JP6371051B2 - Anthraquinone derivative, photoelectric conversion material and photoelectric conversion element - Google Patents

Description

  The present invention relates to a novel p-type organic semiconductor material having a specific structure, a photoelectric conversion material and a photoelectric conversion element using the same.

In recent years, solar cells (solar power generation) that can be used continuously, do not deplete resources, and have low environmental pollution have been actively studied. Solar cells are roughly classified into Si-based and non-Si-based inorganic solar cells, and dye-sensitized and organic thin-film organic solar cells. Inorganic solar cells generally have high photoelectric conversion efficiency, but have a drawback of high manufacturing cost because high vacuum is required or high-temperature heat treatment is required. On the other hand, since the organic solar cell can be formed by a coating method, a printing method, or the like, the manufacturing cost is low and the film can be formed in a large area. Another advantage of organic solar cells is that they can be lighter than inorganic solar cells. In particular, an organic thin film type solar cell is said to be excellent in a printing method and easy to form a film or the like, so that it is easy to manufacture a flexible solar cell.
However, since many organic solar cells have low photoelectric conversion efficiency, increasing the photoelectric conversion efficiency is a problem.

  Currently, P3HT [poly (3-hexylthiophene)], which is a p-type organic semiconductor material, and PCBM [[6, 6], which is an n-type organic semiconductor material, as materials having high photoelectric conversion efficiency in organic thin-film solar cells. ] -Phenyl-C61-butyric acid methyl ester] and a bulk heterojunction made of a mixed material (see Non-Patent Document 1, etc.). In addition, a low molecular compound such as pentacene may be used as the p-type organic semiconductor material. However, it is generally considered that a high molecular weight material is more suitable for device manufacturing by coating, which can reduce cost and increase the screen size. It is considered easy.

A characteristic required for the p-type organic semiconductor material is that the material has a highly planar π-conjugated plane. This is because high π-π interaction and high carrier transport efficiency can be expected, and as a result, high photovoltaic power can be provided.
Patent Documents 1 to 3 disclose a polymer-type p-type organic semiconductor.
However, further improvement in photoelectric conversion efficiency of organic solar cells is desired.

JP 2008-042107 A JP 2009-155891 A Special table 2011-116962 gazette

F. Padinger, et al., Adv. Funct. Mater., 13, 85 (2003)

Accordingly, an object of the present invention is to provide a p-type organic semiconductor material that is easy to manufacture and has high planarity in a polymer skeleton.
Moreover, the objective of this invention is providing the photoelectric conversion material which has the high photoelectric conversion efficiency using the said p-type organic-semiconductor material, a photoelectric conversion layer, a photoelectric conversion element, and an organic thin-film solar cell.

  As a result of intensive studies, the present inventors have found that an anthraquinone derivative having a specific structure is easy to manufacture, has a low manufacturing cost, and is excellent in solubility. Therefore, when used as a p-type organic semiconductor material, the photoelectric conversion layer It was found that can be easily manufactured. As a result of further investigation, it has been found that a photoelectric conversion element having the photoelectric conversion layer exhibits high carrier mobility and can achieve the above object.

  The present invention has been made based on the above knowledge, and has an anthraquinone characterized by having at least one structural unit represented by the following general formula (1) and at least one structural unit selected from the following group Z: A derivative (hereinafter also referred to as a first anthraquinone derivative) is provided.

(In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom, and a hydrogen atom in the structural unit is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group may be substituted, and R ⁴ and R ⁵ may be an optionally substituted hydrocarbon group. Represents.)

Wherein X ³ represents S or NR ⁶ , X ⁴ represents S, NR ⁶ , CR ⁷ R ⁸ or SiR ⁷ R ⁸ , X ⁵ represents S, O or NR ⁶ , R ⁶ , R ⁷ and R ⁸ represent an optionally substituted hydrocarbon group, k represents an integer of 1 to 4, and the hydrogen atom in the structural unit represented by group Z is a fluorine atom, a chlorine atom, or a bromine atom , An iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a —NR ⁹ R ¹⁰ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, ⁹ and R ^{10 each} represents an optionally substituted hydrocarbon group.)

  The present invention also provides the anthraquinone derivative represented by the following general formula (2).

(Wherein R ¹ and R ² represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X ¹ And X ² represents an oxygen atom or a sulfur atom, and Y ¹ and Y ² are a single bond or a group connected by combining 1 to 5 groups selected from the following (Y-1) to (Y-4). And Z ¹ and Z ² represent a single bond or a group selected from the following (Z-1) to (Z-25) (provided that at least one of Z ¹ and Z ² is not a single bond), and n Represents an integer of 1 to 1000. The hydrogen atom of the anthraquinone ring in the formula is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group, or an optionally substituted hydrocarbon group. (It may be substituted by a heterocyclic group.)

(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atom in the groups represented by (Y-1) to (Y-3) is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, It may be substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, an —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ And R ⁵ represents an optionally substituted hydrocarbon group.)

Wherein X ³ represents S or NR ⁶ , X ⁴ represents S, NR ⁶ , CR ⁷ R ⁸ or SiR ⁷ R ⁸ , X ⁵ represents S, O or NR ⁶ , R ⁶ , R ⁷ and R ⁸ represent an optionally substituted hydrocarbon group, k represents an integer of 1 to 4, and hydrogen atoms in the structural units represented by (Z-1) to (Z-25) are , Fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group, —NR ⁹ R ¹⁰ group, optionally substituted hydrocarbon group or optionally substituted heterocyclic group And R ⁹ and R ^{10 each} represents an optionally substituted hydrocarbon group.)

  The present invention also provides a p-type organic semiconductor material containing at least one kind of the anthraquinone derivative.

  Moreover, this invention provides the photoelectric conversion material formed by containing (A) said p-type organic-semiconductor material and (B) n-type organic-semiconductor material.

  Moreover, this invention provides the photoelectric converting layer obtained by forming into a film the said photoelectric converting material.

  Moreover, this invention provides the photoelectric conversion element which has the said photoelectric converting layer.

  Moreover, this invention provides the organic thin film solar cell which has the said photoelectric conversion element.

  The present invention also provides a novel anthraquinone derivative (hereinafter also referred to as a second anthraquinone derivative) represented by the following general formula (4), which is useful as an intermediate for the first anthraquinone derivative.

(In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ^23, and R ²⁴ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or may be substituted. Represents a hydrocarbon group or an optionally substituted heterocyclic group, and at least two of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are —Y—R; A group represented by
X ¹ and X ² represent an oxygen atom or a sulfur atom,
Y represents each independently the group which combined 2-5 groups chosen from the following (Y-1)-(Y-4),
Each R independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. )

(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atom in the groups represented by (Y-1) to (Y-3) is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, It may be substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, an —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ And R ⁵ represents an optionally substituted hydrocarbon group.)

  According to the present invention, it is possible to provide a novel anthraquinone derivative useful as an organic semiconductor material that can be produced at low cost and is excellent in solubility and coatability. If the photoelectric conversion material of the present invention containing the derivative is used, the coating process in semiconductor production is facilitated by excellent solubility, and high performance of the device can be realized by high carrier mobility.

FIG. 1A is a cross-sectional view showing an example of the configuration of the photoelectric conversion element of the present invention, FIG. 1B is a cross-sectional view showing another example of the configuration of the photoelectric conversion element of the present invention, FIG.1 (c) is sectional drawing which shows another example of a structure of the photoelectric conversion element of this invention.

  Hereinafter, an anthraquinone derivative of the present invention and an intermediate thereof, and a photoelectric conversion material, a photoelectric conversion layer, a photoelectric conversion layer, and an organic thin-film solar cell using the anthraquinone derivative will be described in detail based on preferred embodiments.

<First anthraquinone derivative>
The first anthraquinone derivative has at least one constitutional unit represented by the general formula (1) and at least one constitutional unit selected from the group Z. In addition, * in the said Formula (1) means that group represented by these formulas couple | bonds with adjacent group in * part (the following is same).

  Among the first anthraquinone derivatives, those having 2 or more and 100 or less of the structural unit represented by the general formula (1) and having 2 or more and 100 or less of the structural unit selected from the group Z have a film forming property. It is preferable because it is excellent. In the first anthraquinone derivative of the present invention, the ratio of the structural unit represented by the general formula (1) and the structural unit selected from the group Z is 5 to 5 in the structural unit of the general formula (1). It is preferably 90 mol%, more preferably 10 to 80 mol%, and particularly preferably 20 to 70 mol%.

The structural unit represented by the general formula (1) and the hydrocarbon group which may be substituted with a hydrogen atom in the structural unit selected from the group Z, and the optionally substituted hydrocarbon group represented by R ⁴ and R ⁵ Examples thereof include an aromatic hydrocarbon group, an aromatic hydrocarbon group substituted with an aliphatic hydrocarbon group, and an aliphatic hydrocarbon group, and those having 1 to 40 carbon atoms, particularly 4 to 22 carbon atoms are preferred.
Examples of the aromatic hydrocarbon group include phenyl, naphthyl, cyclohexylphenyl, biphenyl, terphenyl, fluoryl, thiophenylphenyl, furanylphenyl, 2′-phenyl-propylphenyl, benzyl, naphthylmethyl, and the like.
Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n. -Linear, branched and cyclic alkyl groups such as octyl, isooctyl, t-octyl, nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc., and these aliphatic hydrocarbon groups Is interrupted by —O—, —COO—, —OCO—, —CO—, —S—, —SO—, —SO ₂ —, —NR ¹⁵ —, —HC═CH— or —C≡C—. (Note that the interruption may interrupt the portion to which the aliphatic hydrocarbon group is bonded), and R ¹⁵ is substituted. Examples of the optionally substituted hydrocarbon group may include the same groups as the optionally substituted hydrocarbon group represented by R ⁴ and R ⁵ , among which perfluoroalkyl is preferable.
Examples of the aromatic hydrocarbon group substituted with the aliphatic hydrocarbon group include phenyl, naphthyl, benzyl and the like substituted with the aliphatic hydrocarbon group.
Examples of the group that may substitute these hydrocarbon groups include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, and a —NR′R ″ group. 'And R ″ represent an optionally substituted hydrocarbon group, and the optionally substituted hydrocarbon group is the same group as the optionally substituted hydrocarbon group represented by R ⁴ and R ^5. Is mentioned.

Examples of the heterocyclic group that may substitute a hydrogen atom in the structural unit represented by the general formula (1) and the structural unit selected from group Z include thiazolyl, imidazolyl, oxazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thiophenyl , Furanyl, bithiophenyl, terthiophenyl and the like, and those having 1 to 40 carbon atoms, particularly 4 to 22 carbon atoms are preferred.
Examples of the group that may substitute these heterocyclic groups include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, and a —NR′R ″ group. 'And R ″ represent an optionally substituted hydrocarbon group, and examples of the optionally substituted hydrocarbon group include the same groups as the optionally substituted hydrocarbon group.

The optionally substituted hydrocarbon group represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ used in the formula in the group Z may be substituted represented by R ⁴ and R ^5. The same group as a hydrocarbon group is mentioned.

  In the first anthraquinone derivative of the present invention, the structural unit represented by the general formula (1) and the structural unit selected from the group Z are essential, but further includes a structural unit selected from the following group Y. May be. Having a structural unit selected from Group Y is preferable in terms of improving solubility and conjugation extension.

(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atom in the structural unit represented by group Y is a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, It may be substituted with a thiol group, —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ and R ⁵ are substituted. Represents an optionally hydrocarbon group.)

The optionally substituted hydrocarbon group represented by R ³ , R ⁴ and R ⁵ used in the formula in the group Y may be substituted represented by R ⁴ and R ⁵ in the general formula (1). The group similar to a good hydrocarbon group is mentioned.

  A preferred example of the first anthraquinone derivative is a compound represented by the following general formula (2).

(Wherein R ¹ and R ² represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X ¹ And X ² represents an oxygen atom or a sulfur atom, and Y ¹ and Y ² are a single bond or a group connected by combining 1 to 5 groups selected from the above (Y-1) to (Y-4). There, Z ¹ and Z ^2, Z ¹ and Z ² represents a group selected from a single bond or the (Z-1) ~ (Z -25) ( provided that at least one of Z ¹ and Z ² N is an integer of 1 to 1000. The hydrogen atom of the anthraquinone ring in the formula is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an optionally substituted hydrocarbon group. Alternatively, it may be substituted with an optionally substituted heterocyclic group.)

The hydrocarbon group and heterocyclic group which may substitute the hydrogen atom in the anthraquinone ring represented by the general formula (2), the optionally substituted hydrocarbon group represented by R ¹ and R ² , and the substituted Examples of the heterocyclic group which may be included include those exemplified as the hydrocarbon and heterocyclic group which may substitute the hydrogen atom of the structural unit represented by the general formula (1).

The position of the two groups (—Y ¹ —Z ¹ —R ¹ and —Y ² —Z ² —R ² ) substituting the anthraquinone ring in the general formula (2) is not particularly limited, but the production process is simplified. From the viewpoints of improving the device characteristics and improving the device characteristics, those at the substitution positions represented by the following general formulas (2-1) to (2-4) are preferable, and represented by the following general formula (2-1) or (2-3). Particularly preferred are those at the substitution positions.

(In the formula, R ¹ , R ² , X ¹ , X ² , Y ¹ , Y ² , Z ¹ , Z ² and n represent the same groups as in the general formula (2), and the hydrogen atom of the anthraquinone ring is In the same manner as in the general formula (2), it may be substituted with an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group.

Among the anthraquinone derivatives represented by the general formula (2), a compound in which at least one of Y ¹ , Y ^2, or Z ¹ is not a single bond is preferable because it is easy to produce.

Among the anthraquinone derivatives represented by the general formula (2), those in which R ¹ or R ² is an optionally substituted aromatic hydrocarbon or an optionally substituted aromatic heterocyclic ring are preferable, More preferably, both R ¹ and R ² are an optionally substituted aromatic hydrocarbon or an optionally substituted aromatic heterocycle.
Further, Y ¹ or Y ² is preferably a single bond, (Y-2) or (Y-3), and at least one of Y ¹ or Y ² is (Y-2) or (Y-3). What has a unit is more preferable.
Z ¹ or Z ² is (Z-2), (Z-8), (Z-9), (Z-10), (Z-13), (Z-15), (Z-22), What is (Z-23) or (Z-24) is preferable.

Specific examples of the first anthraquinone derivative include the following compound No. 1-No. 32, but is not limited to these compounds. In the following compounds, R ¹ , R ² and n are the same as those in the general formula (2).

  Any of the first anthraquinone derivatives is not limited to the production method thereof, and can be obtained by a method using a known general reaction. An example of a method for producing the anthraquinone derivative represented by the general formula (2) will be described based on the following reaction formula.

A boronic acid pinacol ester derivative (Y ¹ -Bpin or Y ² -Bpin) having a corresponding Y ¹ -or Y ² -is coupled to a dihalogenated anthraquinone (A) to form an intermediate (B), Bisboronic acid pinacol ester derivatives (pinB-Z ¹ -Bpin or pinB) having the corresponding Z ¹ — or Z ² — by iodination with 3-diiodo-5,5-dimethylhydantoin (DIH) The compound represented by the above general formula (2) can be obtained by increasing the molecular weight with -Z ² -Bpin) to obtain an intermediate (D) and capping the terminal. In addition, when it quenches after the production | generation of an intermediate body (D), R < ¹ > and R < ² > becomes a hydrogen atom.

(In the formula, R ¹ , R ² , Y ¹ , Y ² , Z ¹ , Z ² and n are the same as those in the general formula (2).)

  In the above reaction formula, when the intermediate (C) is excessive in the reaction between the intermediate (C) and the bisboronic acid pinacol ester derivative, it is considered that the following iodine-substituted product (D ′) is also produced. Even if it is a bromine-substituted product (D ′) or is further reacted with a boronic acid pinacol ester derivative to obtain the following compound (2 ′), there is no particular limitation because the same effect is exhibited in the present invention.

(In the formula, R ¹ , R ² , Y ¹ , Y ² , Z ¹ , Z ² and n are the same as those in the general formula (2).)

In the above reaction formula, when performing various coupling reactions, the functional groups to which the intermediates (A), (B) and (C) are bonded are not only bromine and iodine, but also corresponding halogen compounds, triflates, boron compounds, silicon Bibenzofuran derivatives converted into compounds, zinc compounds, and tin compounds may be used. Corresponding to the above intermediates, R ¹ -Br, R ² -Br, Bpin-Z ¹ -Bpin and Bpin-Z ² -Bpin are intermediates (A), (B) and (C) used. Corresponding to the present invention even when the target bibenzofuran derivative is synthesized with each intermediate converted to a halogen compound, triflate, boron compound, silicon compound, zinc compound, and tin compound In order to produce the effect of, it is not particularly limited.

  As a weight average molecular weight (Mw) which the 1st anthraquinone derivative of this invention shows, about 1000-200000 are used preferably. When Mw is 1000 or less, film formation failure may occur, and when it is 200000 or more, the solubility of the compound may decrease, which is not preferable.

  The first anthraquinone derivative of the present invention is suitable as an organic semiconductor material described below, and can also be used for applications such as antioxidants.

<Photoelectric conversion material>
The photoelectric conversion material of the present invention contains (A) a p-type organic semiconductor material containing at least one first anthraquinone derivative, and (B) an n-type organic semiconductor material.

(A) As a p-type organic-semiconductor material, what is necessary is just to contain at least 1 type of the 1st anthraquinone derivative, and it can use it combining another well-known material. For example, phthalocyanine pigments, indigo or thioindigo pigments, quinacridone pigments, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof (for example, polyphenylene vinylene) [2-Methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene]: MEH-PPV, poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1,4 -Phenylene vinylene]), polythiophene and derivatives thereof (for example, poly (3-dodecylthiophene), poly (3-hexylthiophene): P3HT, poly (3-octylthiophene)), poly-N-vinylcarbazole derivatives, and the like. It is done.

  (A) When other known materials are used as the p-type organic semiconductor material, the content of the first anthraquinone derivative is preferably 1 to 99% by mass, more preferably 1 in the (A) p-type organic semiconductor material. -80 mass%.

  (B) As an n-type organic semiconductor material, a perylene pigment, a perinone pigment, a polycyclic quinone pigment, an azo pigment, C60 fullerene, C70 fullerene, and a derivative thereof can be used. For example, tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], oxadiazole derivative [for example, 1,3- Bis [5 ′-(p-tert-butylphenyl) -1,3,4-oxadiazol-2′-yl] benzene], triazole derivatives [eg 3- (4′-tert-butylphenyl) -4 -Phenyl-5- (4 ''-biphenyl) -1,2,4-triazole], phenanthroline derivatives [e.g. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, BCP)], triazine derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives, etc. It can also be used. (B) Among n-type organic semiconductor materials, C60 fullerene, C70 fullerene, and derivatives thereof are preferable because they have high carrier mobility as n-type materials and / or high charge separation efficiency. In addition, the compound quoted as an example as an n-type organic-semiconductor material may be used independently, or may be used together.

  Examples of the C60 fullerene, C70 fullerene, and derivatives thereof include the following C1 to C6 compounds. Among them, C1 PCBM (phenyl) is preferable because it has excellent electronic level matching and is easily available. -C61-butyric acid methyl ester) is preferably used.

  In the photoelectric conversion material of the present invention, the weight ratio of the component (A) to the component (B) (the former: the latter) is 10:90 to 90:10, preferably 10:90 to 70:30, and more preferably Is 20: 80-50: 50.

  Moreover, the photoelectric conversion material of this invention may contain a 1 type, or 2 or more types of solvent as needed.

  The solvent is not particularly limited as long as it can dissolve or disperse the component (A) and the component (B). For example, water, alcohol solvent, diol solvent, ketone solvent, ester solvent, ether Examples thereof include an aliphatic solvent, an aliphatic or alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent having a cyano group, a halogenated hydrocarbon solvent, and other solvents. A photoelectric conversion material using a solvent can be used as a coating solution.

  Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, and third. Pentanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol , Benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2- (N, N-dimethylamino) ethanol, 3 (N, N-dimethylamino) propanol, etc. Can be mentioned.

  Examples of the diol solvent include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol ( 3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl) -1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol 1,4-cyclohexanedimethanol and the like.

  Examples of the ketone solvent include acetone, ethyl methyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, ethyl butyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, and methyl. Examples include amyl ketone, cyclohexanone, and methylcyclohexanone.

  Examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, second butyl acetate, third butyl acetate, amyl acetate, isoamyl acetate, and third amyl acetate. , Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, amyl propionate, Phenyl propionate, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate Methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol mono secondary butyl ether acetate, ethylene glycol mono isobutyl ether acetate, ethylene glycol mono tertiary butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Pyrether acetate, Propylene glycol monoisopropyl ether acetate, Propylene glycol monobutyl ether acetate, Propylene glycol mono secondary butyl ether acetate, Propylene glycol monoisobutyl ether acetate, Propylene glycol mono tertiary butyl ether acetate, Butylene glycol monomethyl ether acetate, Butylene glycol monoethyl Ether acetate, butylene glycol monopropyl ether acetate, butylene glycol monoisopropyl ether acetate, butylene glycol monobutyl ether acetate, butylene glycol mono sec-butyl ether acetate, butylene glycol monoisobutyl ether acetate, butylene glycol mono Examples include tertiary butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, dimethyl malonate, dimethyl succinate, propylene glycol diacetate, and δ-lactone.

  Examples of the ether solvent include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, and dioxane.

  Examples of the aliphatic or alicyclic hydrocarbon solvents include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, solvent naphtha, turpentine oil, D-limonene, pinene, and minerals. Spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd., Solvesso # 100 (Exxon Chemical Co., Ltd.)) and the like.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene, and tetralin.

  Examples of the hydrocarbon solvent having a cyano group include acetonitrile, 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, , 6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.

  Examples of the halogenated hydrocarbon solvent include carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, chlorobenzene, dichlorobenzene, and trichlorobenzene.

  Examples of the other organic solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, aniline, triethylamine, pyridine, and carbon disulfide.

  Among these, preferable solvents include chloroform, dichloromethane, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene and the like.

  When the above-described solvent is contained in the photoelectric conversion material of the present invention, the content is not particularly limited as long as it does not hinder the formation of a photoelectric conversion layer using the photoelectric conversion material. It is preferable that the total amount of the component (A) and the component (B) is 0.1 to 20 parts by weight when it is 100 parts by weight, more preferably 1 to 10 parts by weight, particularly preferably. Is preferably selected from the range of 3 to 7 parts by weight.

<Photoelectric conversion layer>
Next, the photoelectric conversion layer of the present invention will be described. The photoelectric conversion layer of the present invention is obtained by forming the photoelectric conversion material of the present invention into a film. The film forming method is not particularly limited. For example, vapor deposition method, physical vapor deposition method (PVD), chemical vapor deposition method (CVD), atomic layer deposition method (ALD), atomic layer epitaxy method (ALE). ), Dry processes such as molecular beam epitaxy (MBE), vapor phase epitaxy (VPE), sputtering, plasma polymerization, etc .; dip coating, casting, air knife coating, curtain coating, roller coating, wire Forming a coating on a support by wet processes such as bar coating, gravure coating, spin coating, LB, offset printing, screen printing, flexographic printing, dispenser printing, ink jet, and extrusion coating The method of doing is mentioned.

  Although the film thickness of the said photoelectric converting layer is not specifically limited, Generally, it is preferable to set to about 5 nm-5 micrometers, and heat processing, such as annealing, may be performed.

  The photoelectric conversion layer is used for an element in which p-type and n-type organic semiconductor materials are mixed. In addition to the organic bulk heterojunction element which is a preferred embodiment, a super hierarchical nanostructure junction element, a hybrid heterojunction type, pi Used for the i layer and the like in an -n junction type element.

<Photoelectric conversion element and organic thin film solar cell>
The photoelectric conversion element of this invention is comprised similarly to a conventionally well-known photoelectric conversion element except having at least one photoelectric conversion layer of this invention. For example, taking FIG. 1A as an example, the support 1, the electrode 2, the charge transfer layer 3, the photoelectric conversion layer 4, and the electrode 5 are sequentially stacked. Further, a structure excluding the charge transfer layer 3 as shown in FIG. 1B or a structure further having a charge transfer layer 6 as shown in FIG. 1C may be used.

  In the photoelectric conversion element of the present invention, light needs to reach the photoelectric conversion layer 4 from the support 1. In order to allow irradiation light to reach the photoelectric conversion layer 4 from the support 1, the electrode 2 and the charge transfer layer 3, the support 1, the electrode 2 and the charge transfer layer 3 are formed of a light transmissive material, and the light transmittance Is preferably set to be 70% or more.

  As long as the support 1 can stably hold the electrode 2 on the surface, the support 1 is not limited by the material and thickness, but needs to have transparency. Therefore, the shape of the support may be plate or film. Transparency refers to the property of transmitting light in a predetermined wavelength region used in a photoelectric conversion element, for example, visible light region at a high rate. For the support 1, for example, glass, transparent polymer film (polyethylene terephthalate (PET), tetraacetyl cellulose (TAC), polycarbonate, polyethylene naphthalate, polyphenylene sulfide, polyester sulfone, syndiotactic polystyrene) or the like can be used. The photoelectric conversion element of the present invention is preferably formed on the surface of the support 1. However, when the electrode 2 itself has a certain degree of hardness and is self-supporting, the structure in which the electrode 2 also serves as the support 1. In this case, the support 1 may be omitted.

  In the present invention, the work functions of a pair of electrodes (electrode 2 and electrode 5) arranged opposite to each other may have a relatively large relationship with each other (that is, the work functions are different from each other). Therefore, it is sufficient that the work function of the electrode 2 is relatively larger than that of the electrode 5. In this case, the work function difference between the two electrodes is preferably 0.5 V or more. In addition, when a buffer layer is provided between each electrode and the semiconductor layer and the compound of the buffer layer on the electrode and the electrode are chemically bonded, these restrictions may be relaxed.

  Examples of the electrodes 2 and 5 include noble metals such as gold, platinum, and silver, metals such as zinc oxide, indium oxide, tin oxide (NESA), tin-doped indium oxide (ITO), and fluorine-doped tin oxide (FTO). Oxide, lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, aluminum, aluminum-lithium alloy, aluminum- In addition to calcium alloys, aluminum-magnesium alloys, chromium, graphite thin films, organic conductive compounds such as PEDOT-PSS can be used as appropriate. These electrode materials may be used alone or in combination. Since the electrode 2 needs to have transparency, a transparent material such as zinc oxide, NESA, ITO, FTO, and PEDOT-PSS is used. The electrode 2 and the electrode 5 can be formed by using a dry process or a wet process using these electrode materials in the same manner as the photoelectric conversion layer 4. Further, it may be formed by firing by a sol-gel method or the like. Moreover, although the thickness of an electrode is based also on the material of the electrode substance to be used, both the electrode 2 and the electrode 5 are generally set to about 5-1000 nm, More preferably, about 10-500 nm.

The charge transfer layers 3 and 6 prevent the electrode material from entering and reacting with the photoelectric conversion layer, and prevent recombination of charges separated by the photoelectric conversion layer, thereby efficiently transferring the charge to the electrodes 2 and 5. There is a role such as letting. Examples of the material include charge transfer materials such as PEDOT: PSS, PEO, V ₂ O ₅ , zinc oxide, lithium fluoride, TiOx, and naphthalenetetracarboxylic acid anhydride. The charge transfer layer 3 needs to have transparency. When the photoelectric conversion layer 4 is a P3HT: PCBM bulk hetero type, PEDOT: PSS is often used for the charge transfer layer 3, and LiF is often used for the charge transfer layer 6. The charge transfer layers 3 and 6 can be formed using these charge transfer materials by a dry process method or a wet process method in the same manner as the photoelectric conversion layer 4. The thickness of the charge transfer layers 3 and 6 is generally set to 0.01 to 100 nm, more preferably about 0.1 to 50 nm.

  The photoelectric conversion element of this invention can be used for a photodiode, a photodetector, etc. other than the organic thin-film solar cell of this invention.

<Second anthraquinone derivative>
The second anthraquinone derivative is represented by the general formula (4).
In addition, about the part which is not demonstrated especially, the description in a 1st anthraquinone derivative is applied suitably.

R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ^{24 in the} above general formula (4) may be substituted hydrocarbon groups and optionally substituted heterocycles. Examples of the group include those exemplified as the optionally substituted hydrocarbon and optionally substituted heterocyclic group which may substitute the hydrogen atom of the structural unit represented by the general formula (1).
Further, (Y-1) ~ The R ^3, R ⁴ and optionally substituted hydrocarbon group represented by R ⁵ in the group selected from ^(Y-4), R 4 in the general formula (1) And a group similar to the optionally substituted hydrocarbon group represented by R ⁵ .

Preferable examples of the second anthraquinone derivative include a compound represented by the following general formula (5).
(In the formula, R ²⁵ and R ²⁶ represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are a hydrogen atom, Represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, X ¹ and X ² represent an oxygen atom or a sulfur atom, Y ³ and Y ⁴ represent a group in which 2 to 5 groups selected from the above (Y-1) to (Y-4) are combined.

As the optionally substituted hydrocarbon group and optionally substituted heterocyclic group represented by R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R ³⁴ in the general formula (5), And those exemplified as the optionally substituted hydrocarbon and the optionally substituted heterocyclic group which may substitute the hydrogen atom of the structural unit represented by the general formula (1).

  The second anthraquinone derivative is not limited to its production method, and can be obtained by a method using a well-known general reaction. However, the second anthraquinone derivative is in the middle of the production method of the first anthraquinone derivative. Since it corresponds to the intermediate (B) or intermediate (C) produced in step 1, it can be produced by the same method as the intermediate (B) or intermediate (C) in the production method of the first anthraquinone derivative.

  The second anthraquinone derivative is suitable as an intermediate for the first anthraquinone derivative and can also be used for applications such as an antioxidant.

  Hereinafter, the present invention will be described in more detail with reference to intermediate synthesis examples, examples and comparative examples. However, the present invention is not limited by the following examples.

  Intermediate synthesis examples 1 to 5 show synthesis examples of an intermediate (second anthraquinone derivative) necessary for the synthesis of the first anthraquinone derivative, and Examples 1 to 15 are synthesis examples of the first anthraquinone derivative. is there. In Examples 16 to 37 and Comparative Examples 1 to 7, the photoelectric conversion material of the present invention was prepared using the obtained first anthraquinone derivative or the comparative compound, and the photoelectric conversion layer and the photoelectric conversion were prepared using the photoelectric conversion material. A conversion element was produced and the photoelectric conversion element was evaluated.

[Intermediate Synthesis Example 1] Synthesis of AQN-4T <Step 1> Synthesis of AQN-2T (compound shown in [Chemical Formula 19] below) In a reaction vessel, 10.0 g (27.3 mmol) of 2,6-dibromoanthraquinone, 3-hexyl-2-thiopheneboronic acid pinacol ester 24.1 g (82.0 mmol), potassium carbonate aqueous solution 69 ml (2.0 M 136.6 mmol) and tetrahydrofuran (THF) 2200 ml were charged and replaced with nitrogen. Under this atmosphere, 947 mg (0.82 mmol) of tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ] was added and reacted at 80 ° C. for 4 hours. Further, 500 mg (0.43 mmol) of Pd (PPh ₃ ) ₄ was added, reacted at 80 ° C. for 6 hours, filtered through radiolite, separated into oil and water by adding ultrapure water and toluene, and the organic layer was washed with ultrapure water. did. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, further washed with methanol, and concentrated under reduced pressure to obtain 15.2 g of a pale yellow powder (crude yield: 102%). It was confirmed by ¹ H-NMR and ¹³ C-NMR that the obtained pale yellow powder was the target AQN-2T. The analysis results are shown below. AQN-2T was used in the next reaction without purification.
¹ H-NMR (CDCl ₃ ) δ: 8.40 (2H, s), 8.36 (2H, d, J = 7.9 Hz), 7.86 (2H, d, J = 7.9 Hz), 7.36 (2H, d, J = 4.9 Hz), 7.05 (2H, d, J = 4.9 Hz), 2.75 (4H, t, J = 7.9 Hz), 1.65 (2H, m), 1.31 (12H, m), 0.86 (6H, t, J = 6.7 Hz).
¹³ C-NMR (CDCl ₃ ) δ: 182.61, 141.15, 140.83, 135.65, 134.17, 133.73, 131.80, 130.18, 127.73, 127.35, 125.59, 31.60, 30.88, 29.15, 28.99, 22.59, 14.07

<Step 2> Synthesis of AQN-2TI ₂ (compound shown in [Chemical Formula 20] below) A reaction vessel was charged with 14.7 g (27.0 mmol) of AQN-2T obtained in <Step 1> and 213 ml of THF, After cooling to 0 ° C., 25.6 g (67.4 mmol) of 1,3-diiodo-5,5-dimethylhydantoin (DIH) was added and stirred. Concentrated sulfuric acid (11 ml) was added dropwise, and the mixture was reacted for 1 hour in an ice-cooled state and at room temperature for 1 hour. Methanol was added, followed by filtration to obtain a yellow solid. This yellow solid was dried under reduced pressure, washed with a mixed solution of methanol / ultra pure water, and dried under reduced pressure to obtain 21.5 g of a yellow powder (crude yield: 100%). . It was confirmed by ¹ H-NMR and ¹³ C-NMR that the obtained yellow powder was the target AQN-2TI ₂ . The analysis results are shown below. AQN-2TI ₂ was used in the next reaction without purification.
¹ H-NMR (CDCl ₃ ) δ: 8.35 (2H, d, J = 7.9 Hz), 8.32 (2H, d, J = 1.8 Hz), 7.79 (2H, dd, J = 7.9, 1.8 Hz), 7.19 ( 2H, s), 2.69 (4H, t, J = 7.9 Hz), 1.66-1.59 (4H, m), 1.34-1.26 (12H, m), 0.85 (6H, t, J = 6.7 Hz).
¹³ C-NMR (CDCl ₃ ) δ: 182.31, 142.64, 141.64, 139.86, 139.85, 133.98, 133.70, 132.01, 127.86, 127.19, 73.97, 31.52, 30.77, 29.03, 28.59, 22.50, 14.04

<Step 3> Synthesis of AQN-4T (compound shown in the following [Chemical Formula 21]) In a reaction vessel, 3.4 g (4.3 mmol) of AQN-2TI ₂ obtained in <Step 2>, 3-hexyl-2 -Thiophenboronic acid pinacol ester 3.8g (12.9mmol), potassium carbonate aqueous solution 11ml (2.0M 21.5mmol), and THF 600ml were prepared, and it substituted by nitrogen. Under this atmosphere, 150 mg (0.14 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 90 ° C. for 5 hours. Further, 450 mg (0.42 mmol) of Pd (PPh ₃ ) ₄ was added, reacted at 100 ° C. for 20 hours, filtered through radiolite, separated into oil and water by adding ultrapure water and toluene, and the organic layer was washed with ultrapure water. did. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, further washed with methanol, dried under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane-toluene) to obtain 2.6 g of an orange powder. Obtained (yield: 69%). It was confirmed by ¹ H-NMR and ¹³ C-NMR that the obtained orange powder was the target AQN-4T. The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: 8.43 (2H, d, J = 1.8 Hz), 8.37 (2H, d, J = 7.9 Hz), 7.89 (2H, dd, J = 7.9, 1.8 Hz), 7.20 ( 2H, d, J = 5.5 Hz), 7.06 (2H, s), 6.96 (2H, d, J = 5.5 Hz), 2.79 (8H, m), 1.74-1.64 (8H, m), 1.35 (24H, m ), 0.88 (12H, q, J = 7.3 Hz).
¹³ C-NMR (CDCl ₃ ) δ: 182.59, 141.31, 140.81, 140.07, 136.57, 135.35, 133.88, 133.86, 131.74, 130.25, 130.20, 128.93, 127.88, 127.11, 124.02, 31.76, 31.67, 30.85, 30.72, 29.39, 29.38, 29.30, 29.22, 22.69, 22.65, 14.17, 14.14

[Intermediate Synthesis Example 2] Synthesis of AQN-4TBr ₂ (compound shown in [Chemical Formula 22] below) In a reaction vessel, 10.0 g (11.4 mmol) of AQN-4T obtained in Intermediate Synthesis Example 1 and THF 115 ml was charged, and 21.5 g (57.2 mmol) of trimethylphenylammonium bromide (PTMA-Br ₃ ) dissolved in 54 ml of THF was added dropwise to the solution over 30 minutes, followed by stirring for 4 hours. Further, 8.6 g (22.9 mmol) of PTMA-Br ₃ dissolved in 22 ml of THF was added dropwise and reacted for 1 hour. An aqueous sodium thiosulfate solution and toluene were added to separate the oil and water, and the organic layer was washed with ultrapure water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane-toluene) to obtain 8.8 g of a red powder (yield: 74%). It was confirmed by ¹ H-NMR and ¹³ C-NMR that the obtained red powder was the target AQN-4TBr ₂ . The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: 8.41 (2H, d, J = 1.8 Hz), 8.37 (2H, d, J = 7.9 Hz), 7.87 (2H, dd, J = 7.9, 1.8 Hz), 7.00 ( 2H, s), 6.92 (2H, s), 2.75 (8H, t, J = 7.6 Hz), 1.65 (8H, m), 1.39-1.27 (24H, m), 0.91-0.85 (12H, m).
¹³ C-NMR (CDCl ₃ ) δ: 182.41, 141.29, 140.56, 140.49, 135.7, 135.07, 133.82, 133.77, 132.74, 131.76, 131.68, 129.17, 127.83, 127.08, 110.75, 31.63, 31.59, 30.77, 30.51, 29.26, 29.15, 29.12, 29.10, 22.61, 22.60, 14.10, 14.07

[Intermediate Synthesis Example 3] Synthesis of AQN-2TI ₂ (dihexyl) <Step 1> Synthesis of AQN-2T (dihexyl) (compound shown in [Chemical Formula 22-1] below) In a reaction vessel, 2,6-dibromoanthraquinone 190 mg (0.53 mmol), 3,4-dihexyl-2-thiopheneboronic acid pinacol ester 500 mg (1.33 mmol), potassium carbonate aqueous solution 1.4 ml (2.0 M 2.64 mmol) and THF 38 ml were charged with nitrogen. Replaced. Under this atmosphere, 61 mg (0.05 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 100 ° C. for 5 hours. Further, 30 mg (0.03 mmol) of Pd (PPh ₃ ) ₄ was added, reacted at 100 ° C. for 3 hours, filtered through radiolite, separated into oil and water by adding ultrapure water and toluene, and the organic layer was washed with ultrapure water. did. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, further washed with methanol, and concentrated under reduced pressure to obtain 320 mg of a pale yellow powder (crude yield: 85%). It was confirmed by ¹ H-NMR that the obtained pale yellow powder was the target AQN-2T (dihexyl). The analysis results are shown below. AQN-2T (dihexyl) was used in the next reaction without purification.
¹ H-NMR (CDCl ₃ ) δ: 8.39 (2H, d, J = 1.8 Hz), 8.35 (1H, s), 8.33 (1H, s), 7.85 (2H, dd, J = 7.9, 1.8 Hz), 7.03 (2H, s), 2.66 (4H, t, J = 8.2 Hz), 2.58 (4H, t, J = 7.6 Hz), 1.73-1.65 (4H, m), 1.52 (4H, dd, J = 8.5, 6.7 Hz), 1.43 (4H, d, J = 6.1 Hz), 1.37-1.33 (12H, m), 1.26 (12H, m), 0.92 (6H, t, J = 7.0 Hz), 0.85 (6H, t, (J = 7.0 Hz)

<Step 2> Synthesis of AQN-2TI ₂ (dihexyl) (compound shown in [Chemical Formula 22-2] below) In a reaction vessel, 100 mg (0.14 mmol) of AQN-2T (dihexyl) obtained in Step 1 and THF After charging 6 ml and cooling to 0 ° C., 160 mg (0.42 mmol) of 1,3-diiodo-5,5-dimethylhydantoin was added and stirred. Four drops of concentrated sulfuric acid were added dropwise, and the mixture was reacted for 1 hour in an ice-cooled state and at room temperature for 1 hour, and then methanol was added and filtered to obtain a yellow solid. This yellow solid was dried under reduced pressure, washed with a mixed solution of methanol-ultra pure water, and dried under reduced pressure to obtain 120 mg of a yellow powder (crude yield: 89%). It was confirmed by ¹ H-NMR that the obtained yellow powder was the target AQN-2TI ₂ (dihexyl). The analysis results are shown below. AQN-2TI ₂ (dihexyl) was used in the next reaction without purification.
1H-NMR (CDCl3) δ: 8.34 (2H, d, J = 6.1 Hz), 8.33 (2H, s), 7.79 (2H, d, J = 7.9 Hz), 2.69 (4H, t, J = 7.9 Hz) , 2.57 (4H, t, J = 7.9 Hz), 1.50-1.24 (32H, m), 0.88 (12H, m)

[Intermediate Synthesis Example 4] Synthesis of 1,4-AQN-2TBr ₂ <Step 1> Synthesis of 1,4-AQN-OTf (compound shown in the following [Chemical Formula 22-3]) In a reaction vessel, 2.0 g of quinizarin (8.3 mmol) and 100 mg (0.83 mmol) of dimethylaminopyridine were charged and replaced with nitrogen. Under this atmosphere, 25 ml of dehydrated chloroform and 2.8 g (19.1 mmol) of diisopropylethylamine were added, and the mixture was stirred for 30 minutes under ice cooling. Further, 2.9 g (17.4 mmol) of trifluoromethanesulfonyl chloride was added, and the mixture was reacted for 2 hours under ice cooling and further for 3 hours at room temperature. The reaction was stopped by adding 1.2 M-hydrochloric acid, washed with methanol, filtered, and dried under reduced pressure to obtain 3.6 g (crude yield: 83%) of a pale yellow powder. It was confirmed by ¹ H-NMR that the obtained pale yellow powder was the desired 1,4-AQN-OTf. The analysis results are shown below. 1,4-AQN-OTf was used for the next reaction without purification.
¹ H-NMR (CDCl ₃ ) δ: 8.31 (2H, td, J = 6.4, 3.7 Hz), 7.85 (2H, dq, J = 16.8, 4.4 Hz), 7.68 (2H, d, J = 17.1 Hz).

<Step 2> Synthesis of 1,4-AQN-2T (compound shown in [Chemical Formula 22-4] below) In a reaction vessel, 1,4-AQN-OTf 300 mg (0.59 mmol) obtained in Step 1 and 3 -Hexyl-2-thiopheneboronic acid pinacol ester (520 mg, 1.77 mmol), potassium carbonate aqueous solution (1.5 ml, 2.0 M, 3.00 mmol) and THF (43 ml) were charged and the solution was replaced with nitrogen. Under this atmosphere, 68 mg (0.06 mmol) of Pd (PPh ₃ ) ₄ was added, reacted at 80 ° C. for 5 hours, filtered through radiolite, ultrapure water and toluene were added, and oil-water separation was performed. Washed with pure water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column to obtain 300 mg of an orange oil (yield: 93%). It was confirmed by ¹ H-NMR that the obtained orange oil was the desired 1,4-AQN-2T. The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: 8.07 (2H, dd, J = 5.8, 3.4 Hz), 7.69 (2H, dd, J = 5.8, 3.4 Hz), 7.62 (2H, s), 7.35 (2H, d , J = 5.5 Hz), 7.03 (2H, d, J = 4.9 Hz), 2.36 (4H, t, J = 6.7 Hz), 1.50 (4H, t, J = 7.3 Hz), 1.14 (12H, m), 0.77 (6H, t, J = 7.0 Hz).

<Step 3> Synthesis of 1,4-AQN-2TBr ₂ (compound shown in [Chemical Formula 22-5] below) In a reaction vessel, 100 mg (0.18 mmol) of 1,4-AQN-2T obtained in Step 2 was added. And 1.8 ml of THF were charged, and 210 mg (0.54 mmol) of trimethylphenylammonium bromide (PTMA-Br ₃ ) dissolved in 0.4 ml of THF was added dropwise to this solution and stirred. 3 drops of concentrated sulfuric acid was added dropwise and reacted at room temperature for 3 hours. Further, 210 mg (0.54 mmol) of PTMA-Br ₃ dissolved in THF was added dropwise and reacted for 4 hours. An aqueous sodium thiosulfate solution and hexane were added to separate the oil and water, and the organic layer was washed with ultrapure water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column to obtain 110 mg of an orange oil (yield: 85%). It was confirmed by ¹ H-NMR that the resulting orange oil was the desired 1,4-AQN-2TBr ₂ . The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: 8.09 (2H, dd, J = 5.5, 3.0 Hz), 7.73 (2H, dd, J = 5.8, 3.4 Hz), 7.60 (2H, s), 6.97 (2H, s ), 2.29 (4H, t, J = 7.0 Hz), 1.46 (4H, t, J = 6.4 Hz), 1.13 (12H, m), 0.77 (6H, t, J = 7.0 Hz).

[Intermediate Synthesis Example 5] Synthesis of 1,4-AQN-Cl ₂ -2TBr ₂ <Step 1> Synthesis of 1,4-AQN-Cl ₂ -OTf (compound shown in [Chemical Formula 22-6] below) Reaction vessel Into this, 0.5 g (1.61 mmol) of 5,8-dichloro-1,4-dihydroxyanthraquinone was charged and replaced with nitrogen. Under this atmosphere, 40 ml of dehydrated chloroform and 20 ml of dehydrated pyridine were added, and the mixture was stirred for 10 minutes under ice cooling. Further, 1.4 g (4.83 mmol) of trifluoromethanesulfonic anhydride was added, and the mixture was reacted for 3 hours under ice cooling and further for 1 hour at room temperature. 1.2M-hydrochloric acid and hexane were added thereto for oil / water separation, and the organic layer was washed with ultrapure water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and column purified to obtain 580 mg of an orange oil (yield: 63%). It was confirmed by ¹ H-NMR that the obtained orange oil was the desired 1,4-AQN-Cl ₂ -OTf. The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: ¹ H-NMR (CD ₂ Cl ₂ ) δ: 7.72 (2H, s), 7.69 (2H, s)

<Step 2> Synthesis of 1,4-AQN-Cl ₂ -2T (compound shown in [Chemical Formula 22-7] below) In a reaction vessel, 1,4-AQN-Cl ₂ -OTf 200 mg obtained in Step 1 ( 0.35 mmol), 300 mg (1.05 mmol) of 3-hexyl-2-thiopheneboronic acid pinacol ester, 0.7 ml of potassium carbonate aqueous solution (2.0M 1.75 mmol), and 25 ml of THF were charged and replaced with nitrogen. Under this atmosphere, 40 mg (0.04 mmol) of Pd (PPh ₃ ) ₄ was added, reacted at 85 ° C. for 6 hours, filtered through radiolite, separated into oil and water by adding ultrapure water and toluene, and the organic layer was separated from ultrapure. Washed with water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column to obtain 200 mg of an orange oil (yield: 94%). It was confirmed by ¹ H-NMR that the obtained orange oil was the desired 1,4-AQN-Cl ₂ -2T. The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: 7.59 (2H, s), 7.54 (2H, s), 7.35 (2H, d, J
= 4.9 Hz), 7.00 (2H, d, J = 4.9 Hz), 2.46 (4H, t, J = 7.9 Hz), 1.53 (4H, t, J = 7.6 Hz), 1.16 (12H, s), 0.80 ( (6H, t, J = 7.0 Hz).

<Step 3> Synthesis of 1,4-AQN-Cl ₂ -2TBr ₂ (compound shown in [Chemical Formula 22-8] below) In a reaction vessel, 1,4-AQN-Cl ₂ -2T obtained in Step 2 was added. 90 mg (0.15 mmol) and 1.8 ml of THF were charged, and 160 mg (0.45 mmol) of trimethylphenylammonium bromide (PTMA-Br ₃ ) dissolved in 0.4 ml of THF was added dropwise to this solution and stirred. 3 drops of concentrated sulfuric acid was added dropwise and reacted at room temperature for 5 hours. Further, 160 mg (0.45 mmol) of PTMA-Br ₃ dissolved in THF was added dropwise and reacted overnight at room temperature. An aqueous sodium thiosulfate solution and hexane were added to separate the oil and water, and the organic layer was washed with ultrapure water. The organic layer was dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by column to obtain 90 mg of an orange oil (yield: 79%). It was confirmed by ¹ H-NMR that the obtained orange oil was the desired 1,4-AQN-Cl ₂ -2TBr ₂ . The analysis results are shown below.
¹ H-NMR (CDCl ₃ ) δ: ¹ H-NMR (CDCl ₃ ) δ: 7.57 (2H, s), 7.56 (2H, s), 6.95 (2H, s), 2.37 (4H, t, J = 6.7 Hz), 1.49 (4H, t, J = 7.9 Hz), 1.14 (12H, s), 0.79 (6H, t, J = 7.0 Hz).

Example 1 Compound No. 1 Synthesis of 7 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 260 mg (0.33 mmol) of AQN-2TI ₂ synthesized in <Step 2> of Intermediate Synthesis Example 1 and 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester 230 mg (0.35 mmol), Aliquat 13 mg, sodium carbonate aqueous solution 13 ml (2.0 M 26.0 mmol), and toluene 26 ml were charged and replaced with nitrogen. Under this atmosphere, 38 mg (0.03 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 110 ° C. for 16 hours. 38 mg (0.03 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 110 ° C. for 8 hours. After adding 400 mg (3.3 mmol) of phenylboronic acid and 38 mg (0.03 mmol) of Pd (PPh ₃ ) _{4 and} reacting at 110 ° C. for 4 hours, phenylboronic acid was further added to 520 mg (3.3 mmol) of phenylbromide. The same reaction was performed after changing. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. This residue was washed with acetone for 8 hours using a Soxhlet extractor, dissolved in THF, and filtered through radiolite. This was concentrated under reduced pressure, then dispersed in methanol, and the residue obtained by filtration was dried in vacuo to give compound No. 1 which was a black powder. 7 (yield: 53%) was obtained.
The obtained Compound No. 7 had a number average molecular weight (Mn) of 11,663, a weight average molecular weight (Mw) of 20,609, and Mw / Mn of 1.77.

Example 2 Compound No. Synthesis of 9 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 300 mg (0.29 mmol) of AQN-4TBr ₂ synthesized in Intermediate Synthesis Example 2, 180 mg of 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester (0 .32 mmol), Aliquat 20 mg, aqueous sodium carbonate solution 15 ml (2.0 M 40.3 mmol), and toluene 30 ml were charged and replaced with nitrogen. Under this atmosphere, 34 mg (0.03 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 120 ° C. for 20 hours. After 350 mg (2.9 mmol) of phenylboronic acid and 34 mg (0.03 mmol) of Pd (PPh ₃ ) ₄ were added and reacted at 120 ° C. for 4 hours, phenylboronic acid was further added to 460 mg (2.9 mmol) of phenylbromide. The same reaction was performed after changing. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. This residue was washed with acetone using a Soxhlet extractor for 8 hours, dissolved in chloroholom, filtered, and the insoluble fraction was removed, followed by filtration with radiolite. This was concentrated under reduced pressure, dispersed in methanol, and the residue obtained by filtration was dried under vacuum to obtain compound No. 1 which was a dark red flake. 70 mg of 9 was obtained (yield: 19%).
The obtained Compound No. 9 had a number average molecular weight (Mn) of 9277, a weight average molecular weight (Mw) of 11,760, and Mw / Mn of 1.27.

Example 3 Compound no. Synthesis of 8 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 200 mg (0.19 mmol) of AQN-4TBr ₂ synthesized in Intermediate Synthesis Example 2, 140 mg (0.21 mmol) of 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester ), Aliquat 20 mg, sodium carbonate aqueous solution 10 ml (2.0 M 20.0 mmol), and toluene 20 ml were charged and replaced with nitrogen. Under this atmosphere, 22 mg (0.02 mmol) of Pd (PPh ₃ ) ₄ was added and reacted at 120 ° C. for 22 hours. After 240 mg (1.9 mmol) of phenylboronic acid and 22 mg (0.02 mmol) of Pd (PPh ₃ ) ₄ were added and reacted at 120 ° C. for 4 hours, phenylboronic acid was further added to 300 mg (1.9 mmol) of phenylbromide. The same reaction was performed after changing. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. The residue was washed with acetone using a Soxhlet extractor for 8 hours, dissolved in chloroholom, filtered, and the insoluble fraction was removed, followed by filtration with radiolite. This was concentrated under reduced pressure, dispersed in methanol, and the residue obtained by filtration was dried under vacuum to obtain compound No. 1 which was a dark red flake. 200 mg of 8 was obtained (yield: 80%).
The obtained Compound No. The number average molecular weight of 8 (Mn) is 14564, weight average molecular weight (Mw) of 28 072, Mw / Mn was 1.93.

Example 4 Compound no. Synthesis of 16 (R ₁ and R ₂ are phenyl)
The 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester used in the synthesis of Example 3 was changed to the corresponding boronic acid ester 140 mg (0.16 mmol), and the respective molar ratios were changed. Except that the compound No. 1 was a dark red flake in the same procedure as the synthesis of Example 3. 68 mg of 16 was obtained (yield: 30%).
The obtained Compound No. The number average molecular weight (Mn) of 16 was 5392, the weight average molecular weight (Mw) was 7417, and Mw / Mn was 1.38.

Example 5 Compound no. Synthesis of 17 (R ₁ and R ₂ are phenyl)
The 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester used in the synthesis of Example 3 was changed to the corresponding boronic ester 17 mg (0.04 mmol), and the respective molar ratios were changed. Except that the compound No. 1 was a dark red flake in the same procedure as the synthesis of Example 3. 16 mg of 17 was obtained (yield: 40%).
The obtained Compound No. The number average molecular weight (Mn) of 17 was 3154, the weight average molecular weight (Mw) was 5090, and Mw / Mn was 1.61.

Example 6 Compound no. Synthesis of 18 (R ₁ and R ₂ are phenyl)
The 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester used in the synthesis of Example 3 was changed to the corresponding boronic acid ester 25 mg (0.04 mmol), and the respective molar ratios were changed. Except that the compound No. 1 was a dark red flake in the same procedure as the synthesis of Example 3. 32 mg of 18 was obtained (yield: 78%).
The obtained Compound No. The number average molecular weight (Mn) of 18 was 30038, the weight average molecular weight (Mw) was 140439, and Mw / Mn was 4.68.

Example 7 Compound no. Synthesis of 25 (R ₁ and R ₂ are phenyl)
The 9- (9-heptadecanyl) -9H-carbazole-2,7-diboronic acid bispinacol ester used in the synthesis of Example 3 was changed to the corresponding boronic acid ester 25 mg (0.04 mmol), and the respective molar ratios were changed. Except that the compound No. 1 was a vermilion flake in the same procedure as the synthesis of Example 3. 30 mg of 25 was obtained (yield: 58%).
The obtained Compound No. The number average molecular weight (Mn) of 25 was 6493, the weight average molecular weight (Mw) was 8655, and Mw / Mn was 1.33.

Example 8 Compound no. Synthesis of 9 (R ₁ and R ₂ are naphthyl)
Dark red flakes were prepared in the same manner as in the synthesis of Example 3 except that the phenyl bromide used in the synthesis of Example 3 was changed to 39 mg (0.19 mmol) of the corresponding 2-bromonaphthalene and the respective molar ratios were changed. Compound No. 17 mg of 9 was obtained (yield: 68%).
The obtained Compound No. 9 had a number average molecular weight (Mn) of 13975, a weight average molecular weight (Mw) of 26228, and Mw / Mn of 1.87.

Example 9 Compound no. Synthesis of 26 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 100 mg (0.11 mmol) of AQN-2TI ₂ (dihexyl) synthesized in Intermediate Synthesis Example 3, 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester 60 mg (0.12 mmol), Pd (PPh ₃ ) ₄ 1.3 mg (0.01 mol), tetrabutylammonium bromide 3.4 mg (0.01 mol), sodium carbonate aqueous solution 3.3 ml (2.0 M 0.66 mmol), And 10 ml of toluene were charged and reacted at 150 ° C. for 2 hours in a microwave synthesizer. After adding 130 mg (1.1 mmol) of phenylboronic acid and 1.2 mg (0.01 mmol) of Pd (PPh ₃ ) ₄ , the mixture was reacted at 120 ° C. for 2 hours, and then phenylboronic acid was added to 170 mg of phenylbromide. (1.1 mmol), and the same reaction was performed. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. The residue was washed with acetone using a Soxhlet extractor for 8 hours, dissolved in chloroholom, filtered, and the insoluble fraction was removed, followed by filtration with radiolite. This was concentrated under reduced pressure, methanol was added, and the mixture was recovered after dispersion. By vacuum drying, compound no. 89 mg of 26 was obtained (yield: 74%).
Compound No. The number average molecular weight (Mn) of 26 was 10124, the weight average molecular weight (Mw) was 16590, and Mw / Mn was 1.64.

Example 10 Compound no. Synthesis of 20 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 70 mg (0.10 mmol) of 1,4-AQN-2TBr ₂ synthesized in Intermediate Synthesis Example 4 and 9- (9-heptadecanyl) -2,7-bis (boronic acid bispinacol ester) 9H- Carbazole 69 mg (0.11 mmol), Pd (PPh ₃ ) ₄ 1.2 mg (0.01 mol), tetrabutylammonium bromide 3.2 mg (0.01 mol), sodium carbonate aqueous solution 3.2 ml (2.0 M 0.64 mmol) , And 9.8 ml of toluene were allowed to react at 150 ° C. for 2 hours in a microwave synthesizer. After 120 mg (1.0 mmol) of phenylboronic acid and 1.2 mg (0.01 mmol) of Pd (PPh ₃ ) ₄ were added and reacted at 120 ° C. for 2 hours in the same apparatus, further phenylboronic acid was added to 160 mg of phenylbromide. (1.0 mmol) and the same reaction was carried out. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. The residue was washed with acetone using a Soxhlet extractor for 8 hours, dissolved in chloroholom, filtered, and the insoluble fraction was removed, followed by filtration with radiolite. This was concentrated under reduced pressure, methanol was added, and the mixture was recovered after dispersion. By vacuum drying, compound no. 13 mg of 20 was obtained (yield: 19%).
Compound No. The number average molecular weight (Mn) of 20 was 13988, the weight average molecular weight (Mw) was 15537, and Mw / Mn was 1.11.

Example 11: Compound no. Synthesis of 28 (R ₁ and R ₂ are phenyl)
9- (9-Heptadecanyl) -2,7-bis (boronic acid bispinacol ester) 9H-carbazole used in the synthesis of Example 10 was changed to 44 mg (0.11 mmol) of the corresponding boronic acid ester, Except for changing the ratio, the same procedure as in Example 10 was repeated, except that compound No. 1 was a vermilion flake. 13 mg of 28 was obtained (yield: 19%).
Compound No. The number average molecular weight (Mn) of 28 was 7296, the weight average molecular weight (Mw) was 9031, and Mw / Mn was 1.24.

[Example 12] Compound No. Synthesis of 29 (R ₁ and R ₂ are phenyl)
9- (9-Heptadecanyl) -2,7-bis (boronic acid bispinacol ester) 9H-carbazole used in the synthesis of Example 10 was changed to 67 mg (0.15 mmol) of the corresponding boronic acid ester, Except for changing the ratio, the same procedure as in Example 10 was repeated, except that compound No. 1 was a vermilion flake. 20 mg of 29 was obtained (yield: 20%).
Compound No. The number average molecular weight (Mn) of 29 was 1233, the weight average molecular weight (Mw) was 1700, and Mw / Mn was 1.44.

[Example 13] Compound No. Synthesis of 30 (R ₁ and R ₂ are phenyl)
In a reaction vessel, 90 mg (0.11 mmol) of 1,4-AQN-Cl ₂ -2TBr ₂ synthesized in Intermediate Synthesis Example 5 and 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3- Propanediol) ester 69 mg (0.12 mmol), Pd (PPh ₃ ) ₄ 1.4 mg (0.01 mol), tetrabutylammonium bromide 3.7 mg (0.01 mol), sodium carbonate aqueous solution 4.0 ml (2.0M 0 .80 mmol), and 12 ml of toluene were charged and reacted at 150 ° C. for 2 hours in a microwave synthesizer. After 140 mg (1.1 mmol) of phenylboronic acid and 1.4 mg (0.01 mmol) of Pd (PPh ₃ ) ₄ were added and reacted at 120 ° C. for 2 hours in the same apparatus, phenylboronic acid was further added to 180 mg of phenylbromide. (1.0 mmol) and the same reaction was carried out. The mixture was cooled to room temperature, methanol was added, and the resulting residue was washed with methanol and ultrapure water. The residue was washed with acetone using a Soxhlet extractor for 8 hours, dissolved in chloroholom, filtered, and the insoluble fraction was removed, followed by filtration with radiolite. This was concentrated under reduced pressure, methanol was added, and the mixture was recovered after dispersion. By vacuum drying, compound no. 58 mg of 30 was obtained (yield: 49%).
The obtained Compound No. The number average molecular weight (Mn) of 30 was 6266, the weight average molecular weight (Mw) was 8913, and Mw / Mn was 1.42.

[Example 14] Compound No. Synthesis of 31 (R ₁ and R ₂ are phenyl)
The 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester used in Example 13 was changed to the corresponding boronic acid ester 54 mg (0.07 mmol), and the respective molar ratios were changed. Except for the change, the same procedure as in Example 13 was followed, except that compound No. 34 mg of 31 was obtained (yield: 44%).
The obtained Compound No. The number average molecular weight (Mn) of 31 was 27823, the weight average molecular weight (Mw) was 149626, and Mw / Mn was 5.38.

[Example 15] Compound No. Synthesis of 32 (R ₁ and R ₂ are phenyl)
The 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester used in Example 13 was changed to the corresponding boronic acid ester 40 mg (0.10 mmol), and the respective molar ratios were changed. Except for the change, the same procedure as in Example 13 was followed, except that compound No. 13 mg of 32 was obtained (yield: 18%).
The obtained Compound No. The number average molecular weight (Mn) of 32 was 7732, the weight average molecular weight (Mw) was 9664, and Mw / Mn was 5.38.

Example 16
A photoelectric conversion element having the layer structure shown in FIG. 1C was produced by the following procedure. After the glass substrate (support 1) having a 150 nm ITO film formed as the electrode 2 was subjected to IPA boiling cleaning and UV-ozone cleaning, PEDOT: PSS (3,4-ethylenedioxythiophene: polystyrene sulfone) was formed as the charge transfer layer 3. Acid) was formed into a film by 20 nm spin coating method, and dried under reduced pressure at 100 ° C. for 10 minutes. A photoelectric conversion material of Example 16 was prepared by dissolving 20 mg of the compound of Example 1 as (A) p-type organic semiconductor and 80 mg of PCBM as (B) n-type organic semiconductor in 2 mL of 1,2-dichlorobenzene. . The prepared photoelectric conversion material was formed into a film by a spin coat method, and dried under reduced pressure at 100 ° C. for 30 minutes to obtain a photoelectric conversion layer 4. On the organic thin film layer thus obtained, LiF 0.5 nm (charge transfer layer 6) and aluminum 100 nm (electrode 5) were sequentially deposited by vacuum vapor deposition using a metal mask to obtain the photoelectric conversion element of Example 16. Produced.
The photoelectric conversion element thus obtained was irradiated with pseudo sunlight having an air mass of 1.5 G and 100 mW / cm ² from the ITO electrode side, and the photoelectric conversion characteristics (efficiency (%)) were measured. The results are shown in [Table 1].

[Examples 17 to 37]
In the production of the photoelectric conversion element of Example 16, the Example (A), the component (B), and the composition ratio thereof were changed as shown in [Table 1] in the same manner as Example 16, except that 17 to 37 photoelectric conversion elements were produced. In addition, the photoelectric conversion characteristics (efficiency (%)) of the photoelectric conversion elements of Examples 17 to 37 were measured in the same manner as in Example 16. The results are shown in [Table 1].

[Comparative Examples 1-7]
In preparation of the photoelectric conversion element of the above Example 16, as the component (A), instead of the compound of the present invention, the comparative compound No. 1 to 5 were used, and the photoelectric conversion elements of Comparative Examples 1 to 7 were prepared in the same manner as in Example 16 according to the blending amounts described in [Table 1]. The photoelectric conversion characteristics (efficiency (%)) of the photoelectric conversion elements of 7 to 7 were measured. The results are shown in [Table 1].

Comparative Compound No. 1: 1-Material, number average molecular weight 55000
Comparative Compound No. 2: In-house synthesized product Comparative compound No. 3: Made by Aldrich, number average molecular weight> 20,000
Comparative Compound No. 4: Made by Aldrich, number average molecular weight 10000 to 2000
Comparative Compound No. 5: In-house synthesized product, number average molecular weight (Mn): 988, weight average molecular weight (Mw): 1373, Mw / Mn: 1.39

From the above results, it can be confirmed that the anthraquinone derivative of the present invention exhibits high photoelectric conversion efficiency when used as a p-type organic semiconductor.
Therefore, the photoelectric conversion material using the anthraquinone derivative of the present invention is useful for a photoelectric conversion element and an organic thin film solar cell.

DESCRIPTION OF SYMBOLS 1 Support body 2 Electrode 3 Charge transfer layer 4 Photoelectric conversion layer 5 Electrode 6 Charge transfer layer

Claims (8)

An anthraquinone derivative having 2 to 100 structural units represented by the following general formula (1) and 2 to 100 structural units selected from the following group Z:
(Wherein, X ¹ and X ² represent an oxygen atom or a sulfur atom, and a hydrogen atom in the structural unit is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group may be substituted, and R ⁴ and R ⁵ may be an optionally substituted hydrocarbon group. Represents.)
Wherein X ³ represents S or NR ⁶ , X ⁴ represents S, NR ⁶ , CR ⁷ R ⁸ or SiR ⁷ R ⁸ , X ⁵ represents S, O or NR ⁶ , R ⁶ , R ⁷ and R ⁸ represent an optionally substituted hydrocarbon group, k represents an integer of 1 to 4, and the hydrogen atom in the structural unit represented by group Z is a fluorine atom, a chlorine atom, or a bromine atom , An iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a —NR ⁹ R ¹⁰ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, ⁹ and R ¹⁰ represent an optionally substituted hydrocarbon group.) The anthraquinone derivative according to claim 1, further comprising at least one structural unit selected from the following group Y.
(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atom in the structural unit represented by group Y is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, It may be substituted with a thiol group, —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ and R ⁵ are substituted. Represents an optionally hydrocarbon group.) The anthraquinone derivative according to claim 1 or 2 represented by the following general formula (2).
Wherein R ¹ and R ² represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X ¹ And X ² represents an oxygen atom or a sulfur atom, and Y ¹ and Y ² represent a single bond or a group connected by combining 1 to 5 groups selected from the following (Y-1) to (Y-4). There, ^{Z 1} and ^{Z 2} is a single bond or the following (Z-1) and (Z-3) ~ (Z -25) represents a group selected from (provided that at least one single of ^{Z 1} and ^{Z 2} N represents an integer of 2 to 100. The hydrogen atom of the anthraquinone ring in the formula is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or (It may be substituted with an optionally substituted heterocyclic group.)
(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atoms in the groups represented by (Y-1) to (Y-3) are a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, It may be substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ And R ⁵ represents an optionally substituted hydrocarbon group.)
Wherein X ³ represents S or NR ⁶ , X ⁴ represents S, NR ⁶ , CR ⁷ R ⁸ or SiR ⁷ R ⁸ , X ⁵ represents S, O or NR ⁶ , R ⁶ , R ⁷ and R ⁸ represent an optionally substituted hydrocarbon group, k represents an integer of 1 to 4, and is represented by (Z-1) and (Z-3) to (Z-25). The hydrogen atom in the unit is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a —NR ⁹ R ¹⁰ group, an optionally substituted hydrocarbon group or a substituted group. And may be substituted with an optionally substituted heterocyclic group, and R ⁹ and R ^{10 each} represents an optionally substituted hydrocarbon group.)   A p-type organic semiconductor material comprising at least one anthraquinone derivative according to any one of claims 1 to 3.   (A) A photoelectric conversion material comprising the p-type organic semiconductor material according to claim 4 and (B) an n-type organic semiconductor material.   A photoelectric conversion layer obtained by forming a film of the photoelectric conversion material according to claim 5.   A photoelectric conversion element comprising the photoelectric conversion layer according to claim 6. An anthraquinone derivative represented by the following general formula (4).
(In the formula, R ¹⁷ , R ¹⁸ , R ²⁰ , R ²¹ , R ²² and R ²⁴ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or a substituted group. An optionally substituted heterocyclic group, and R ¹⁹ and R ²³ are groups represented by —Y—R, or R ¹⁸ , R ¹⁹ , R ²¹ , R ²² , R ²³ and R ²⁴ are A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group is represented, and R ¹⁷ and R ²⁰ are represented by —Y—R. Is a group to be
X ¹ and X ² represent an oxygen atom or a sulfur atom,
Y represents each independently the group which combined 2-5 groups chosen from the following (Y-1)-(Y-4),
Each R independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. )
(In the formula, X ⁶ represents S, O or NR ^3, and the hydrogen atoms in the groups represented by (Y-1) to (Y-3) are a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, It may be substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a —NR ⁴ R ⁵ group, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and R ³ , R ⁴ And R ⁵ represents an optionally substituted hydrocarbon group.)