TW201920345A - Polymer compound, method for producing the same, organic semiconductor material containing the same, and organic solar cell containing the same - Google Patents

Abstract

Provided is a polymer compound which has better characteristics as a p-type organic semiconductor material, and is capable of contributing to achieving good short-circuit current density or photoelectric conversion efficiency when used in a solar cell. The polymer compound is represented by general formula (I) (in general formula (I), R1, R2, R3, and R4 are each independently a hydrogen atom, a fluorine atom, or a C1-60 aliphatic hydrocarbon group, and n is an integer of at least 2).

Description

Polymer compound and manufacturing method thereof, organic semiconductor material containing the compound, and organic solar cell containing the compound

The present invention relates to a polymer compound and a manufacturing method thereof, an organic semiconductor material using the same, and an organic solar cell including the compound.

In recent years, research and development of organic thin-film transistors or organic thin-film solar cells using organic semiconductor materials are prevailing. When an organic semiconductor material is used, a thin-film organic semiconductor layer can be produced by a simple method using a wet process such as a printing method or a spin coating method. Therefore, compared with an inorganic semiconductor material, there is an advantage that a manufacturing cost is cheaper and a semiconductor element which is thin and excellent in flexibility is obtained. Therefore, research and development of various organic semiconductor materials are prevailing. For example, in Patent Document 1 and Non-Patent Document 1, it is disclosed that the following polymer compounds composed of naphthobisthiadiazole and thiophene as repeating units exhibit high photoelectric conversion when used as p-type organic semiconductor materials. effectiveness.

In addition, Patent Documents 2 and 3 disclose structures of polymer compounds composed of naphthobisthiadiazole and thiophene having various substituents at the 5- and 10-positions as repeating units. In the example of Patent Document 2, a method for producing a naphthobisthiadiazole intermediate containing a nitro or chlorine atom or a substituent having 1 to 20 carbon atoms at the 5- and 10-positions is disclosed. The manufacturing method of such high molecular compounds is not specifically described. Patent Document 3 discloses a structure of a polymer compound described below that includes a naphthobisthiadiazole and a thiophene having fluorine atoms at the 5- and 10-positions as repeating units.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/015298 [Patent Document 2] US Patent No. 8735536 Specification [Patent Document 3] Japanese Patent Laid-Open No. 2014-53383 [Non-Patent Document]

[Non-Patent Document 1] Kazuaki Kawashima et al., J. Am. Chem. Soc., 138, 12065-10275 (2016)

[Questions to be Solved by the Invention]

Since the solar cells using the polymer compounds described in Patent Literature 1 and Non-Patent Literature 1 as p-type organic semiconductor materials have not obtained sufficient short-circuit current density and photoelectric conversion efficiency, further improvements are being sought. Further, in Patent Document 2, it is unknown what kind of characteristics an apparatus for manufacturing an organic solar cell or the like using the described polymer compound has. Furthermore, in Patent Document 3, although the performance evaluation results of the open voltage and durability of organic solar cells using the described polymer compounds are disclosed, characteristic values such as short-circuit current density and photoelectric conversion efficiency are not disclosed. It is unclear whether the polymer material has sufficient characteristics. [Means to solve the problem]

The present inventors have searched for a polymer compound having more excellent characteristics, especially when used as a solar cell, which can contribute to the achievement of a good short-circuit current density or photoelectric conversion efficiency, and found that the following general formula (I) The polymer compound has a desired effect and completed the present invention. That is, the present invention resides in the following.

[1]. A polymer compound represented by the following general formula (I),

(In general formula (I), R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; n is an integer of 2 or more). [2]. The polymer compound according to [1], wherein the R ³ and R ⁴ are each independently a hydrogen atom or a fluorine atom. [3]. The polymer compound according to [2], wherein R ³ and R ⁴ are fluorine atoms. [4]. An organic semiconductor material comprising the polymer compound according to any one of [1] to [3]. [5]. An organic solar cell comprising the organic semiconductor material according to [4]. [6]. A method for producing a polymer compound represented by the following general formula (I-1), which comprises polymerizing a compound represented by the following general formula (a) and a compound represented by the following general formula (b) Reaction steps, (In general formula (a), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^a represents a linear, branched chain, or (Cyclic aliphatic hydrocarbon group) (In general formula (b), R ^1b and R ^2b are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^b represents a bromine atom or an iodine atom) (In general formula (I-1), R ^1b and R ^2b are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or a carbon atom 1 An aliphatic hydrocarbon group of ~ 60; n is an integer of 2 or more). [7]. A method for producing a polymer compound represented by the following general formula (I-2), which comprises polymerizing a compound represented by the following general formula (c) and a compound represented by the following general formula (d) Reaction steps, (In general formula (c), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^C represents a straight chain, branched chain, or (Cyclic aliphatic hydrocarbon group) (In general formula (I-2), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; n is an integer of 2 or more). [Effect of the invention]

Since the polymer compound of the present invention has a skeleton combining naphthobisthiadiazole and thiophene substituted fluorine atoms, it has more excellent characteristics as a p-type organic semiconductor material, and can be particularly helpful when used as a solar cell. To achieve a good short-circuit current density or photoelectric conversion efficiency. Therefore, it is useful as an organic solar cell having more excellent photoelectric conversion efficiency.

(Structure of Polymer Compound) The polymer compound of the present invention is represented by general formula (I).

In the above general formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms. The number of carbon atoms in the hydrocarbon group is preferably 20 to 60, and more preferably 20 to 40. The aliphatic hydrocarbon group may be linear or branched, or may be cyclic. R ³ and R ^{4 are} preferably each independently a hydrogen atom or a fluorine atom, and R ³ and R ⁴ are each preferably a fluorine atom.

In the general formula (I), n is an integer of 2 or more, and the conditions are not particularly limited, but for example, an integer of 100 or less is preferable, 5 to 100 is more preferable, and 20 to 60 is more preferable. Although the molecular weight is not particularly limited, the number average molecular weight is, for example, 3,000 to 100,000, and the weight average molecular weight is, for example, 5,000 to 1,000,000.

(Production method of polymer compound) Although the production method of polymer compound (I) is not particularly limited, as an example, it can be produced by synthesizing a compound sold along the following reaction scheme. A more specific example is described in Examples described later.

When R ³ in the polymer compound (I-1) is a fluorine atom and R ⁴ is a fluorine atom, a general formula (from a compound represented by a general formula (II-F) commercially available) is synthesized through steps A, B, C, and D ( VI-F). <Step A> First, from a compound represented by general formula (II-F) (hereinafter referred to as "compound (II-F)"), a compound represented by general formula (III-F) (hereinafter referred to as "compound (III) -F) ") (step A). In the compound (II-F), A ¹ represents a bromine atom or an iodine atom. In the compound (III-F), A ² represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent.

Step A Specifically, for example, in a solvent, n-butyllithium, lithium diisopropylamidine (LDA), or Grignard reagent is reacted with compound (II-F), and then A ² ₃ SiCl reacts to produce compound (III-F). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (III-F) is preferably used for purification before step B.

<Step B> Next, a compound represented by general formula (IV-F) (hereinafter referred to as "compound (IV-F)") is produced from compound (III-F) (step B). In compound (IV-F), A ² is as described above.

Step B Specifically, for example, n-butyllithium, lithium diisopropylamidine (LDA), or Grignard reagent is reacted with the compound (III-F) in a solvent, and then N-fluorophenylhydrazine is reacted. The hydrazone imine reacts to produce a compound (IV-F). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. The compound (IV-F) is preferably used for purification before step C.

<Step C> Next, from the compound (IV-F), a compound represented by the general formula (VF) (hereinafter referred to as "compound (VF)") is produced (step C). In the compound (VF), A ³ represents a bromine atom or an iodine atom.

Step C Specifically, for example, in a solvent such as dichloromethane and / or chloroform, bromine, N-bromosuccinimide (NBS), iodine, and N-iodosuccinimide in compound (IV-F) are used. (NIS), iodine chloride, or the like to react to form compound (VF). The reaction temperature can be set to, for example, -78 ° C to 60 ° C. Compound (V-F) is preferably used for purification before step D.

<Step D> Next, from compound (VF), a compound represented by general formula (VI-F) (hereinafter referred to as "compound (VI-F)") is produced (step D). In the compound (VI-F), A ⁴ represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent.

Step D Specifically, for example, after reacting n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent with a compound (VF) in a solvent, A ⁴ ₃ SnCl is reacted to Compound (VF) is formed. Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (VI-F) is preferably used for purification before step Y.

When R ³ in the polymer compound (I-1) is a hydrogen atom and R ⁴ is a hydrogen atom, the compound represented by the general formula (II-H) commercially available is subjected to step E to synthesize the general formula (VI-H) Of compounds. <Step E> From the compound (II-H), a compound represented by the general formula (VI-H) (hereinafter referred to as "compound (VI-H)") is produced (step E). In compound (VI-H), A ⁴ is as described above.

Step E Specifically, for example, in a solvent, n-butyllithium, lithium diisopropylamidamine (LDA), or a Grignard reagent are reacted with compound (II-H), and then A ⁴ ₃ SnCl is reacted. The reaction produces a compound (VI-H). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (VI-H) is preferably used for purification before Step Y.

When R ³ in the polymer compound (I-1) is an aliphatic hydrocarbon group having 1 to 60 carbon atoms, and R ⁴ is an aliphatic hydrocarbon group having 1 to 60 carbon atoms, a compound represented by general formula (XIX) described below is synthesized, This compound can be used to synthesize the polymer compound (I-1) through step Y.

On the other hand, when R ¹ in the polymer compound (I-1) is an aliphatic hydrocarbon group R ^1a having 1 to 60 carbon atoms, and R ² is an aliphatic hydrocarbon group R ^2a having 1 to 60 carbon atoms, it is commercially available. The compounds represented by general formulae (VII) and (VIII) are subjected to steps F, G, H, I, J to synthesize compounds represented by general formula (XIV-a) or general formula (XV-a). <Step F> First, a compound represented by the general formula (VII) (hereinafter referred to as "compound (VII)") and a compound represented by the general formula (VIII) (hereinafter referred to as "compound (VIII)") are prepared to produce a general formula Compound represented by (IX) (hereinafter referred to as "compound (IX)") (step F). In compound (VII), A ⁵ and A ⁶ each independently represent a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent. In compound (VIII), A ⁷ represents a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent. In compound (IX), A ⁸ represents a linear, branched or cyclic aliphatic hydrocarbon group in which one methylene chain is removed from A ⁵ in compound (VII). X ¹ represents a bromine atom or an iodine atom.

Step F Specifically, for example, in a solvent, n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent are reacted in compound (VII), and then 1,3-dimethyl is reacted. -3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and the like react the compound (VIII) to produce the compound (IX). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (IX) is preferably purified before use in step G.

<Step G> Next, a compound represented by general formula (X) (hereinafter referred to as "compound (X)") is produced from compound (IX) (step G). In compound (X), A ⁷ and A ⁸ are as described above.

Step G specifically, for example, reacts lithium aluminum hydride or the like with a compound (IX) in a solvent to produce a compound (X). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (X) is preferably purified before being used in Step H.

<Step H> Next, a compound represented by general formula (XI) (hereinafter referred to as "compound (XI)") is produced from compound (X) (step H). In the compound (XI), X ² is a bromine atom or an iodine atom, and A ⁷ and A ⁸ are as described above.

Step H specifically, for example, reacts triphenylphosphine and the like with a compound (X) in a solvent, and then reacts N-bromosuccinimide and the like to produce a compound (XI). Examples of the solvent include dichloromethane and the like. The reaction temperature can be set to, for example, -78 ° C to 50 ° C. Compound (XI) is preferably used for purification before Step I.

<Step I> Next, from compound (XI), a compound represented by general formula (XII-a) (hereinafter referred to as "compound (XII-a)") or a compound represented by general formula (XIII-a) (hereinafter referred to as "Compound (XIII-a)") (Step I). The compound (XII-a) and the compound (XIII-a) may be the same as or different from each other. In the compound (XII-a), R ^1a is (A ⁷ ) (A ⁸ ) CHCH ₂ , and A ⁷ and A ⁸ are as described above. In compound (XIII-a), R ^2a is (A ⁷ ) (A ⁸ ) CHCH ₂ , and A ⁷ and A ⁸ are as described above.

Step I Specifically, for example, compound (XI) is reacted with magnesium in a solvent to generate a Grignard reagent, and then 3-iodothiophene or 3-bromothiophene is reacted in the presence of a catalyst to produce a compound ( XII-a) or compound (XIII-a). Examples of the solvent include tetrahydrofuran and diethyl ether. Examples of the catalyst include dichloro [1,3-bis (diphenylphosphino) propane] nickel (II) and the like. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. The compound (XII-a) or the compound (XIII-a) is preferably used for purification before step J.

<Step J> Next, from compound (XII-a) or compound (XIII-a), a compound represented by general formula (XIV-a) or general formula (XV-a) (hereinafter referred to as "compound (XIV-a) ) "Or" compound (XV-a) ") (step J). The compound (XIV-a) and the compound (XV-a) may be the same as or different from each other. In the compound (XIV-a), A ⁹ represents a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent. In the compound (XV-a), A ⁹ represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent. In compound (XIV-a), R ^1a is as described above. In the compound (XV-a), R ^2a is as described above.

Step J Specifically, for example, in a solvent, compound (XII-a) or compound (XIII-a) is reacted with n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent. A ⁹ ₃ SnCl is reacted to produce a compound (XIV-a) or a compound (XV-a). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. The compound (XIV-a) or the compound (XV-a) is preferably used for purification before step W.

In addition, the compound of the formula (XIV-a) or the compound of the formula (XV-a) is also included, and the compound of the following formula (XIV-b) or the compound of the formula (XV-b) may be in accordance with step J or step J Method synthesis.

(Wherein R ^1b and R ^2b are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms).

On the other hand, when R ¹ and R ² in the polymer compound (I-2) are both a fluorine atom, the compound represented by the general formula (XXVI) can be obtained from the compound represented by the general formula (XII) through step K. The compound represented by (XVI) and the compound represented by general formula (XVII) are synthesized through steps M, N, O, P, Q, R, and S. The compound represented by general formula (XVII) is synthesized from general formula (XIII) The indicated compound is obtained through step L. Details are described below.

<Step K> First, from a compound represented by general formula (XII) (hereinafter referred to as "compound (XII)"), a compound represented by general formula (XVI) (hereinafter referred to as "compound (XVI)") is produced (step K ). In the compound (XII), R ³ is a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms. In the compound (XVI), A ¹⁰ represents a bromine atom or an iodine atom.

Step K Specifically, for example, bromine, N-bromosuccinimide (NBS), iodine, N-iodosuccinimide (NIS) in compound (XII) in a solvent such as dichloromethane and / or chloroform. ) Or iodine chloride and the like to react to produce compound (XVI). The reaction temperature can be set to, for example, -78 ° C to 60 ° C. Compound (XVI) is preferably used for purification before step M.

<Step L> Next, a compound represented by general formula (XVII) (hereinafter referred to as "compound (XVII)") is produced from a compound represented by general formula (XIII) (hereinafter referred to as "compound (XIII)") (step L ). In the compound (XIII), R ⁴ is a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms. In the compound (XVII), A ¹¹ represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent.

Step L is specifically, for example, after reacting n-butyllithium, lithium diisopropylamidine (LDA), or Grignard reagent with a compound (XIII) in a solvent, A ¹¹ ₃ SnCl is reacted to form Compound (XVII). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (XVII) is preferably purified before use in step M.

<Step M> Next, a compound represented by general formula (XVIII) (hereinafter referred to as "compound (XVIII)") is produced from compound (XVI) and compound (XVII) (step M). In the compound (XVIII), R ³ and R ⁴ are as described above.

Step M specifically, for example, a compound (XVI) and a compound (XVII) are reacted in a solvent in the presence of a catalyst to produce a compound (XVIII). Examples of the solvent include toluene, chlorobenzene, DMF, and tetrahydrofuran. Examples of the catalyst include Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , and Pd ₂ (dba) ₃ . As the ligand, triphenylphosphine and tri (o-tolyl) phosphine can be added. The reaction temperature can be set to, for example, 0 ° C to 200 ° C. Compound (XVIII) is preferably used for purification before Step N.

<Step N> Next, a compound represented by general formula (XIX) (hereinafter referred to as "compound (XIX)") is produced from compound (XVIII) (step N). In the compound (XIX), A ¹² represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent.

Step N specifically, for example, after reacting n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent with a compound (XVIII) in a solvent, A ¹² ₃ SnCl is reacted to Compound (XIX) is formed. Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (XIX) is preferably used for purification before step O.

<Step O> Next, from compound (XIX) and a compound represented by general formula (XX) (hereinafter referred to as "compound (XX)") and / or a compound represented by general formula (XXI) (hereinafter referred to as "compound (XXI) ) "To produce a compound represented by general formula (XXII) (hereinafter referred to as" compound (XXII) ") (step O). In compound (XX), A ¹³ and A ¹⁴ are each independently a bromine atom or an iodine atom. In the compound (XXI), A ¹⁵ and A ¹⁶ are each independently a bromine atom or an iodine atom. In the compound (XXII), R ³ and R ⁴ are as described above.

Step O Specifically, for example, the compound (XIX) is reacted with the compound (XX) and / or the compound (XXI) in a solvent in the presence of a catalyst to produce the compound (XXII). Examples of the solvent include toluene, chlorobenzene, DMF, and tetrahydrofuran. Examples of the catalyst include Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , and Pd ₂ (dba) ₃ . As the ligand, triphenylphosphine and tri (o-tolyl) phosphine can be added. The reaction temperature can be set to, for example, 0 ° C to 200 ° C. Compound (XXII) is preferably used for purification before step P.

<Step P> Next, from the compound (XXII), a compound represented by the general formula (XXIII) (hereinafter referred to as "compound (XXIII)") is produced (step P). In the compound (XXIII), R ³ , R ⁴ , A ¹³ and A ¹⁵ are as described above, and A ¹⁷ represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent.

Step P specifically, for example, after reacting n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent with a compound (XXII) in a solvent, A ¹⁷ ₃ SiCl is reacted to Compound (XXIII) is formed. Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (XXIII) is preferably used for purification before step Q.

<Step Q> Next, from compound (XXIII), a compound represented by general formula (XXIV) (hereinafter referred to as "compound (XXIV)") is produced (step Q). In compound (XXIV), R ³ , R ⁴ and A ¹⁷ are as described above.

Step Q Specifically, for example, in a solvent, n-butyllithium, lithium diisopropylamidine (LDA), or Grignard reagent is reacted with compound (XXIII), and then N-fluorophenylarsine is reacted. The amine reacts to form a compound (XXIV). Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (XXIV) is preferably used for purification before step R.

<Step R> Next, from the compound (XXIV), a compound represented by the general formula (XXV) (hereinafter referred to as "compound (XXV)") is produced (step R). In the compound (XXV), A ¹⁸ represents a bromine atom or an iodine atom.

Step R Specifically, for example, in a solvent such as dichloromethane and / or chloroform, bromine, N-bromosuccinimide (NBS), iodine, and N-iodosuccinimide (NIS) are reacted in compound (XXIV). ) Or iodine chloride and the like to react to produce compound (XXV). The reaction temperature can be set to, for example, -78 ° C to 60 ° C. The compound (XXV) is preferably used for purification before step S.

<Step S> Next, a compound represented by general formula (XXVI) (hereinafter referred to as "compound (XXVI)") is produced from compound (XXV) (step S). In the compound (XXVI), A ¹⁹ represents a linear, branched or cyclic aliphatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are as described above.

Step S specifically, for example, after reacting n-butyllithium, lithium diisopropylamidamine (LDA), or Grignard reagent with a compound (XXV) in a solvent, A ¹⁹ ₃ SnCl is reacted to Compound (XXVI) is formed. Examples of the solvent include tetrahydrofuran and diethyl ether. The reaction temperature can be set to, for example, -78 ° C to 80 ° C. Compound (XXVI) is preferably used for purification before Step Z.

On the other hand, a compound represented by general formula (XXX) is synthesized from commercially available naphthalene and the like represented by general formula (XXVII) through steps T, U, and V, and further, a compound represented by general formula (XXXII) is synthesized through W, X. .

<Step T> First, from a compound represented by the general formula (XXVII) (hereinafter referred to as "compound (XXVII)"), a compound represented by the general formula (XXVIII) (hereinafter referred to as "compound (XXVIII)") is produced (step T ).

Step T specifically includes, for example, at least one step of nitration, halogenation, halogen substitution, boronization, hydroxylation, amination, protection or deprotection, but it is not particularly limited, and may be adopted from this Among the steps, the necessary steps are appropriately selected and combined for construction. The selection and combination of necessary steps (the order of performing the selected steps) can be easily understood by those having ordinary knowledge in the field of the present invention.

<Step U> (2) Next, from the compound (XXVIII), a compound represented by the general formula (XXIX) (hereinafter referred to as "compound (XXIX)") is produced (Step U).

Step U Specifically, for example, the compound (XXVIII) or a salt thereof can be reacted with a vulcanizing agent (vulcanization reaction) to produce the compound (XXIX). The vulcanizing agent is not particularly limited as long as it is a vulcanizing agent for performing the reaction, and examples thereof include sulfur, sulfur monochloride, sulfur dichloride, thionyl chloride, thionyl chloride, and 2,4-bis (4 -Methoxyphenyl) -1,3,2,4-Dithiadiphosphetane-2,4-disulfide and the like. As the vulcanizing agent, a ratio of preferably 1 to 20 equivalents, more preferably 2 to 5 equivalents can be used with respect to 1 equivalent of the compound (XXVIII). The reaction of Step L can usually be performed in the presence of a base and a solvent. The base is not particularly limited as long as it is a base for performing the reaction. The ratio of the base to 1 equivalent of the compound (XXVIII) is preferably 1 to 20 equivalents, and more preferably 2 to 5 equivalents. The solvent is not particularly limited as long as it is a solvent for performing the reaction. The reaction temperature is usually preferably 0 to 200 ° C, and more preferably 0 to 120 ° C. The reaction time is usually 1 to 48 hours. Compound (XXIX) is preferably used for purification before Step V.

<Step V> (2) Next, from compound (XXIX), a compound represented by general formula (XXX) (hereinafter referred to as "compound (XXX)") is produced (step V).

Step V Specifically, for example, compound (XXIX) is reacted with a halogenating agent (brominating agent) (halogenation reaction) to produce compound (XXX). The halogenating agent is not particularly limited as long as it is a halogenating agent that performs the reaction, and examples thereof include bromine and N-bromosuccinimide. The ratio of the halogenating agent to 1 equivalent of the compound (XXIX) is preferably 1 to 20 equivalents, and more preferably 2 to 5 equivalents. The reaction of Step V can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent for performing the reaction. The reaction temperature is usually preferably 0 to 200 ° C, and more preferably 0 to 120 ° C. The reaction time is usually 1 to 48 hours. Compound (XXX) is preferably used for purification before Step W or Step Z.

<Step W> Next, a compound represented by general formula (XXXI) (hereinafter referred to as "compound (XXXI)") is produced from compound (XXX), and compound (XIV) and / or compound (XV) (step W). In the compound (XXXI), R ¹ and R ² are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms.

Step W Specifically, for example, the compound (XXX) is reacted with the compound (XIV) and / or the compound (XV) in a solvent in the presence of a catalyst to produce the compound (XXXI). Examples of the solvent include toluene, chlorobenzene, DMF, and tetrahydrofuran. Examples of the catalyst include Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , and Pd ₂ (dba) ₃ . As the ligand, triphenylphosphine and tri (o-tolyl) phosphine can be added. The reaction temperature can be set to, for example, 0 ° C to 200 ° C. Compound (XXXI) is preferably used for purification before Step X.

<Step X> Next, a compound represented by general formula (XXXII) (hereinafter referred to as "compound (XXXII)") is produced from compound (XXXI) (step X). In the compound (XXXII), A ²⁰ represents a bromine atom or an iodine atom. In compound (XXXII), R ¹ and R ² are as described above.

Step X Specifically, for example, in a solvent such as dichloromethane and / or chloroform, bromine, N-bromosuccinimide (NBS), iodine, N-iodosuccinimide (NIS) in compound (XXXI) ) Or iodine chloride or the like to react to produce compound (XXXII). The reaction temperature can be set to, for example, -78 ° C to 60 ° C. Compound (XXXII) is preferably used for purification before Step Y.

<Step Y> Next, compound (VI-H), compound (VI-F) or compound (XIX) is polymerized with compound (XXXII) to produce a compound represented by general formula (I-1) (hereinafter (Referred to as "compound (I-1)") (step Y). In the compound (VI-F) and the compound (VI-H), A ⁴ represents a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent as described above. Further, in the compound (XIX), A ¹² represents a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent, as described above. Furthermore, in this specification, the compound (VI-F), the compound (VI-H), or the compound (XIX) may be referred to as a compound represented by the general formula (a). In this case, in the general formula (a), A ⁴ or A ¹² may be represented as A ^a , and A ^a may represent a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent. In the compound (I-1), R ¹ , R ² , R ³ and R ⁴ are as described above.

In step Y, specifically, for example, the compound (VI-H), the compound (VI-F) or the compound (XIX) is reacted with the compound (XXXII) in a solvent to generate a polymer compound (I- 1). In the compound (XXXII), A ²⁰ represents a bromine atom or an iodine atom as described above. In the present specification, the compound (XXXII) may be referred to as a compound represented by general formula (b). In this case, in the general formula (b), A ²⁰ may be expressed as A ^b , and A ^{b may be} a bromine atom or an iodine atom. Examples of the solvent include toluene, chlorobenzene, DMF, and tetrahydrofuran. Examples of the catalyst include Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , and Pd ₂ (dba) ₃ . As the ligand, triphenylphosphine and tri (o-tolyl) phosphine can be added. The reaction temperature can be set to, for example, 80 ° C to 200 ° C. The obtained polymer compound (I-1) can be purified. In this manner, the polymer compound (I-1) of the present invention can be produced.

<Step Z> A compound represented by general formula (I-2) (hereinafter referred to as "compound (I-2)") can be produced by subjecting compound (XXVI) to a polymerization reaction with compound (XXX) (step Z). In the compound (I-2), R ¹ and R ² are fluorine atoms. In the general formula (I-2), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms.

Step Z Specifically, for example, the compound (XXVI) and the compound (XXIX) are reacted in a solvent in the presence of a solvent to produce a polymer compound (I-2). In the compound (XXVI), A ¹⁹ represents a linear, branched chain or cyclic aliphatic hydrocarbon group which may have a substituent as described above. In addition, in this specification, a compound (XXVI) may be called the compound represented by general formula (c). In this case, in the general formula (c), A ¹⁹ may be represented as A ^c , and A ^c may represent a linear, branched, or cyclic aliphatic hydrocarbon group which may have a substituent. Examples of the solvent include toluene, chlorobenzene, DMF, and tetrahydrofuran. Examples of the catalyst include Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , and Pd ₂ (dba) ₃ . As the ligand, triphenylphosphine and tri (o-tolyl) phosphine can be added. The reaction temperature can be set to, for example, 80 ° C to 200 ° C. The obtained polymer compound (I-2) can be purified. By doing so, the polymer compound (I-2) of the present invention can be produced.

(Solar cell element) The polymer compound (I) of the present invention can be used as a semiconductor material (p-type semiconductor material). Therefore, the polymer compound (I) of the present invention can be used, for example, as a material for a solar cell element. The solar cell element may be an organic thin film solar cell element.

When the polymer compound (I) of the present invention is used as a p-type semiconductor material, examples of the n-type semiconductor material used together include C ₆₀ fullerene, C ₇₀ fullerene, and C ₈₄ fullerene. Examples of the fullerene derivative include compounds in which the fullerene is added with at least one substituent. For example, the fullerene derivative is a part of the carbon atom of the fullerene, and an alkyl group having 1 to 20 carbon atoms is preferred. , More preferably an alkyl group having 1 to 10 carbon atoms; an epoxy group; a dioxolane structure of 1 to 2 degrees (dioxolane group); an indolyl group, and a benzofuran And other condensed organic groups; Specific examples of the fullerene derivative include various fullerene epoxides, 1,3-dioxolane-fullerene derivatives, and phenyl C ₆₁ butyrate (PC ₆₁ BM) , Phenyl C ₆₁ Butyl Butyrate (PCBB), Phenyl C ₆₁ Octyl Butyrate (PCBO), Phenyl C ₇₁ Methyl Butyrate (PC ₇₁ BM), Indica Fullerene Derivatives (ICMA, ICBA, etc.), silylmethyl addition fullerene derivatives, indololinyl-fullerene derivatives, benzofuranyl-fullerene derivatives, etc., and Bis-PCBM, etc. Examples of the n-type semiconductor material include ActivInk N2200 (manufactured by Polyera).

The solar cell element may be produced according to a known method, for example. A solar cell element according to an embodiment of the present invention includes, for example, an electrode layer, an electron transport layer (electron extraction layer), a photoelectric conversion layer (photoactive layer), a hole transport layer (hole extraction layer), and a substrate on the substrate. A structure in which electrode layers are sequentially laminated. Examples of the substrate include a substrate having a light-transmitting property that does not impede light-receiving performance. As such a substrate, for example, in addition to using colorless or colored glass, wired glass, glass blocks, etc., a resin having colorless or colored transparency can be used. Specific examples of such resins include polyesters such as polyethylene terephthalate, polyamides, polyfluorenes, polyethers, polyetheretherketones, polyphenylene sulfides, and polycarbonates. Esters, polyimide, polymethyl methacrylate, polystyrene, triethyl cellulose, and polymethylpentene. Examples of the electrode include an ITO (Indium Tin Oxide) electrode, a silver electrode, an aluminum electrode, a gold electrode, a chromium electrode, a titanium oxide electrode, and a zinc oxide electrode. Examples of the electron-transporting layer (electron extraction layer) include organic semiconductor molecules such as phenanthroline, bathhopropro, and europium, and derivatives thereof; organic materials such as transition metal complexes; LiF, CsF, CsO, Cs ₂ CO ₃ , TiOx (x is any number from 0 to 2) and inorganic compounds such as ZnO; metals such as Ca and Ba; etc. Examples of the hole transport layer (hole extraction layer) include PEDOT (polyethylenedioxythiophene) / PSS (polystyrenesulfonate), polypyrrole, polyaniline, and polyfuran. Conductive polymers such as polypyridine and polycarbazole; inorganic compounds such as MoO ₃ and WO ₃ ; organic semiconductor molecules such as phthalocyanine and porphyrin and derivatives thereof; transition metal complexes; triphenyl Charge transfer agents such as amine compounds and hydrazine compounds; charge transfer complexes such as TTF (Tetrathiafulvalene); materials with a high degree of successful transfer. The polymer system according to the present invention is contained in a photoelectric conversion layer (photoactive layer). However, the solar cell element of the present invention is not limited to the above-mentioned structure, and may have other structures as long as it can be used as a solar cell element.

(Other applications) 高分子 The polymer compound (I) of the present invention has the above-mentioned semiconductor characteristics, so even in organic electronics, such as photoelectric conversion elements, transistors (photoelectric crystals, etc.), EL elements, sensors (light sensors, etc.), Memory, electrophotographic photoreceptors, capacitors, and / or batteries can also be used. It can also be used as a material for a proton conductive film. [Example]

Hereinafter, the synthesis of various polymer compounds constituting an organic semiconductor material and the characteristics of an organic solar cell using an organic semiconductor material containing a polymer compound will be described based on examples. However, these are examples, and the present invention is not limited to these examples.

[Compounds 0 to 5] (Synthesis of Compound 0) Synthesis of 1,2,5,6-tetraamino-4,8 by appropriately selecting a combination of commercially available naphthalenes, such as halogenation and amination. -Difluoronaphthalene (compound 0).

(Synthesis of Compound 1) Secondly, 5,10-difluoronaphtho [1,2-c: 5,6-c '] bis [1,2,5] thiadiazole (Compound 1) was synthesized. First, put the obtained compound 0 (174 mg), pyridine (18 mL), and thionyl chloride (1.12 g) in a reaction container, and stir at 90 ° C for 2 hours. Then, the reaction liquid was dried under reduced pressure to obtain a solid. After methanol was added to the obtained solid for filtration, the filtered solid was washed with methanol. The washed solid was dried to obtain a brown solid object (130 mg, 99%). The reaction formula is shown below.

The physical property data of the obtained compound 1 are as follows. ¹ HNMR (400 MHz, CDCl ₃ ): δ = 8.08-8.03 (m, 2H). ¹⁹ FNMR (565 MHz, CDCl ₃ ): δ = -107.71.

(Synthesis of Compound 2) Under a nitrogen atmosphere, trifluoroacetic acid (25 mL), compound 1 (140 mg, 0.5 mmol), and N-bromosuccinimide (1.78 g, 10 mmol) were added to the reaction vessel, and the mixture was stirred at 70 ° C for 16 hours. Then, water (200 mL) was added to the reaction solution, and the precipitated yellow body was filtered and washed with methanol (50 mL) to obtain Compound 2 (160 mg, yield 73%).

(Synthesis of compound 3) 3- (2-decylhexadecyl) -5-trimethylstannylthiophene (compound 3) Reference document: Synthesis in the order described in Nature Energy, 1, 15027 (2016).

(Synthesis of compound 4) 加入 Add compound 2 (100 mg, 0.228 mmol), compound 3 (532 mg, 0.91 mmol), tris (triphenylphosphine) palladium (0) (9 mg, 4 mol%), and toluene (3 mL) in a reaction vessel. . After the reaction vessel was replaced with argon, the reaction vessel was sealed and reacted at 100 ° C. for 3 hours using a μ-wave reactor. After cooling to room temperature, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine and water. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained reaction mixture was separated and purified by silica gel column chromatography using a hexane: chloroform (3: 1) solvent as a transfer layer, and then ethyl acetate: chloroform (4: 1) was performed once. Recrystallization gave Compound 4 (177 mg, yield 70%) as a red solid.

The physical property data of the obtained compound 4 are as follows. ¹ HNMR (400MHz, CDCl ₃ , TMS) δ = 8.34 (d, J = 0.8Hz, 2H), 7.26 (s, 2H), 2.69 (d, J = 6.8Hz, 4H), 1.69-1.76 (m, 2H ), 1.23-1.33 (m, 96H), 0.85-0.88 (m, 12H) MS (EI) m / z = 1230 (M ⁺ )

(Synthesis of Compound 5) Compound 4 (157 mg, 0.141 mmol) was added to chloroform (10 mL) in a reaction vessel under a nitrogen atmosphere to dissolve it. Then, N-bromosuccinimide (148 mg, 0.84 mmol) was added and stirred at 50 ° C for 6 hours. Then, an aqueous sodium thiosulfate solution (10 mL) was added to the reaction solution, and the mixture was stirred for 30 minutes. Then, water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with saturated brine and water. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained reaction mixture was separated and purified by silica gel column chromatography using a hexane: chloroform (3: 1) solvent as a transfer layer, and then ethyl acetate: chloroform (4: 1) was performed once. Recrystallization gave Compound 5 (146 mg, yield 80%) as a red solid. The reaction formula is shown below.

The physical property data of the obtained compound 5 are as follows. ¹ HNMR (400MHz, CDCl ₃ , TMS) δ = 8.20 (s, 2H), 2.64 (d, J = 7.2Hz, 4H), 1.74-1.83 (m, 2H), 1.22-1.34 (m, 96H), 0.84 -0.87 (m, 12H) MS (EI) m / z = 1388 (M ⁺ )

[Synthesis of Polymer Compound P1 and P2] (Synthesis of Polymer Compound P1) Next, add compound 5 (34.7 mg, 0.025 mmol) and compound 6 (12.3 mg, 0.025 mmol, (Commercial product), (triphenylphosphine) palladium (0) (0.5 mg, 2 mol%), toluene (2 mL). After replacing the reaction vessel with argon, the reaction vessel was sealed and reacted at 200 ° C. for 2 hours using a μ-wave reactor. After cooling to room temperature, the reaction solution was poured into a mixed solution of methanol (50 mL) and hydrochloric acid (2 mL) to reprecipitate. The precipitate was filtered, washed with methanol and hexane using a Soxhlet extractor, and then extracted with chloroform. After concentrating the chloroform solution, reprecipitation was performed using methanol to obtain a polymer compound P1 (20 mg, 62%) as a dark purple solid. The reaction formula is shown below.

The number average molecular weight of polymer compound P1 is 33500, the weight average molecular weight is 79100, the band gap obtained from the absorption spectrum of the film is 1.46eV, and the HOMO level obtained by Cyclic voltammetry is − 5.28eV. As a result of measuring the UV-vis absorption spectrum of the thin film, the absorption end of the polymer compound P1 was 845 nm.

(Synthesis of Polymer Compound P2) 化合物 Compound 7 used in the following reaction formula was synthesized in accordance with the procedure described in Non-Patent Document 1. Next, compound 5 (34.7 mg, 0.025 mmol), compound 7 (13.2 mg, 0.025 mmol), tris (triphenylphosphine) palladium (0) (0.5 mg, 2 mol%), and toluene (2 mL) were added to the reaction vessel. After the reaction vessel was replaced with argon, the reaction vessel was sealed and reacted at 200 ° C. for 2 hours using a μ-wave reactor. After cooling to room temperature, the reaction solution was poured into a mixed solution of methanol (50 mL) and hydrochloric acid (2 mL) to reprecipitate. The precipitate was filtered, washed with methanol, hexane, and chloroform using a Soxhlet extractor, and then extracted with chloroform. After concentrating the chloroform solution, reprecipitation was performed using methanol to obtain a polymer compound P2 (20 mg, 57%) as a dark purple solid. The reaction formula is shown below.

The number average molecular weight of the polymer compound P2 is 66300, the weight average molecular weight is 529,000, the band gap obtained from the absorption spectrum of the film is 1.53eV, and the HOMO level obtained by photoelectron spectroscopy in the atmosphere is -5.50eV. As a result of measuring the UV-vis absorption spectrum of the thin film, the absorption end of the polymer compound P2 was 810 nm.

Next, the synthesized polymer compounds P1 and P2 are used to manufacture solar cell elements and evaluate the performance of photoelectric conversion efficiency and the like.

[Performance Evaluation of Solar Cell Element] (Example 1) Evaluation of a solar cell element was performed using a polymer compound P1. First, the glass substrate of the patterned ITO film was sufficiently washed, and then subjected to UV ozone treatment. Next, a solution of 0.5 g of zinc (II) acetate dihydrate and 0.142 mL of ethanolamine in 5 mL of 2-methoxyethanol was spin-coated at 5000 rpm for 30 seconds. The substrate was heated at 180 ° C for 30 minutes to form an electron extraction layer. The substrate on which the electronic extraction layer was formed was placed in a glove box, and a PC ₇₁ BM (phenyl C ₇₁ -methyl butyrate) chlorobenzene solution (polymer compound P1 / The weight ratio of PC ₇₁ BM = 1/2), and a photoactive layer (film thickness 200 nm) was formed by spin coating. Further, on the active layer, a molybdenum trioxide (MoO ₃ ) film having a thickness of 7.5 nm as a hole extraction layer was sequentially formed, and then a silver film having a thickness of 100 nm as an electrode layer was formed by a resistance heating vacuum deposition method. , Manufacturing 4mm square organic thin film solar cell elements.

A solar simulator (AM1.5G filter, irradiance of 100 mW / cm ² ) was used for the obtained organic thin-film solar cell, and a certain amount of light was irradiated to measure the generated current and voltage. Fig. 1 (a) shows a graph of current density-voltage characteristics, and Fig. 1 (b) shows a spectral sensitivity characteristic.

From the obtained FIG. 1, when the short-circuit current density Jsc (mA / cm ² ), the open voltage Voc (V), and the form factor FF were obtained, Jsc = 14.0mA / cm ² , Voc = 0.74V, and FF = 0.64. When the photoelectric conversion efficiency (η) was calculated by the formula η = (Jsc × Voc × FF) / 100, it was 6.6%.

(Example 2) Evaluation of a solar cell element was performed using a polymer compound P2. First, a PC ₇₁ BM (phenyl C ₇₁ -methyl butyrate) chlorobenzene solution containing polymer compound P2 and a fullerene derivative is used (weight ratio of polymer compound P2 / PC ₇₁ BM = 1/2) An organic thin-film solar cell (thickness: 300 nm) was produced in the same manner as above except that the photoactive layer was formed by spin coating, and its characteristics were evaluated. The current density-voltage characteristics shown in Fig. 2 (a) were obtained, which were Jsc = 17.6 mA / cm ² , Voc = 0.84V, FF = 0.72, and η was 10.7%. The spectral sensitivity characteristics are shown in FIG. 2 (b).

Comparative Example 1 As Comparative Example 1, first, the following polymer compound P3 was synthesized in the order described in Non-Patent Document 1.

As a result of measuring the UV-vis absorption spectrum of the thin film of the polymer compound P3, the absorption end of the polymer compound P3 was 803 nm.

Next, the evaluation of the solar cell element was performed using the polymer compound P3. Use a chlorobenzene solution of PC ₇₁ BM (phenyl C ₇₁ -methyl butyrate) containing polymer compound P3 and fullerene derivatives (weight ratio of polymer compound P3 / PC ₇₁ BM = 1/2), except An organic thin-film solar cell (thickness: 200 nm) was produced in the same manner as described above except that the photoactive layer was formed by spin coating, and its characteristics were evaluated. The current density-voltage characteristics shown in Fig. 3 (a) were obtained, which were Jsc = 12.0 mA / cm ² , Voc = 0.73V, FF = 0.67, and η was 5.8%. The spectral sensitivity characteristic is shown in FIG. 3 (b).

The results obtained from the examples and comparative examples are shown in Table 1. As shown in Table 1, it was understood that the solar cell elements of Examples 1 and 2 using the polymer compounds P1 and P2 showed good Jsc (short-circuit current density) and η compared to Comparative Example 1 using the polymer compound P3. (Photoelectric conversion efficiency).

[Industrial availability]

Since the organic semiconductor material of the present invention exhibits good short-circuit current density and photoelectric conversion efficiency, it can be used in the field of organic thin-film solar cells and the like.

[Fig. 1] A graph showing a current density-voltage characteristic of the solar cell in Example 1 and a graph showing a measurement of a spectral sensitivity. [Fig. 2] A graph showing the current density-voltage characteristics of the solar cell in Example 2 and a graph showing the measurement of the spectral sensitivity. [Fig. 3] A graph showing the current density-voltage characteristics of the solar cell in Comparative Example 1 and a graph showing the measurement of the spectral sensitivity.

Claims (7)

A polymer compound represented by the following general formula (I), (In general formula (I), R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; n is an integer of 2 or more). The polymer compound according to claim 1, wherein R ³ and R ⁴ are each independently a hydrogen atom or a fluorine atom. The polymer compound according to claim 2, wherein R ³ and R ⁴ are fluorine atoms. An organic semiconductor material comprising the polymer compound according to any one of claims 1 to 3. An organic solar cell comprising an organic semiconductor material as claimed in claim 4. A method for producing a polymer compound represented by the following general formula (I-1), comprising a step of polymerizing a compound represented by the following general formula (a) and a compound represented by the following general formula (b), (In general formula (a), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^a represents a linear, branched chain, or (Cyclic aliphatic hydrocarbon group) (In general formula (b), R ^1b and R ^2b are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^b represents a bromine atom or an iodine atom) (In general formula (I-1), R ^1b and R ^2b are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 60 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or a carbon atom 1 An aliphatic hydrocarbon group of ~ 60; n is an integer of 2 or more). A method for producing a polymer compound represented by the following general formula (I-2), which comprises a step of polymerizing a compound represented by the following general formula (c) and a compound represented by the following general formula (d), (In general formula (c), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; A ^C represents a straight chain, branched chain, or (Cyclic aliphatic hydrocarbon group) (In general formula (I-2), R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom, or an aliphatic hydrocarbon group having 1 to 60 carbon atoms; n is an integer of 2 or more).