,7,11,15,19-penta Methyl-2-methoxyeicosyl group, 2,6,10,14-tetramethyl-18-ethoxidecosyl group, 3,7,11-trimethyl-15-isopropoxyhexadecyl group, 3,7,11-trimethyl-2-methoxy-4-dodecenyl group, 3,7-dimethyl-10-oxododecyl group, 3,7,11,15-tetramethyl-2-oxohexadecyl group, 2,6,10,14-tetramethyl-18-oxodocosyl group, 3,7,11 Examples include the trimethyl-2-oxo-4-dodecenyl group, methoxycarbonyl-3,7,11-trimethyldodecyl group, ethoxycarbonyl-3,7,11,15-tetramethylhexadecyl group, 2-methoxycarbonyl-3,7,11-trimethyltridecyl group, 3-ethoxycarbonyl-7,11-dimethylpentadecyl group, and 2-(3,7,11,15-tetramethylhexadecyloxycarbonyl)ethyl group.

[0129] In general formula (2), R １ , R ２ , R ３ and R ４ Particularly preferred are the 3,7,11-trimethyldodecyl group, the 3,7,11,15-tetramethylhexadecyl group, or the 12-butyloctadecyl group.

[0130] In general formula (2), R ５ and R ６In this embodiment, hydrogen atoms, fluorine atoms, or C1-C34 alkyl groups are preferred in terms of increasing the carrier mobility of the conjugated polymer, hydrogen atoms, fluorine atoms, or C1-C20 alkyl groups are more preferred, and hydrogen atoms, fluorine atoms, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, eicosyl groups, 2-ethylhexyl groups, 3,7-dimethyloctyl groups, 2-hexyloctyl groups, or 2-octyldodecyl groups are even more preferred in terms of increasing the carrier mobility of the conjugated polymer. ５ and R ６ It is especially preferable that it be a hydrogen atom.

[0131] In general formula (2), J １ and J ２ As the chalcogen atom represented by , an oxygen atom, a sulfur atom, or a selenium atom is preferred, more preferably an oxygen atom or a sulfur atom, and even more preferably a sulfur atom, in that it increases the solubility of the conjugated polymer of this embodiment.

[0132] The conjugated polymer of this embodiment does not have any particular restrictions on the order of the structural units, as long as it contains structural units represented by general formula (2) and structural units represented by general formula (3) or general formula (4). Examples of copolymerization modes include alternating, random, block, or gradient.

[0133] Examples of the conjugated polymers in this embodiment include the structural units shown below, but the present invention is not limited to these. In the formulas, a to i represent natural numbers from 1 to 50, which may be the same or different. Examples of specific structural units included therein are also shown below.

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] In terms of achieving higher film-forming properties and carrier mobility of the conjugated polymer in this embodiment, any structural unit represented by formulas (5-1-7) to (5-1-9), formulas (5-1-13) to (5-1-15), formulas (5-1-7f) to (5-1-9f), and formulas (5-1-13f) to (5-1-15f) is preferred, any structural unit represented by formulas (5-1-7), (5-1-13), (5-1-7f), and (5-1-13f) is more preferred, and any structural unit represented by formulas (5-1-7) and (5-1-13) is particularly preferred.

[0155] The conjugated polymer of this embodiment may contain structural units other than the structural unit represented by general formula (2) and the structural unit represented by general formula (3) or general formula (4), to the extent that the effects of the present invention are not impaired. Preferably, the total content of the structural unit represented by general formula (2) and the structural unit represented by general formula (3) or general formula (4) in the conjugated polymer of this embodiment is 90% by mass or more, and more preferably 95% by mass or more.

[0156] There are no particular restrictions on the terminal structure of the conjugated polymer in this embodiment, but examples include hydrogen atoms, boron-containing groups such as dihydroxyboryl groups and dialkoxyboryl groups, tin-containing groups such as trimethylstanyl groups and tributylstanyl groups, 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.

[0157] The weight-average molecular weight (Mw) of the conjugated polymer in this embodiment is preferably 3,000 to 1,000,000, more preferably 3,000 to 1,000,000, and even more preferably 3,000 to 500,000.

[0158] The molecular weight distribution (PDI) of the conjugated polymer in this embodiment is preferably 1.05 to 20.0, more preferably 1.2 to 10.0, even more preferably 1.2 to 9.0, and particularly preferably 1.2 to 8.0.

[0159] In the conjugated polymer of this embodiment, the molar ratio of structural units represented by general formula (2) to structural units represented by general formula (3) or general formula (4) (structural units represented by general formula (2): structural units represented by general formula (3) or general formula (4)) 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, even more preferably in the range of 2:1 to 1:2, particularly preferably in the range of 1.2:1 to 1:1.2, and especially preferably 1:1.

[0160] [Method for producing conjugated polymers] Next, the method for producing the conjugated polymer of this embodiment (hereinafter referred to as "the method for producing this embodiment") will be described. The method for producing the conjugated polymer of this embodiment is as shown in the following manufacturing steps (A) to (C).

[0161] <Manufacturing Process (A)> Manufacturing process (A) is a method for producing the conjugated polymer of this embodiment by coupling a compound represented by general formula (1a) (hereinafter sometimes simply referred to as compound (1a)) (monomer) included in compound (1) of this embodiment with a compound (monomer) represented by general formula (TT-B) or (T2-B) in the presence of a transition metal catalyst.

[0162] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ This expresses the same meaning as above. M １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom. ３－Ｂ and M ４－Ｂ Each of these independently represents a boron-containing group.

[0163] Said M １－ｈａｌ and M ２－ｈａｌ As the halogen atom represented, chlorine, bromine, or iodine is preferred, more preferably bromine or iodine, and even more preferably bromine, in terms of improving the production efficiency of the conjugated polymer in this embodiment.

[0164] Said M ３－Ｂ , and M ４－Ｂ Examples of boron-containing groups represented by the formulas are dihydroxyboryl group, dialkoxyboryl group, and the like. Dihydroxyboryl group or dialkoxyboryl group are preferred in terms of improving the production efficiency of the conjugated polymer in this embodiment, any of the groups represented by the following formulas (12-1) to (12-6) are more preferred, groups represented by formulas (12-1), (12-3), (12-5), or (12-6) are even more preferred, formula (12-1) or (12-3) are even more preferred, and formula (12-3) is particularly preferred.

[0165]

[0166] The manufacturing process (A) must be carried out in the presence of a transition metal catalyst, and examples of such transition metal catalysts 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, and oxides of metals," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, and acetylacetonate complexes." Palladium catalysts or nickel catalysts are preferred for their good reaction yield, and palladium catalysts are even more preferred. Furthermore, these metals, supported metals, metal salts, or complex compounds can be used in combination with tertiary phosphorus compounds or carbene compounds, etc.

[0167] The aforementioned palladium catalyst is not particularly limited, but examples include palladium metals such as palladium black and palladium sponge, as well as supported palladium metals such as palladium / alumina, palladium / carbon, palladium / silica, and palladium / Y-type zeolite. Furthermore, examples include metal salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, and palladium nitrate, as well as π-allyl palladium chloride dimers, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, and tris(dibenzylideneacetone)dipalladium (Pd ２ (dba) ３), dichlorodiaminepalladium, 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(diphenylphosphino)butane]palladium, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine) 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).

[0168] Among these palladium catalysts, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, and tetrakis(triphenylphosphine)palladium (Pd(PPh)) are selected based on their good reaction yield. ３ ) ４ Bis(tri-tert-butylphosphine)palladium is preferred.

[0169] The nickel catalysts mentioned above are not particularly limited, but specific examples include nickel(II) chloride, bis(triphenylphosphine)nickel(II) dichloride, bis(2,4-pentanedionato)nickel(II) hydrate, bis(1,5-cyclooctadiene)nickel(0), dichloro(1,1'-bis(diphenylphosphine)ethane)nickel, dichloro(1,1'-bis(diphenylphosphine)propane)nickel, and [1,3-bis(2,6-diisopropylphenyl)imidazo-l-2-ylidene]triphenylphosphinenickel(II) dichloride.

[0170] These palladium or nickel catalysts may be used alone or in combination with tertiary phosphorus compounds or carbene compounds. Examples of usable tertiary phosphorus compounds include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine, tri(o-tolyl)phosphine, tris(2-methoxyphenyl)phosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino)propane. Examples include 1,4-bis(diphenylphosphino)butane, 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, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, etc. Examples of carbene compounds that can be used include 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene, 1,3-di-tert-butylimidazole-2-ylidene, and 1,3-dimethyylimidazole-2-ylidene.

[0171] As the tertiary phosphorus compound, triphenylphosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine, or tri(o-tolyl)phosphine are preferred in terms of good reaction yield.

[0172] There are no particular restrictions on the amount of the transition metal catalyst used, but in terms of good reaction yield, 0.001 to 50 mole percent relative to compound (1a) is preferred, and 0.1 to 20 mole percent is more preferred.

[0173] 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 for good reaction yield.

[0174] In manufacturing process (A), it is also possible to use a co-catalyst. There are no particular limitations on the co-catalyst, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide.

[0175] The manufacturing process (A) can be carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, and includes 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; and N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP). Examples of solvents include amide solvents; 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 o-dichlorobenzene (DCB); fluorine solvents such as bis(2,2,2-trifluoroethyl)=N,N-diisopropylphosphoramidate (PF-37) and phosphoric acid=tris(2,2,2-trifluoroethyl) (TFEP); nitromethane; water; and these may be mixed and used in any ratio.Of these, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogen solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogen solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogen solvents and fluorine solvents, or mixed solvents of ether solvents and fluorine solvents are preferred in terms of good reaction yield, and aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred. Elementary solvents, halogen solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogen solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogen solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogen solvents and fluorine solvents or mixed solvents of ether solvents and fluorine solvents are more preferred, and tetralin, toluene, chlorobenzene, o-DCB, CPME, THF, mixed solvents of toluene and water or mixed solvents of tetralin and water are even more preferred.

[0176] There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL / mg relative to the weight of compound (1a).

[0177] The manufacturing process (A) can also be carried out by adding a phase transfer catalyst. The phase transfer catalysts include ethyltrimethylammonium iodide, didodecyldimethylammonium chloride, dimethyldioctadecylammonium iodide, dimethyldioctylammonium bromide, didecyldimethylammonium bromide, dimethyldimyristylammonium bromide, dihexadecyldimethylammonium bromide, diallyldimethylammonium chloride, dimethyldioctadecylammonium chloride, didodecyldimethylammonium bromide, and 4-dimethylamino-1-neopentylpyridinium Mouchloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, 1,1-dimethyl-4-phenylpiperazinium iodide, decamethonium iodide, decamethonium bromide, decyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, carbachol, corinchloride, chlorocorinchloride, bis(2-hydroxyethyl)dimethylammonium chloride, benzyldodecyldimethyl Ammonium 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 bromide, benzoylcholine bromide, zephyrancholine hydrate, tetrabutylammonium p-toluenesulfonate, tetrabutylammonium nitrate, tetrahexylammonium bisulfate, tetraethylammonium nitrate, tributylammonium chloride, trimethylpropylammonium bromide,Trimethylnonylammonium bromide, tetrabutylammonium acetate, tetrabutylammonium tetrafluoroborate, trimethyl[2-[(trimethylsilyl)methyl]benzyl]ammonium iodide, triethylammonium tetrafluoroborate, tris(2-hydroxyethyl)methylammonium hydroxide, tetrapropylammonium chloride, tetraethylammonium trifluoromethanesulfonate, tetra-n-octylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, tetrabutylammonium triflate, tetrabutylammonium tetraphenylborate, tetrapentylammonium chloride, tetrapentylammonium bromide, tetramethylammonium acetate, tetraheptylammonium iodide, methyltri-n-octylammonium chloride, tetramethylammonium hexafluorophosphate, tetrabutylammonium bifluoride, tetrabutylammonium tribromide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium thio Cyanate, 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 bisulfate, trioctylmethylammonium chloride (Aliquat 336), tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide,(Ferrocenylmethyl)trimethylammonium bromide, (Ferrocenylmethyl)trimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexyltrimethylammonium bromide, triethylammonium chloride, methyltri-n-octylammonium bisulfate, trimethyl-n-octylammonium bromide, trimethyl-n-octylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, trimethylphenylammonium tribromide, octadecyltrimethylammonium bromide, tetrabutylammonium bromide, and other ammonium salts, tetrabutylphosphonium tetraphenyl borate, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetrabutylphosphonium Examples of phosphonium salts include 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, tributyl(cyanomethyl)phosphonium chloride, etc., and these may be mixed in any ratio. Of these, ammonium salts are preferred in terms of good reaction yield, and Aliquat 336 is more preferred.

[0178] Manufacturing step (A) is carried out in the presence of a base. Examples of the base 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-tetramethylpiperidinyl lithium, and 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate; 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 bases are preferred from the viewpoint of good reaction yield, and sodium carbonate, potassium carbonate or tripotassium phosphate is more preferred.

[0179] There are no particular restrictions on the amount of the base used, but from the viewpoint of good reaction yield, the amount is preferably 0.1 to 10 molar equivalents relative to compound (1a), more preferably 1 to 5 molar equivalents.

[0180] Manufacturing step (A) can be carried out at a temperature appropriately selected from 0°C to 240°C. From the viewpoint of good reaction yield, it is preferably carried out at a temperature appropriately selected from 70°C to 220°C, and more preferably carried out at a temperature appropriately selected from 80°C to 200°C.

[0181] Manufacturing step (A) can also be carried out using a microwave reactor.

[0182] Manufacturing step (A) is preferably carried out under an inert gas atmosphere such as argon gas or nitrogen gas, or under reduced pressure.

[0183] In manufacturing process (A), the reaction time varies depending on the compounds used (compound (1a) and the compound represented by general formula (TT-B) or general formula (T2-B)), the solvent, and the reaction temperature, but is usually preferably 0.1 to 100 hours, and more preferably 1 to 78 hours.

[0184] There are no particular restrictions on the terminal structure of the conjugated polymer in this embodiment, but the terminal structure can be converted to an aromatic group by adding one or more reagents selected from the group consisting of aryl monohalides and arylboric acid after the completion of step (A). In terms of good reactivity, 2-bromothiophene or bromobenzene is preferred as the aryl monohalide, and thiophene-2-boronic acid or phenylboric acid is preferred as the arylboric acid.

[0185] The conjugated polymer of this embodiment is obtained by performing a normal treatment after the completion of manufacturing step (A). If necessary, it may be purified using general 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.

[0186] To improve the carrier mobility or solubility of the resulting conjugated polymer, organoboron compounds or organotin compounds can be added during or after the reaction to produce a conjugated polymer in which functional groups such as thienyl groups or phenyl groups are introduced at the ends of the conjugated polymer of this embodiment. The functional groups may be introduced by combining known methods, for example, according to the methods disclosed in non-patent literature (Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.).

[0187] The compound represented by general formula (TT-B) used in manufacturing process (A) is not limited in its method of acquisition, but can be manufactured by referring to methods described in non-patent literature (e.g., Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012, or Nature Chem, Vol. 11, pp. 271-277, 2019). Commercially available products may also be used.

[0188] The compound represented by the general formula (T2-B) used in manufacturing process (A) is not limited by its method of acquisition, and commercially available products may be used.

[0189] <Manufacturing Process (B)> Manufacturing process (B) is a method for producing the conjugated polymer of this embodiment by coupling a compound (monomer) represented by general formula (1a) with a compound (monomer) represented by general formula (TT-Sn) or (T2-Sn) in the presence of a transition metal catalyst.

[0190] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ J ２ M １－ｈａｌ and M ２－ｈａｌ This expresses the same meaning as above. M ３－Ｓｎ and M ４－Ｓｎ Each of these independently represents a tin-containing group.

[0191] Said M １－ｈａｌ and M ２－ｈａｌ As the halogen atom represented, chlorine, bromine, or iodine is preferred, more preferably bromine or iodine, and even more preferably bromine, in terms of improving the production efficiency of the conjugated polymer in this embodiment.

[0192] Said M ３－Ｓｎ , and M ４－Ｓｎ Examples of tin-containing groups represented by include trialkylstanyl groups, dialkylarylstanyl groups, alkyldiarylstanyl groups, and triarylstanyl groups. In terms of improving the production efficiency of the conjugated polymer in this embodiment, trialkylstanyl groups or triarylstanyl groups are preferred, any of the groups represented by formulas (13-1) to (13-5) are more preferred, and the group represented by formula (13-1) is even more preferred. In this specification, Me, Et, Pr, Bu, and Ph represent methyl, ethyl, propyl, butyl, and phenyl groups, respectively.

[0193]

[0194] The manufacturing process (B) must be carried out in the presence of a transition metal catalyst, and examples of such transition metal catalysts 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." Palladium catalysts or nickel catalysts are preferred for good reaction yield, and palladium catalysts are even more preferred. Furthermore, these metals, supported metals, metal salts, or complex compounds can be used in combination with tertiary phosphorus compounds or carbene compounds, etc.

[0195] The palladium catalyst is not particularly limited, but the palladium catalyst exemplified in manufacturing process (A) can be used as an example.

[0196] Among these palladium catalysts, those with good reaction yields include palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, and tetrakis(triphenylphosphine)palladium (Pd(PPh)). ３ ) ４ ), it is preferable to use bis(tri-tert-butylphosphine)palladium.

[0197] The nickel catalyst is not particularly limited, but the nickel catalyst exemplified in manufacturing process (A) can be used as an example.

[0198] These palladium catalysts or nickel catalysts may be used alone, or they may be used in combination with tertiary phosphorus compounds or carbene compounds. Examples of tertiary phosphorus compounds or carbene compounds that can be used include those exemplified in manufacturing step (A).

[0199] As the tertiary phosphorus compound, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, or tri(o-tolyl)phosphine, as these offer good reaction yields.

[0200] 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 for good reaction yield.

[0201] There are no particular restrictions on the amount of transition metal catalyst used, but in terms of good reaction yield, 0.001 to 50 mole percent relative to compound (1a) is preferred, and 0.1 to 20 mole percent is more preferred.

[0202] In manufacturing process (B), it is also possible to use a co-catalyst. There are no particular limitations on the co-catalyst, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide.

[0203] Manufacturing step (B) can be carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, and the solvents exemplified in manufacturing step (A) can be used as examples. Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine solvents, mixed solvents of aromatic hydrocarbon solvent and water, mixed solvents of halogen solvent and water, mixed solvents of ether solvent and water, mixed solvents of aromatic hydrocarbon solvent and sulfoxide solvent, mixed solvents of halogen solvent and sulfoxide solvent, mixed solvents of ether solvent and sulfoxide solvent, mixed solvents of aromatic hydrocarbon solvent and fluorine solvent, mixed solvents of halogen solvent and fluorine solvent, and mixed solvents of ether solvent and fluorine solvent are preferred in terms of good reaction yield, and more preferably are aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvent and fluorine solvent, mixed solvents of halogen solvent and fluorine solvent, or mixed solvents of ether solvent and fluorine solvent, and even more preferably are tetralin, toluene, chlorobenzene, o-DCB, or THF.

[0204] There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL / mg relative to the weight of compound (1a).

[0205] Manufacturing process (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, and more preferably at a temperature appropriately selected from 100°C to 200°C, in order to obtain a good reaction yield.

[0206] Manufacturing process (B) can also be carried out using a microwave reactor.

[0207] The manufacturing process (B) is preferably carried out under an inert gas atmosphere such as argon gas or nitrogen gas, or under reduced pressure.

[0208] In manufacturing step (B), the reaction time varies depending on the compound used (compound (1a), and the compound represented by the general formula (TT-Sn) or (T2-Sn)), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, and more preferably 1 to 90 hours.

[0209] There are no particular restrictions on the terminal structure of the conjugated polymer in this embodiment, but the terminal structure can be converted to an aromatic group by adding one or more reagents selected from the group consisting of aryl monohalides and aryltins after the completion of step (B). In terms of good reactivity, 2-bromothiophene or bromobenzene is preferred as the aryl monohalide, and 2-(tributylstanyl)thiophene, 2-(trimethylstanyl)thiophene, tributylphenylstannan, or trimethylphenylstannan is preferred as the aryltin.

[0210] The conjugated polymer of this embodiment is obtained by conventional processing after the completion of manufacturing step (B). If necessary, it may be purified using general 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.

[0211] For the purpose of improving carrier mobility or solubility in the resulting conjugated polymer, an organic boron compound or an organic tin compound is added during or after the reaction, whereby a conjugated polymer in which a functional group such as a thienyl group or a phenyl group is introduced at the terminal of the conjugated polymer of the present embodiment can also be produced. The functional group may be introduced by a combination of known methods, and can be introduced, for example, according to a method disclosed in non-patent literature (Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.).

[0212] There are no limitations on the method of obtaining the compound represented by general formula (TT-Sn) and the compound represented by general formula (T2-Sn) used in the production step (B), but they can be produced with reference to, for example, methods described in non-patent literature (Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012; Nature Chem, Vol. 11, pp. 271-277, 2019, etc.). Commercially available products may also be used.

[0213] <Manufacturing Step (C)> The manufacturing step (C) is a method for producing the conjugated polymer of the present embodiment by subjecting the compound (monomer) represented by (1a) to a coupling reaction with thieno[3,2-b]thiophene or 2,2'-bithiophene in the presence of a transition metal catalyst, a base and an organic acid.

[0214] (wherein R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ , J ２ , M １－ｈａｌ and M ２－ｈａｌ have the same meanings as defined above.)

[0215] The M １－ｈａｌ and M ２－ｈａｌ As the halogen atom represented by, 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, from the viewpoint of improving the production efficiency of the conjugated polymer of the present embodiment.

[0216] The manufacturing process (C) must be carried out in the presence of a transition metal catalyst, and examples of such transition metal catalysts 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." Palladium catalysts or nickel catalysts are preferred for their good reaction yield, and palladium catalysts are even more preferred. Furthermore, these metals, supported metals, metal salts, or complex compounds can be used in combination with tertiary phosphorus compounds or carbene compounds, etc.

[0217] The palladium catalyst or nickel catalyst mentioned above is not particularly limited, but the palladium catalyst or nickel catalyst exemplified in manufacturing process (A) can be used as examples.

[0218] Of these palladium catalysts or nickel catalysts, palladium catalysts are preferred in terms of their good reaction yield, and it is particularly preferable to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, or tris(dibenzylideneacetone)dipalladium.

[0219] These palladium catalysts may be used alone or in combination with tertiary phosphorus compounds. Examples of tertiary phosphorus compounds that can be used include those exemplified in manufacturing step (A).

[0220] As the tertiary phosphorus compound, tris(2-methoxyphenyl)phosphine is preferred because it yields a good reaction yield.

[0221] 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 for good reaction yield.

[0222] There are no particular restrictions on the amount of the transition metal catalyst used, but in terms of good reaction yield, 0.001 to 50 mole percent relative to compound (1a) is preferred, and 0.1 to 20 mole percent is more preferred.

[0223] In the manufacturing process (C), it is also possible to use a co-catalyst. There are no particular limitations on the co-catalyst, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide.

[0224] Manufacturing step (C) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and the solvents exemplified in manufacturing step (A) can be used as examples. Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine solvents, mixed solvents of aromatic hydrocarbon solvent and water, mixed solvents of halogen solvent and water, mixed solvents of ether solvent and water, mixed solvents of aromatic hydrocarbon solvent and sulfoxide solvent, mixed solvents of halogen solvent and sulfoxide solvent, mixed solvents of ether solvent and sulfoxide solvent, mixed solvents of aromatic hydrocarbon solvent and fluorine solvent, mixed solvents of halogen solvent and fluorine solvent, and mixed solvents of ether solvent and fluorine solvent are preferred in terms of good reaction yield, and more preferably are aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogen solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvent and fluorine solvent, mixed solvents of halogen solvent and fluorine solvent, or mixed solvents of ether solvent and fluorine solvent, and even more preferably are CPME, THF, toluene, xylene, or mesitylene.

[0225] There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL / mg relative to the weight of compound (1a).

[0226] Manufacturing step (C) is carried out in the presence of a base. Examples of the base include those exemplified in manufacturing step (A). In terms of good reaction yield, inorganic bases are preferred, and sodium carbonate, potassium carbonate, or cesium carbonate are more preferred.

[0227] There are no particular restrictions on the amount of base used, but in terms of good reaction yield, 0.1 to 10 molar equivalents and more preferably 1 to 5 molar equivalents relative to compound (1a) are preferred.

[0228] Manufacturing step (C) is carried out in the presence of an organic acid. Examples of the organic acid include carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, neodecanoic acid, capric acid, benzoic acid, and 1-adamantanecarboxylic acid; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 10-camphorsulfonic acid (CSA); and these may be mixed in any ratio. Of these, carboxylic acids are preferred in terms of good reaction yield, and acetic acid, pivalic acid, neodecanoic acid, and 1-adamantanecarboxylic acid are more preferred.

[0229] There are no particular restrictions on the amount of the organic acid used, but in terms of good reaction yield, 0.01 to 10 molar equivalents and more preferably 0.1 to 5 molar equivalents relative to compound (1a) are preferred.

[0230] Manufacturing step (C) may use additives. Examples of additives include amines such as N,N,N',N'-tetramethylmethylenediamine (TMMDA), N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethyltrimethylenediamine (TMPDA), N,N,N',N'-tetramethyltetramethylenediamine, N,N,N',N'-tetramethyl-1,6-diaminohexane (TMHDA), and N,N,N',N'-tetraethylethylenediamine (TEEDA), which may be mixed in any ratio. Of these, TMEDA is preferred because it has a good reaction yield.

[0231] There are no particular restrictions on the amount of the additive used, but in terms of good reaction yield, 0.01 to 1 molar equivalent and more preferably 0.05 to 0.5 molar equivalents per compound (1a) are preferred.

[0232] The manufacturing process (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, and more preferably at a temperature appropriately selected from 80°C to 200°C, in order to obtain a good reaction yield.

[0233] There are no particular restrictions on the terminal structure of the conjugated polymer in this embodiment, but the terminal structure can be converted to an aromatic group by adding one or more reagents selected from the group consisting of aryl monohalides and heteroarenes after the completion of step (C). In terms of good reactivity, 2-bromothiophene or bromobenzene is preferred as the aryl monohalide, and 2-methylthiophene, 2-phenylthiophene, 2-methylthiazole or 2-phenylthiazole is preferred as the heteroarene.

[0234] Manufacturing process (C) can also be carried out using a microwave reactor.

[0235] The manufacturing process (C) is preferably carried out under an inert gas atmosphere such as argon gas or nitrogen gas, or under reduced pressure.

[0236] In manufacturing step (C), the reaction time varies depending on the compound used (compound (1a)), the solvent, and the reaction temperature, but is preferably 0.1 to 100 hours, and more preferably 1 to 90 hours.

[0237] The conjugated polymer of this embodiment is obtained by conventional processing after the completion of manufacturing step (C). If necessary, it may be purified using general 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.

[0238] [Film-forming composition] Next, 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.

[0239] The film-forming composition of this embodiment is a film-forming composition comprising the conjugated polymer and solvent of this embodiment.

[0240] The solvent is not particularly limited as long as it can dissolve or disperse the conjugated polymer of this embodiment in the solvent, but examples include: ether solvents such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-fluoroethylene carbonate; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, Examples of solvents include ester solvents such as methyl butyrate and γ-lactone; amide solvents such as DMF, DMAc, and NMP; urea solvents such as TMU and DMPU; sulfoxide solvents such as 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 o-DCB; nitromethane; water; and these may be mixed in any ratio. Of these, aromatic hydrocarbons and halogen solvents are preferred because they have high boiling points and volatilize slowly, with toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, chlorobenzene, and o-DCB being more preferred.

[0241] There are no particular restrictions on the amount of solvent used, and it is more preferable to add the solvent so that the concentration of the conjugated polymer in this embodiment is 0.001 to 95 weight percent, and is appropriately selected from 0.01 to 30 weight percent.

[0242] The film-forming composition of this embodiment is obtained by dissolving or dispersing the conjugated polymer of this embodiment in a solvent. Methods for dissolving or dispersing the conjugated polymer of this embodiment in a solvent can include, for example, stirring, shaking, ball milling, or other methods well known to those skilled in the art. Heating may also be performed during this process.

[0243] 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-conorbornene), polymethyl methacrylate, polytriarylamine, and poly(9,9-dioctylfluorene-co-dimethyltriphenylamine). There are no particular restrictions on the concentration of the binder, but 0.1 to 10.0 weight percent is preferred for good coatability.

[0244] [Organic Thin Film] Next, an organic thin film containing the conjugated polymer of this embodiment (hereinafter referred to as "the organic thin film of this embodiment") will be described.

[0245] The organic thin film of this embodiment is formed using the film-forming composition of this embodiment. There are no particular limitations on the method of forming the film using the film-forming composition of this embodiment. Examples include simple coating methods such as spin coating, drop casting, dip coating, and cast coating; and printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among these, spin coating, drop casting, and inkjet are preferred because they allow for efficient film formation.

[0246] There are no particular restrictions on the thickness of the organic thin film in this embodiment, but a thickness of 1 nm to 1000 nm is preferred, and 10 nm to 500 nm is more preferred, in that it increases carrier mobility.

[0247] [Organic Semiconductor Devices] Examples of organic semiconductor devices containing the conjugated polymer of this embodiment include organic thin-film transistor devices, organic thermoelectric devices, organic photoelectric devices, and organic image sensors. Organic thin-film transistor devices and organic photoelectric devices are preferred, and organic thin-film transistor devices are more preferred.

[0248] This document describes a method for fabricating an organic thin-film transistor element containing a conjugated polymer according to this embodiment (hereinafter referred to as "the organic thin-film transistor element of this embodiment"), and in particular, an organic thin-film transistor element containing a conjugated polymer in the active layer.

[0249] The organic thin-film transistor element of the present invention is obtained by forming the organic thin film of the present invention on a substrate as an insulating layer and an active layer, and then attaching a source electrode, a drain electrode, and a gate electrode thereto.

[0250] Figure 1 shows the structure of the elements included in the organic thin-film transistor element of this embodiment. Here, 1001 is a bottom-gate-top-contact type, 1002 is a bottom-gate-bottom-contact type, 1003 is a top-gate-top-contact type, and 1004 is a top-gate-bottom-contact type transistor element. 1 is the active layer (organic semiconductor layer), 2 is the substrate, 3 is the gate electrode, 4 is the gate insulating layer, 5 is the source electrode, and 6 is the drain electrode.

[0251] Examples of substrates include plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, and cellulose triacetate; inorganic substrates such as glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Of these, glass, silicon, and highly doped silicon are preferred in terms of good transistor performance, with glass being more preferred.

[0252] Examples of gate electrodes include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, and carbon nanotubes, as well as organic electrodes such as doped conductive polymers (PEDOT-PSS). Of these, inorganic electrodes are preferred due to their good conductivity, and gold is more preferred.

[0253] 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™. Of these, an organic insulating layer is preferred due to its good insulating properties, and parylene C (trademark) is more preferred. Furthermore, the surface of these insulating layers may be modified with 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; silylamines such as hexamethyldisilazane; etc. Of these, modification with octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid, octylphosphonic acid, or hexamethyldisilazane is preferred in that it improves the carrier mobility and current on / off ratio of the organic thin-film transistor element of this embodiment and lowers the threshold voltage.

[0254] Examples of electrodes similar to those exemplified for the gate electrode can be used as the source electrode and drain electrode. Of these, inorganic electrodes are preferred due to their good conductivity, and gold is more preferred. Furthermore, in order to improve the carrier injection efficiency, these electrodes can be surface-treated using a surface treatment material. Examples of such surface treatment materials include benzenethiol, pentafluorobenzenethiol, 3,4,5-trifluorobenzenethiol, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzenethiol, and 3,5-bis(trifluoromethyl)benzenethiol.

[0255] <Summary> As can be understood from the above explanation, the present invention has the following aspects.

[0256] [1] A compound represented by the following general formula (1). (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １ and M ２ Each of these independently represents a single group selected from the group consisting of hydrogen atoms, halogen atoms, boron-containing groups, and tin-containing groups.

[0257] [2] In the above general formula (1), R １ , R ２ , R ３ and R ４The compound according to [1], wherein independently, it is a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group.

[0258] [3] A structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom.) A conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0259] [4] In the above general formula (1), R １ , R ２ , R ３ and R ４ The conjugated polymer according to [3], wherein each group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group.

[0260] [5] A compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom.) A compound represented by the following general formula (TT-B) or (T2-B) is reacted in the presence of a transition metal catalyst and a base. (In the formula, M ３－Ｂ and M ４－Ｂ Each of these independently represents a boron-containing group.) The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This has the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0261] [6] In the above general formula (1a), R １ , R ２ , R ３ and R ４ The method for producing a conjugated polymer according to [5], wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group.

[0262] [7] A compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R１ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom.) A compound represented by the following general formula (TT-Sn) or (T2-Sn) is reacted in the presence of a transition metal catalyst. (In the formula, M ３－Ｓｎ and M ４－Ｓｎ Each of these independently represents a tin-containing group.) The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This has the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0263] [8] In the above general formula (1a), R １ , R ２ , R ３ and R ４ The method for producing a conjugated polymer according to [7], wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group.

[0264] [9] A compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom.) Thieno[3,2-b]thiophene or 2,2'-bithiophene is reacted in the presence of a transition metal catalyst, a base, and an organic acid. The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This has the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4).

[0265]

[10] In the above general formula (1a), R １ , R ２ , R ３ and R ４ The method for producing a conjugated polymer according to [9], wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group.

[0266]

[11] A film-forming composition comprising the conjugated polymer described in [3] or [4].

[0267]

[12] An organic thin film comprising the conjugated polymer described in [3] or [4].

[0268]

[13] An organic semiconductor device comprising the conjugated polymer described in [3] or [4].

[0269]

[14] An organic thin-film transistor element comprising the conjugated polymer described in [3] or [4].

[0270] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0271] The monomers and their precursors used as raw materials in the examples are: １ Structural analysis was performed by 1H-NMR measurement. The molecular weight and molecular weight distribution of the conjugated polymers obtained in the examples were estimated by Gel Permeation Chromatography (GPC) measurement. Commercially available reagents were used.

[0272] <NMR Measurement Conditions> Measurement device: Bruker ASCEND ＴＭ ADVANCE III HD (400MHz) Measurement solvent: Deuterated chloroform (CDCl) ３ ) or heavy DMSO (DMSO-d ６ ) Internal standard substance: Tetramethylsilane (TMS) <GPC measurement conditions> Measurement device: Tosoh Corporation high-speed GPC instrument HLC-8320GPC EcoSEC Column: TSKgel SuperH 4000 + 3000 + 2000 + 1000 Measurement solvent: THF Measurement temperature: 40℃ Calibration curve: Polystyrene standard <High temperature GPC measurement conditions> Measurement device: Tosoh Corporation high temperature GPC instrument 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 <TGA measurement conditions> Measurement device: SII Corporation EXSTAR6000 TGA / DTA6200 Sample container: Aluminum pan Measurement atmosphere: Nitrogen Heating rate: 10°C / min. ｄ３ , T ｄ５ and T ｄ１０These represent the temperature at which weight loss occurs at 3%, 5%, and 10%, respectively. <DSC Measurement Conditions> Measurement device: SII Corporation EXSTAR6000 DSC6220 Sample container: Aluminum pan Measurement conditions: Nitrogen atmosphere, 10°C / min, 30-300°C, the third HeatingScan was used for the results. <CV Measurement Conditions> Measurement device: BioLogic VSP-300 Working electrode: Glassy carbon (φ=3mm) Counter electrode: Platinum wire (φ=0.5mm) Reference electrode: Platinum wire (φ=0.5mm) Internal standard: Ferrocene / ferrocenium (Fc / Fc ＋ Electrolyte: 0.10 M tetrabutylammonium hexafluorophosphate (Bu ４ NPF ６ ) / Acetonitrile solution scanning speed: 50 mV / s Redox potential E of the compound being measured ｓａｍｐｌｅ (Vvs.Fc / Fc ＋ ) has Fc / Fc on the horizontal axis. ＋ The HOMO level E is determined from the half-potentials of the oxidation and reduction peaks in the corrected voltammogram. ＨＯＭＯ is Fc / Fc ＋ Assuming that the oxidation-reduction potential of is -5.07 eV relative to the vacuum level, it was calculated using equation (1). ＨＯＭＯ = -5.07 - E ｓａｍｐｌｅ (1) <Ionization potential measurement conditions> Measurement device: Riken Keiki Co., Ltd. Atmospheric photoelectron spectrometer AC-5 Measurement conditions: Measurement under atmospheric conditions, light intensity 3 nW

[0273] [Compound Reference Example 1]

[0274] A mixture of 5-chloro-2,1,3-benzothiadiazole (171 mg, 1.00 mmol) and tetrahydrofuran (4.0 mL) was mixed with tetramethylpiperidinyl magnesium chloride / lithium chloride complex solution (1.2 mL, 1.1 mmol) at -20°C and stirred for 0.5 hours. Subsequently, under an argon stream, zinc chloride tetrahydrofuran solution (1.2 mL, 1.2 mmol) and Pd (PPh) were added. ３ ) ４(46 mg, 40 μmol) and 1,4-diiodo-2,5-dimethylbenzene (161 mg, 450 μmol) were added and the mixture was stirred at 80°C for 22 hours. The resulting mixture was cooled to room temperature, and then saturated ammonium chloride aqueous solution was added and extracted with ethyl acetate. The collected 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 solid was washed with methanol and acetone to obtain a pale yellow solid Compound 1 (142 mg, 71%). １ H-NMR (CDCl ３ , 400MHz) δ (ppm): 8.00 (d, J=9.2Hz, 2H), 7.75 (dd, J=9.2, 2.0Hz, 2H), 7.25 (s, 2H), 2.08 (s, 6H).

[0275] [Compound Reference Example 2]

[0276] Compound 1 (88.6 mg, 200 μmol) obtained in Compound Reference Example 1, palladium(II) acetate (1.8 mg, 8.0 μmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (5.9 mg, 12 μmol), pivalic acid (6.1 mg, 60 μmol), potassium carbonate (156 mg, 1.13 mmol), and toluene (2.0 mL) were mixed and stirred at 120°C for 20 hours. After the resulting mixture was cooled to room temperature, methanol was added to induce precipitation. The resulting solid was collected by filtration and washed with water and methanol to obtain Compound 2 (59 mg, 79%) as a yellow solid. １ H-NMR (CDCl ３ , 400MHz) δ (ppm): 8.84 (s, 2H), 7.98 (d, J = 8.4Hz, 2H), 7.87 (d, J = 8.4Hz, 2H), 4.23 (s, 4H).

[0277] [Compound Example 1]

[0278] A mixture of Compound 2 (230 mg, 0.62 mmol) obtained in Compound Reference Example 2 and tetrahydrofuran (40 mL) was mixed with sodium tert-butoxide (251 mg, 2.61 mmol) at 0°C and stirred for 1 hour. Then, 1-iodo-3,7,11,15-tetramethylhexadecane (1.52 g, 3.73 mmol) was added and stirred at room temperature for 18 hours. The reaction solution was mixed with saturated ammonium chloride aqueous solution and extracted with ethyl acetate. The collected 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 / chloroform) to obtain the yellow liquid compound (1-1-19) (144 mg, 16%). １ H-NMR (CDCl ３ , 400MHz) δ (ppm): 8.49 (s, 2H), 7.96 (d, J = 8.8Hz, 2H), 7.67 (d, J = 8.8Hz, 2H), 2 .36-2.16 (m, 8H), 1.54-1.45 (m, 6H), 1.26-0.78 (m, 116H), 0.66-0.43 (m, 34H).

[0279] [Compound Example 2]

[0280] A mixture of compound (1-1-19) (1380 mg, 0.925 mmol) obtained in Compound Example 1, chloroform (18 mL), and hydrogen bromide (30% acetic acid solution) (9.2 mL) was mixed with bromine (0.29 mL, 3.0 mmol) and refluxed for 2 hours. After the resulting mixture was cooled to room temperature, saturated sodium bicarbonate aqueous solution and saturated sodium thiosulfate aqueous solution were added and extracted with chloroform. The collected 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 / chloroform) to obtain the orange liquid compound (1-1-13) (1160 mg, 94%). １ H-NMR (CDCl ３, 400MHz) δ (ppm): 8.43 (s, 2H), 7.91 (s, 2H), 2.34-2.12 (m, 8H), 1.54-1.45 (m, 6H), 1.22-0.78 (m, 116H), 0.68-0.48 (m, 34H).

[0281] [Compound Example 3]

[0282] A mixture of Compound 2 (180 mg, 0.486 mmol) obtained in Compound Reference Example 2, potassium iodide (81 mg, 0.49 mmol), and tetrahydrofuran (10 mL) was mixed with sodium tert-butoxide (229 mg, 2.04 mmol) at -10°C and stirred for 2 hours. Then, 2-ethylhexyl-11-bromoundecanoate (1.10 g, 2.92 mmol) was added and stirred at room temperature for 22 hours. The reaction solution was mixed with saturated ammonium chloride aqueous solution and extracted with chloroform. The collected 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 crudely purified by silica gel flash column chromatography (hexane / ethyl acetate) to obtain compound A (350 mg) as an orange liquid.

[0283] Next, N-bromosuccinimide (120 mg, 0.675 mmol) was added to a mixture of compound A (350 mg) and chloroform (4.5 mL), and the mixture was stirred at 60°C for 20 hours. After the resulting mixture cooled to room temperature, saturated sodium thiosulfate aqueous solution was added, and the mixture was extracted with chloroform. The collected 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 / chloroform) to obtain the orange liquid compound (1-2-1) (165 mg, 40% in 2 steps). １ H-NMR (CDCl ３ , 400MHz) δ (ppm): 8.42 (s, 2H), 7.92 (s, 2H), 3.95 (dd, J=5.6, 2.0Hz, 8H), 2.3 1-2.10 (m, 18H), 1.35-0.98 (m, 86H), 0.88-0.84 (m, 28H), 0.67-0.59 (m, 8H).

[0284] [Compound Example 4]

[0285] A mixture of Compound 2 (470 mg, 1.27 mmol) obtained in Compound Reference Example 2, potassium iodide (211 mg, 1.27 mmol), and tetrahydrofuran (25 mL) was mixed with sodium tert-butoxide (598 mg, 5.33 mmol) at -10°C and stirred for 2 hours. Then, 1-bromo-10-[(2-ethylhexyl)oxy]decane (1.10 g, 2.92 mmol) was added and stirred at room temperature for 18 hours. The reaction solution was mixed with saturated ammonium chloride aqueous solution and extracted with chloroform. The collected 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 crudely purified by silica gel flash column chromatography (hexane / chloroform) to obtain compound B (416 mg) as an orange liquid.

[0286] Next, N-bromosuccinimide (123 mg, 0.691 mmol) was added to a mixture of compound B (416 mg) and chloroform (5.8 mL), and the mixture was stirred at 50°C for 15 hours. After the resulting mixture was cooled to room temperature, saturated sodium thiosulfate aqueous solution was added, and the mixture was extracted with chloroform. The collected 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 / chloroform) to obtain the orange liquid compound (1-2-4) (212 mg, 13% in 2 steps). １ H-NMR (CDCl ３ , 400MHz) δ (ppm): 8.43 (s, 2H), 7.92 (s, 2H), 3.28 (t, J = 6.8Hz, 8H), 3.22 (dd, J = 5.6, 0.4Hz, 8H), 2 .31-2.23 (m, 4H), 2.18-2.10 (m, 4H), 1.48-1.01 (m, 90H), 0.88-0.82 (m, 26H), 0.67-0.59 (m, 8H).

[0287] [Polymer Example 1]

[0288] A mixture of the compound (1-1-13) (149 mg, 90.5 μmol) obtained in Compound Example 2, 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (42.2 mg, 90.5 μmol), and monochlorobenzene (MCB; 2.3 mL) was bubbling with argon for 30 minutes. Pd ２ (dba) ３ CHCl ３ (1.9 mg, 1.8 μmol) and tris(o-tolyl)phosphine (2.2 mg, 7.2 μmol) were added and the mixture was stirred at 180°C for 2 hours using a microwave reactor. Then, 2-(tributylstannyl)thiophene (290 μL, 0.91 mmol) was added to the reaction solution and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. Furthermore, 2-bromothiophene (87 μL, 0.91 mmol) was added and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. After the resulting mixture was cooled to room temperature, it was precipitated in a methanol / concentrated hydrochloric acid mixture (200 mL / 20 mL) and the precipitated solid was collected by filtration. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. Then, the solid remaining on the filter was dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (125 mg, 85%). GPC (TCB, 140°C): Mn = 26000 g / mol, Mw = 40000 g / mol, PDI = 1.5.

[0289] [Polymer Example 2]

[0290] Compound (1-1-13) obtained in Compound Example 2 (103 mg, 62.3 μmol), 2,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thieno[3,2-b]thiophene (24.4 mg, 62.3 μmol), 2 M tripotassium phosphate aqueous solution (95 μL, 190 μmol), and toluene (0.6 mL) were mixed and bubbled with argon for 30 minutes. Pd ２ (dba) ３ CHCl ３ (1.3 mg, 1.2 μmol) and tri-tert-butylphosphonium tetrafluoroborate (1.4 mg, 5.0 μmol) were added and the mixture was stirred at 90°C for 24 hours. After the resulting mixture cooled to room temperature, it was diluted with chloroform, washed with water, and then precipitated in methanol. The precipitated solid was filtered. The obtained solid was removed from its solvent-soluble components by Soxhlet extraction using methanol and acetone. Furthermore, the filter residue was dissolved in hexane. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered. After washing the obtained solid with methanol, it was dried under reduced pressure at 90°C to obtain a black solid (5-1-13-A) (76 mg, 74%). GPC (TCB, 140°C): Mn = 8000 g / mol, Mw = 10000 g / mol, PDI = 1.3.

[0291] [Polymer Example 3]

[0292] Compound obtained in Compound Example 2 (1-1-13) (97.8 mg, 59.3 μmol), thieno[3,2-b]thiophene (8.31 mg, 59.3 μmol), Pd ２ (dba) ３ CHCl ３A mixture of (1.2 mg, 1.2 μmol), tris(2-methoxyphenyl)phosphine (1.7 mg, 4.7 μmol), pivalic acid (6.1 mg, 60 μmol), cesium carbonate (58 mg, 180 μmol), 0.32 M N,N,N',N'-tetramethylethylenediaminetoluene solution (20 μL, 60 μmol), and toluene (0.38 mL) was stirred at 110°C for 24 hours. After the resulting mixture cooled to room temperature, it was diluted with chloroform, washed with water, and then precipitated in methanol. The precipitated solid was filtered. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Furthermore, the filter residue was dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered after precipitation in methanol. The obtained solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-C) (55 mg, 57%). GPC (TCB, 140°C): Mn = 30,000 g / mol, Mw = 49,000 g / mol, PDI = 1.6.

[0293] [Polymer Example 4]

[0294] The reaction vessel contained the compound (1-2-1) obtained in Compound Example 3 (89.9 mg, 52.4 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (24.4 mg, 52.4 μmol), and Pd ２ (dba) ３ CHCl ３(1.1 mg, 1.0 μmol) and tri(o-tolyl)phosphine (1.3 mg, 4.2 μmol) were added, and the mixture was degassed and purged with argon. Then, monochlorobenzene (MCB; 0.35 mL) was added and the mixture was stirred at 120°C for 24 hours. Next, 2-(tributylstannyl)thiophene (170 μL, 0.52 mmol) was added to the reaction solution and the mixture was stirred at 120°C for 1 hour. Furthermore, 2-bromothiophene (50 μL, 0.52 mmol) was added and the mixture was stirred at 120°C for 1 hour. After the resulting mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was collected by filtration. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Then, the solid remaining on the filter was dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-2-1) (57 mg, 70%). GPC (TCB, 140°C): Mn = 12000 g / mol, Mw = 49000 g / mol, PDI = 4.1.

[0295] [Polymer Example 5]

[0296] The reaction vessel contained the compound obtained in Compound Example 4 (1-2-4) (97.3 mg, 60.7 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (28.3 mg, 60.7 μmol), and Pd ２ (dba) ３ CHCl ３(1.3 mg, 1.2 μmol) and tri(o-tolyl)phosphine (1.5 mg, 4.9 μmol) were added, and the mixture was degassed and purged with argon. Then, monochlorobenzene (MCB; 0.40 mL) was added and the mixture was stirred at 120°C for 24 hours. Next, 2-(tributylstannyl)thiophene (190 μL, 0.61 mmol) was added to the reaction solution and the mixture was stirred at 120°C for 1 hour. Furthermore, 2-bromothiophene (58 μL, 0.61 mmol) was added and the mixture was stirred at 120°C for 1 hour. After the resulting mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was collected by filtration. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Then, the solid remaining on the filter was dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-2-4) (86 mg, 89%). GPC (TCB, 140°C): Mn = 117,000 g / mol, Mw = 373,000 g / mol, PDI = 3.2.

[0297] [Polymer Example 6]

[0298] The reaction vessel contained the compound obtained in Compound Example 2 (1-1-13) (96.5 mg, 58.5 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (27.2 mg, 58.5 μmol), and Pd ２ (dba) ３ CHCl ３(1.2 mg, 1.2 μmol) and tri(o-tolyl)phosphine (1.4 mg, 4.7 μmol) were added, and the mixture was degassed and purged with argon. Then, monochlorobenzene (MCB; 0.39 mL) was added and the mixture was stirred at 120°C for 24 hours. After the resulting mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was collected by filtration. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The solid remaining on the filter was then dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was collected by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (91 mg, 99%). GPC (TCB, 140°C): Mn=103000g / mol, Mw=257000g / mol, PDI=2.5.

[0299] [Polymer Example 7]

[0300] The reaction vessel contained the compound obtained in Compound Example 2 (1-1-13) (92.2 mg, 55.9 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (26.0 mg, 55.9 μmol), and Pd ２ (dba) ３ CHCl ３(1.2 mg, 1.1 μmol) and tri(o-tolyl)phosphine (1.4 mg, 4.5 μmol) were added, and the mixture was degassed and purged with argon. Then, tetralin (0.37 mL) was added and the mixture was stirred at 120°C for 24 hours. The resulting mixture was cooled to room temperature and then precipitated in methanol. The precipitated solid was collected by filtration. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The solid remaining on the filter was then dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was collected by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (88 mg, 96%). GPC (TCB, 140°C): Mn=112000g / mol, Mw=280000g / mol, PDI=2.5.

[0301] [Polymer Example 8]

[0302] The reaction vessel contained the compound obtained in Compound Example 2 (1-1-13) (86.1 mg, 55.2 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (24.3 mg, 55.2 μmol), and Pd ２ (dba) ３ CHCl ３(1.1 mg, 1.0 μmol) and tri(o-tolyl)phosphine (1.3 mg, 4.2 μmol) were added, and the mixture was degassed and purged with argon. Then, tetralin (0.37 mL) was added and the mixture was stirred at 120°C for 24 hours. The resulting mixture was cooled to room temperature and then precipitated in methanol. The precipitated solid was collected by filtration. The obtained solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The solid remaining on the filter was then dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was collected by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (77 mg, 80%). GPC (TCB, 140°C): Mn=82000g / mol, Mw=194000g / mol, PDI=2.4.

[0303] [Polymer Example 9]

[0304] The reaction vessel contained the compound obtained in Compound Example 2 (1-1-13) (103 mg, 62.7 μmol), 5,5'-bis(trimethylstannyl)-2,2''-bithiophene (30.8 mg, 62.7 μmol), and Pd ２ (dba) ３ CHCl ３(1.3 mg, 1.3 μmol) and tri(o-tolyl)phosphine (1.5 mg, 5.0 μmol) were added, and the mixture was degassed and purged with argon. Then, tetralin (0.42 mL) was added and the mixture was stirred at 120°C for 24 hours. Next, 2-(tributylstannyl)thiophene (200 μL, 0.63 mmol) was added to the reaction solution and the mixture was stirred at 120°C for 1 hour. Furthermore, 2-bromothiophene (60 μL, 0.63 mmol) was added and the mixture was stirred at 120°C for 1 hour. After the resulting mixture was cooled to room temperature, it was precipitated in methanol, and the precipitated solid was collected by filtration. The obtained solid was extracted using Soxhlet extraction with methanol, acetone, and hexane to remove components soluble in these solvents. Then, the solid remaining on the filter was dissolved in chloroform. The resulting solution was concentrated under reduced pressure and added to a large amount of methanol to induce precipitation. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain the black solid 5-1-13-b (99 mg, 95%). GPC (TCB, 140°C): Mn = 135,000 g / mol, Mw = 233,000 g / mol, PDI = 2.1.

[0305] [Polymer Example 10]

[0306] The reaction vessel contained the compound obtained in Compound Example 2 (1-1-13) (91.4 mg, 55.4 μmol), 2,5-bis(trimethylstannyl)thieno[3,2-b]thiophene (25.8 mg, 55.4 μmol), and Pd ２ (dba) ３ CHCl ３(1.1 mg, 1.1 μmol) and tri(o-tolyl)phosphine (1.3 mg, 4.4 μmol) were added, and the mixture was degassed and purged with argon. Then, tetralin (0.37 mL) was added and the mixture was stirred at 120°C for 24 hours. Next, 2-(tributylstannyl)thiophene (160 μL, 0.50 mmol) was added to the reaction solution and the mixture was stirred at 120°C for 1 hour. Furthermore, 2-bromothiophene (53 μL, 0.55 mmol) was added and the mixture was stirred at 120°C for 1 hour. The resulting mixture was cooled to room temperature and then diluted with chloroform. The resulting solution was divided into two portions and each portion was subjected to the following treatments.

[0307] (1) One of the solutions was precipitated in a hexane / isopropanol mixture (75 mL / 75 mL), and the precipitated solid was collected by filtration. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (43 mg, 48%). GPC (TCB, 140°C): Mn = 86000 g / mol, Mw = 233000 g / mol, PDI = 2.7.

[0308] (2) The other solution was precipitated in a hexane / acetone mixture (75 mL / 75 mL), and the precipitated solid was collected by filtration. The resulting solid was recovered by filtration, washed with methanol, and then dried under reduced pressure at 90°C to obtain a black solid (5-1-13-B) (37 mg, 41%). GPC (TCB, 140°C): Mn = 89000 g / mol, Mw = 233000 g / mol, PDI = 2.6.

[0309] [Composition Example 1] (Solubility Measurement) Solubility was calculated using ultraviolet-visible spectrophotometric analysis, which utilizes the proportional relationship between concentration and absorbance based on the Lambert-Beer law. First, each polymer was dissolved in o-dichlorobenzene at room temperature (20-25°C) to prepare several dilute solutions with concentrations ranging from 0.0025 to 0.0125 g / L. For each dilute solution, the absorbance at the absorption maximum wavelength derived from the polymer was measured, and a calibration curve of absorbance against concentration was created. A linear relationship was observed between absorbance and concentration within this concentration range. Next, saturated solutions of each polymer were prepared at room temperature by adding an excess amount of polymer to o-DCB, leaving some undissolved solids. After allowing the suspension to stand to reach dissolution equilibrium, the undissolved solids were removed using a 0.45 μm polytetrafluoroethylene (PTFE) syringe filter. The obtained filtrate was appropriately diluted so that the absorbance at the measurement wavelength fell within the linear range of the calibration curve, and then the absorbance was measured using a UV-Vis spectrophotometer. The polymer concentration in the filtrate was calculated using the calibration curve, and this was taken as the solubility of the polymer in o-DCB (converted to mass%).

[0310] Furthermore, the solubility in tetralin and toluene was determined by adding tetralin and toluene, respectively, to the conjugated polymers obtained in each polymer example and the conjugated polymer having a n-hexadecyl group in the alkyl substituent (compound 3-1-6-n16 in the publication) synthesized by the method described in WO2023 / 210569 (1 mg each) to obtain film-forming compositions. The volume of each organic solvent required to completely dissolve the conjugated polymer compound at room temperature (23°C) was measured, and the solubility (mass%) was calculated. The point at which complete dissolution occurred was confirmed visually. The solubility of the evaluated conjugated polymers is shown in Table 1.

[0311]

[0312] [Organic Thin Film Transistor Element Example 1] A composition for forming an organic thin film was prepared by heating a 0.5 wt% o-DCB solution of the conjugated polymer (5-1-13-B) synthesized in Polymer Example 1 in a glove box under a nitrogen atmosphere.

[0313] After cooling to room temperature, the entire volume was filtered through a 0.22 μm filter, confirming that the solution state was maintained and that it is a compound suitable for film formation.

[0314] Next, a parylene C (trademark) film was deposited on a glass substrate as a base layer by CVD. A shadow mask with a channel length of 100 μm and a channel width of 500 μm was then placed on the parylene C layer, and gold was deposited under vacuum to create the source and drain electrodes. The solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to create an organic thin film of a conjugated polymer (5-1-13-B). Next, a 4 wt% toluene solution of TOPAS (registered trademark) (Sigma-Aldrich) was spin-coated under air as the first gate insulating film in contact with the organic semiconductor film. This was heated to 120°C and held for 10 minutes to create a TOPAS insulating film. Furthermore, after depositing parylene C by CVD, a silver electrode was created by vapor deposition to create a top-gate-bottom contact type organic thin-film transistor element (gate electrode is silver, gate insulating layer is parylene C, source and drain electrodes are gold).

[0315] Under atmospheric pressure, the organic thin-film transistor element was connected to a semiconductor parameter analyzer (Keithley, 4200A-SCS type), and the transfer characteristics were evaluated by scanning the gate voltage (Vg) from +10 to -50V in 1V increments with a drain voltage (Vd = -50V). The organic thin-film transistor element exhibited p-type characteristics, and its hole carrier mobility was 5.5 cm². ２ It was / Vs.

[0316] [Organic Thin Film Transistor Element Example 2] The same procedure as in Example 1 was repeated except that the conjugated polymer (5-2-1) synthesized in Polymer Example 4 was used. The obtained organic thin film transistor element exhibited p-type characteristics, and its hole carrier mobility was 0.01 cm ２ It was / Vs.

[0317] [Organic Thin Film Transistor Element Example 3] The same procedure as in Example 1 was repeated except that the conjugated polymer (5-2-4) synthesized in Polymer Example 5 was used. The obtained organic thin film transistor element exhibited p-type characteristics, and its hole carrier mobility was 0.3 cm². ２ It was / Vs.

[0318] [Organic Thin Film Transistor Element Example 4] The same procedure as in Example 1 was repeated except that the conjugated polymer (5-1-13-b) synthesized in Polymer Example 9 was used. The obtained organic thin film transistor element exhibited p-type characteristics, and its hole carrier mobility was 3.2 cm². ２ It was / Vs.

[0319] [Organic Thin Film Transistor Element Example 5] The same procedure as in Example 1 was repeated except that (1) of the conjugated polymer (5-1-13-B) synthesized in Polymer Example 10 was used. The obtained organic thin film transistor element exhibited p-type characteristics, and its hole carrier mobility was 5.2 cm. ２ It was / Vs.

[0320] [Organic Thin Film Transistor Element Example 6] The same procedure as in Example 1 was repeated except that (2) of the conjugated polymer (5-1-13-B) synthesized in Polymer Example 10 was used. The obtained organic thin film transistor element exhibited p-type characteristics, and its hole carrier mobility was 4.0 cm. ２ It was / Vs.

[0321] [Organic Thin Film Example 1] A 0.5 wt% o-DCB solution of the conjugated polymer (5-1-13-B) synthesized in Polymer Example 1 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film. Next, parylene C was deposited as a base layer on a glass substrate by CVD, and then the solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to produce an organic thin film of the conjugated polymer (5-1-13-B). The ionization potential of the obtained organic thin film was 5.59 eV, and it was confirmed that it was highly stable in the atmosphere as it was not easily oxidized by oxygen.

[0322] [Organic Thin Film Example 2] A 0.5 wt% o-DCB solution of the conjugated polymer (5-2-1) synthesized in Polymer Example 4 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film. Next, parylene C was deposited as a base layer on a glass substrate by CVD, and then the solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to produce an organic thin film of the conjugated polymer (5-2-1). The ionization potential of the obtained organic thin film was 5.41 eV, and it was confirmed that it was highly stable in the atmosphere as it was not easily oxidized by oxygen.

[0323] [Organic Thin Film Example 3] A 0.5 wt% o-DCB solution of the conjugated polymer (5-2-4) synthesized in Polymer Example 5 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film. Next, parylene C was deposited as an underlayer on a glass substrate by CVD, and then the solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to produce an organic thin film of the conjugated polymer (5-2-4). The ionization potential of the obtained organic thin film was 5.49 eV, and it was confirmed that it was highly stable in the atmosphere as it was not easily oxidized by oxygen.

[0324] [Organic Thin Film Example 4] A 0.5 wt% o-DCB solution of the conjugated polymer (5-1-13-b) synthesized in Polymer Example 9 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film. Next, parylene C was deposited as an underlayer on a glass substrate by CVD, and then the solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to produce an organic thin film of the conjugated polymer (5-1-13-b). The ionization potential of the obtained organic thin film was 5.51 eV, and it was confirmed that it was highly stable in the atmosphere as it was not easily oxidized by oxygen.

[0325] 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode 1001: Bottom gate-top contact type organic thin film transistor 1002: Bottom gate-bottom contact type organic thin film transistor 1003: Top gate-top contact type organic thin film transistor 1004: Top gate-bottom contact type organic thin film transistor

Claims

A compound represented by the following general formula (1). (wherein R １ , R ２ , R ３ and R ４ each independently represent an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, said alkyl or alkenyl group may optionally contain -O-, -CO- or -COO-, and R １ , R ２ , R ３ and R ４ at least one of which represents a branched alkyl group having 11 to 50 carbon atoms and two or more branches, or a branched alkenyl group having 11 to 50 carbon atoms and one or more branches. R ５ and R ６ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 50 carbon atoms. J １ and J ２ each independently represent a chalcogen atom. M １ and M ２ each independently represent one group selected from the group consisting of a hydrogen atom, a halogen atom, a boron-containing group and a tin-containing group.) In the above general formula (1), R １ , R ２ , R ３ and R ４ The compound according to claim 1, wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group. 　 The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. 　 A conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4). In the above general formula (2), R １ , R ２ , R ３ and R ４ The conjugated polymer according to claim 3, wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group. 　 The compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom. A compound represented by the following general formula (TT-B) or (T2-B) is reacted in the presence of a transition metal catalyst and a base. (In the formula, M ３－Ｂ and M ４－Ｂ Each of these independently represents a boron-containing group. 　 The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This expresses the same meaning as above.) 　 A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4). In the above general formula (1a), R １ , R ２ , R ３ and R ４ The method for producing a conjugated polymer according to claim 5, wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group. 　 The compound represented by the following general formula (1a) (In the formula, R １ , R ２ , R ３ and R ４ Each independently represents an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, and the alkyl or alkenyl group may contain -O-, -CO-, or -COO-, R １ , R ２ , R ３ and R ４ At least one of these represents a branched alkyl group having two or more branches with 11 to 50 carbon atoms, or a branched alkenyl group having one or more branches with 11 to 50 carbon atoms. ５ and R ６ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 50 carbon atoms. １ and J ２ Each of these independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ Each of these independently represents a halogen atom. 　 A compound represented by the following general formula (TT-Sn) or (T2-Sn) is reacted in the presence of a transition metal catalyst. (In the formula, M ３－Ｓｎ and M ４－Ｓｎ Each of these independently represents a tin-containing group. 　 The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This expresses the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4). In the above general formula (1a), R １ , R ２ , R ３ and R ４ are each independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group, the method for producing a conjugated polymer according to claim 7. 　 The compound represented by the following general formula (1a) (wherein R １ , R ２ , R ３ and R ４ each independently represent an alkyl group having 1 to 50 carbon atoms or a branched alkenyl group having 11 to 50 carbon atoms, wherein the alkyl or alkenyl group may contain -O-, -CO- or -COO-, R １ , R ２ , R ３ and R ４ at least one of which represents a branched alkyl group having 11 to 50 carbon atoms with two or more branches or a branched alkenyl group having 11 to 50 carbon atoms with one or more branches. R ５ and R ６ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 50 carbon atoms. J １ and J ２ each independently represent a chalcogen atom. M １－ｈａｌ and M ２－ｈａｌ each independently represent a halogen atom.) Thieno[3,2-b]thiophene or 2,2'-bithiophene is reacted in the presence of a transition metal catalyst, a base, and an organic acid. The structural unit represented by the following general formula (2), (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ J １ and J ２ (This expresses the same meaning as above.) A method for producing a conjugated polymer containing a structural unit represented by the following general formula (3) or general formula (4). In the above general formula (1a), R １ , R ２ , R ３ and R ４ The method for producing a conjugated polymer according to claim 9, wherein the group is independently a 3,7,11-trimethyldodecyl group or a 3,7,11,15-tetramethylhexadecyl group. 　 A film-forming composition comprising the conjugated polymer described in claim 3 or 4. 　 An organic thin film comprising the conjugated polymer described in claim 3 or 4. 　 An organic semiconductor device comprising the conjugated polymer described in claim 3 or 4. 　 An organic thin-film transistor element comprising the conjugated polymer described in claim 3 or 4.

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