JP2020070289A - Fluorine-containing polycyclic aromatic compound and method for producing the same, and organic thin film transistor, solar cell, electrophotographic photoreceptor and method for producing organic light emitting element each of which uses the fluorine-containing polycyclic aromatic compound - Google Patents

Abstract

To provide novel fluorine-containing pentacene and naphthalocyanine compounds having various structural formulas and properties, and methods for producing them with ease and in high yield, and an organic thin film transistor, a solar cell, an electrophotographic photoreceptor and a method for producing an organic light emitting element each of which uses the novel compounds.SOLUTION: The present invention provides a fluorine-containing polycyclic aromatic compound in which at least one of aromatic groups at both terminals of a tricyclic or more conjugated polycyclic aromatic group is nuclear-substituted with a perfluoroalkyl group, and a production method characterized by using a reaction intermediate of the compound of the following formula [where X1-2, Y1-2, Z1-2 are specific groups].SELECTED DRAWING: Figure 1

Description

  INDUSTRIAL APPLICABILITY The present invention has a novel chemical structure as a fluorine-containing pentacene compound and a fluorine-containing naphthalocyanine compound, and is capable of improving various physical properties and properties, and a fluorine-containing polycyclic aromatic compound, and easily synthesized with a small number of steps. The present invention relates to a method for producing a fluorinated polycyclic aromatic compound that can be used, and a method for producing an organic thin film transistor, a solar cell, an electrophotographic photoreceptor and an organic light emitting device using the fluorinated polycyclic aromatic compound.

  Acene compounds such as naphthacene and pentacene, phthalocyanine compounds, aromatic polycyclic compounds such as naphthalocyanine compounds, organic thin film transistors, organic electroluminescence elements, organic electronic materials such as organic solar cells, display materials such as electrophotographic photoreceptors, or It can be used in a wide range of fields such as polymer functional materials, and application to various elements or devices is being studied in these fields.

  These polycyclic aromatic compounds can be given new functions and characteristics by introducing fluorine element into the molecule. For example, in Patent Documents 1 and 2, as an n-type organic semiconductor material, a fluorinated acene compound having high electron mobility (tetradecafluoropentacene, tetradecafluoronaphthacene, or the number of fluorine atoms to be introduced into a molecular skeleton) is disclosed. However, various types of pentacene) that are less than tetradecafluoropentacene have been proposed.

  Further, Patent Document 3 proposes pentacene in which a perfluoroalkyl group is introduced into the molecular skeleton in order to improve the solubility in a solvent. Non-Patent Document 1 also discloses a method for producing a perfluoroalkyl group-containing pentacene. Further, since the solubility of the pentacene compound in an organic solvent can be improved by substituting silylethynyl, a fluorinated silylethynylpentacene compound is disclosed as an example thereof (see, for example, Patent Document 4).

  On the other hand, a phthalocyanine compound or a naphthalocyanine compound has maximum absorbance in the near infrared region, and therefore is applied to a charge generation layer of an electrophotographic photoreceptor, a dye-sensitized solar cell, a light absorption filter or a heat ray shielding interlayer film. ing. Among them, Patent Documents 5 and 6 propose a fluorinated phthalocyanine compound that can be easily adjusted in an organic solvent or a fluorinated naphthalocyanine compound that has good solubility in an organic solvent or a resin. In Patent Document 6, as a reaction intermediate used when synthesizing a fluorinated naphthalocyanine compound, a naphthalene-2 having a fluorine atom or an aryl group nucleus-substituted with a fluorine atom or an alkyl group containing a fluorine atom, The use of 3-dicarbonitrile compounds is described.

  Non-Patent Document 2 discloses a method for producing a fluorinated phthalocyanine in which a plurality of trifluoromethyl groups are introduced into the skeleton.

JP, 2005-235923, A International Publication No. 2005/042445 International Publication No. 2014/115823 JP, 2005-7049, A Special table 2012-507743 gazette International Publication No. 2014/208484

Ogino et al. Bull. Chem. Soc. J. , Vol. 81, p. 530-535 Hanack et al. , Synth. Commun. , 1981, Vol. 11, p. 351-363

  Fluorine-containing pentacene compounds and fluorine-containing polycyclic aromatic compounds such as fluorine-containing phthalocyanine compounds and fluorine-containing naphthalocyanine compounds have excellent functions and characteristics as compared with fluorine-free polycyclic aromatic compounds, as described above. However, it is difficult to synthesize and manufacture, and the cost of the raw material is high. So far, several kinds of fluorine-containing polycyclic aromatic compounds have been proposed, but the kind and number of fluorine-containing substituents to be introduced are small, and in addition, the bonding position of the fluorine-containing substituent is a specific part of the skeleton structure. The material selection range is very narrow. Therefore, the characteristics and advantages originally possessed by the fluorine-containing polycyclic aromatic compound have not been fully utilized in the fields of organic electronic materials, display materials such as electrophotographic photoreceptors, or polymer functional materials.

  Therefore, by proposing a novel fluorine-containing polycyclic aromatic compound as a fluorine-containing pentacene compound, a fluorine-containing phthalocyanine compound, a fluorine-containing naphthalocyanine compound, etc., the material can be selected from a wide range and a new fluorine-containing polycyclic aromatic compound can be obtained. It is expected that the application to various fields including the field of organic electronics will be expanded if the synthesis of compounds is easy and the cost of materials can be reduced at the same time as the manufacturing process is simplified.

  However, the fluorine-containing pentacene compound, the fluorine-containing phthalocyanine compound, and the fluorine-containing naphthalocyanine compound disclosed in Patent Documents 1 to 6 and Non-Patent Documents 1 and 2 need to use (i) a special raw material. However, in some cases, the raw material may not be commercially available, and (ii) the synthesis is complicated and performed in multiple stages, and thus the production is difficult, and the synthesis is difficult and difficult to obtain. There is a problem that the kinds of compounds are limited. In addition, since the synthesis is performed in multiple steps, it is difficult to remove reaction by-products and impurities, and it is unavoidable that the yield of the synthesized product is significantly reduced.

  For example, in the method for synthesizing a fluorine-containing naphthalocyanine compound disclosed in Patent Document 6, a naphthalene-2,3-dicarbonitrile compound having a fluorine atom or a substituent containing a fluorine atom is used as a synthetic raw material. However, actually disclosed are only the compounds in which the substituent bonded to the carbon atom forming the naphthalene skeleton is a fluorine atom. This is because the synthesis of a naphthalene-2,3-dicarbonitrile compound containing fluorine is described in, for example, Russia Journal of General Chemistry, Vol 75, No. 5, 2005, p795-799, 2-methylbenzophenone is used as a starting material, and the halogenating agent and radical generator are used to pass through the three compounds. This is considered to be troublesome, and as a result, the kinds of naphthalene-2,3-dicarbonitrile compounds that can be synthesized are limited. As described above, in the synthesis method disclosed in Patent Document 6, the types of fluorine-containing naphthalocyanine compounds obtained are limited.

  Therefore, in order to increase the utility value of the fluorine-containing pentacene compound and the fluorine-containing naphthalocyanine compound and to expand the range of application thereof, the compounds are not limited to the compounds disclosed in Patent Documents 1 to 6 and Non-Patent Documents 1 and 2 above. Therefore, a novel fluorine-containing polycyclic aromatic compound in which a fluorine atom and various fluorine-containing substituents are introduced at a desired bonding position in the molecular skeleton of the fluorine-containing polycyclic aromatic compound is desired. There is also a demand for a manufacturing method for synthesizing a polycyclic aromatic compound easily and at low cost.

  The present invention has been made in view of the above-mentioned conventional problems, and in the synthesis of a fluorine-containing pentacene compound and a fluorine-containing naphthalocyanine compound, a well-known or well-known general-purpose synthesis without using a special raw material. By utilizing the method, a novel fluorine-containing polycyclic aromatic compound having various chemical structural formulas and properties, and a fluorine-containing polycyclic aromatic compound which can be easily synthesized with a small number of steps It is an object of the present invention to provide a manufacturing method and a method for manufacturing an organic thin film transistor, a solar cell, an electrophotographic photoreceptor and an organic light emitting device using the fluorine-containing polycyclic aromatic compound.

  The present invention, in the production of fluorine-containing pentacene and fluorine-containing naphthalocyanine, by using a special fluorine-containing monocyclic aromatic compound that has not been studied in conventional synthetic methods as a reaction intermediate, The present invention has been accomplished by finding that the above can be solved.

［式中、Ｍは２個の水素原子、２価の金属、又は３価若しくは４価の金属若しくは半金属の誘導体を示し、Ｘ_１及びＸ_２は、それぞれ独立にパーフルオロアルキル基であり、Ｘ_３及びＸ_４は、それぞれ独立に水素原子、フッ素原子、塩素原子、フッ素化若しくはパーフルオロ化されてもよいアルキル基、フッ素化されないアルキル基、又はフッ素化されないフェニル基である。Ｙ_１及びＹ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（１ａ）式で表される置換基、下記（１ｂ）式で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。Ｚ_１及びＺ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（１ａ）式で表される置換基、下記（１ｂ）で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に、水素、フッ素、塩素、フッ素化されていない直鎖状又は分岐状のアルキル基又はアルコキシ基、フッ素化又はパーフルオロ化されてもよい直鎖状又は分岐状のアルキル基又はアルコキシ基、フッ素化又はパーフルオロ化されてもよいアリール基である。］

［式中、Ａ_１、Ａ_２及びＡ_３は、アルキル基、フェニル基、又は含フッ素アルキル基である。］

［式中、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４及びＢ_５は、それぞれ独立に水素原子、フッ素原子、塩素原子、第３級アルキル基、含フッ素第３級アルキル基、パーフルオロアルキル基、アルコキシ基、アシル基、エステル置換基、アミド置換基、又はフェニル基である。］
［２］本発明は、前記［１］に記載の含フッ素多環芳香族化合物が、前記一般式（１）又は前記一般式（２）で表される化合物であり、且つ、前記Ｘ_１及びＸ_２が、それぞれ独立に、−ＣＦ_３、−Ｃ_４Ｆ_９、−Ｃ_６Ｆ_１３、−Ｃ_８Ｆ_１７、及び−Ｃ_１０Ｆ_２１の群から選ばれるいずれか１つのパーフルオロアルキル基であることを特徴とする含フッ素多環芳香族化合物を提供する。
［３］本発明は、前記［１］に記載の含フッ素多環芳香族化合物が、前記一般式（３）又は前記一般式（４）で表される化合物であり、且つ、前記Ｘ_１及びＸ_２が、それぞれ独立に、−ＣＦ_３、−Ｃ_４Ｆ_９、−Ｃ_６Ｆ_１３、−Ｃ_８Ｆ_１７、及び−Ｃ_１０Ｆ_２１のいずれかのパーフルオロアルキル基であり、前記Ｘ_３及びＸ_４が、それぞれ独立に、水素原子又は−ＣＦ_３、−Ｃ_４Ｆ_９、−Ｃ_６Ｆ_１３、−Ｃ_８Ｆ_１７、及び−Ｃ_１０Ｆ_２１の群から選ばれるいずれか１つのパーフルオロアルキル基であることを特徴とする含フッ素多環芳香族化合物を提供する。
［４］本発明は、含フッ素ペンタセン化合物及び含フッ素ナフタロシアニン化合物の合成において、反応中間体として下記（５）式で表される含フッ素単環芳香族化合物を使用することを特徴とする含フッ素多環芳香族化合物の製造方法を提供する。

［式中、Ｘ_１及びＸ_２は、それぞれ独立にフッ素原子又は含フッ素アルキル基であり、Ｙ_１及びＹ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（１ａ）式で表される置換基、下記（１ｂ）式で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。Ｚ_１及びＺ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（１ａ）式で表される置換基、下記（１ｂ）で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。］

［式中、Ａ_１、Ａ_２及びＡ_３は、アルキル基、フェニル基、又は含フッ素アルキル基である。］

［式中、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４及びＢ_５は、それぞれ独立に水素原子、フッ素原子、塩素原子、第３級アルキル基、含フッ素第３級アルキル基、パーフルオロアルキル基、アルコキシ基、アシル基、エステル置換基、アミド置換基、又はフェニル基である。］
［５］本発明は、前記Ｘ_１及びＸ_２が、それぞれ独立にフッ素原子又は含フッ素アルキル基であり、
前記Ｙ_１及びＹ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、パーフルオロアルキル基、前記Ａ_１、Ａ_２及びＡ_３がそれぞれ独立にアルキル基若しくはパーフルオロアルキルアルキル基である前記（５ａ）で表される置換基、又は前記Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４、及びＢ_５がそれぞれ独立に水素原子、フッ素原子、塩素原子、若しくはパーフルオロアルキル基である前記（５ｂ）で表されるフェニル基であり、
前記Ｚ_１及びＺ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、パーフルオロアルキル基、前記Ａ_１、Ａ_２及びＡ_３がそれぞれ独立にアルキル基、若しくはパーフルオロアルキルアルキル基である前記（５ａ）式で表される置換基、又は前記Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４、及びＢ_５がそれぞれ独立に水素原子、フッ素原子、塩素原子、若しくはパーフルオロアルキル基である前記（５ｂ）式で表されるフェニル基であることを特徴とする前記［４］に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［６］本発明は、前記含フッ素単環芳香族化合物が、下記（６）式又は式（７）で表される化合物を用いて、臭素（Ｂｒ）又はヨウ素（Ｉ）が核置換された位置に前記Ｘ_１及びＸ_２の置換基を導入することにより下記（８）式で表される化合物を合成する工程、及び下記（８）式で表される化合物のＷ_１及びＷ_２の置換基において単環芳香環と化学結合する炭素に結合する２つの水素原子を臭素化する工程、を有する合成方法によって製造されることを特徴する前記［４］又は［５］に記載の含フッ素多環芳香族化合物の製造方法を提供する。

［式中、Ｙ_１、Ｙ_２、Ｘ_１及びＸ_２は、前記と同じ置換基であり、Ｗ_１、Ｗ_２は、それぞれ独立にメチル基、又はメチル基の１つの水素原子が前記Ｚ_１，Ｚ_２で置換される基である。］
［７］本発明は、前記含フッ素単環芳香族化合物が、前記（６）式で示す化合物を用いて、臭素（Ｂｒ）が核置換された位置に前記Ｘ_１及びＸ_２の置換基を導入することにより前記（８）式に示す化合物を合成する工程、及び前記（８）式に示す化合物のＷ_１及びＷ_２の置換基において単環芳香環と化学結合する炭素に結合する２つの水素原子を臭素化する工程、を有する合成方法によって製造されることを特徴する前記［６］に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［８］本発明は、前記Ｘ_１及びＸ_２が、それぞれ独立にフッ素原子又はパーフルオロアルキル基であることを特徴とする前記［４］〜［７］のいずれか一項に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［９］本発明は、前記Ｙ_１及びＹ_２が、それぞれ独立に水素原子、フッ素原子又はパーフルオロアルキル基であることを特徴とする請求項８に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［１０］本発明は、前記Ｚ_１及びＺ_２が、水素原子であることを特徴とする前記［９］に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［１１］本発明は、前記含フッ素単環芳香族化合物と、フマロニトリル又はマレオニトリルとのディールス・アルダー環化付加反応を行い、引き続いて環化四量化又は環化三量化の反応を行うことで含フッ素ナフタロシアニン化合物を製造することを特徴とする前記［４］〜［１０］のいずれか一項に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［１２］本発明は、前記含フッ素単環芳香族化合物と、パラ−ベンゾキノンとのディールス・アルダー環化付加反応によって酸素原子が含まれる含フッ素多環芳香族化合物を合成する工程、及び前記酸素原子が含まれる含フッ素多環芳香族化合物をシリルエチニル化した後、還元することによって含フッ素シリルエチニルペンタセン化合物を合成する工程、を有することを特徴とする前記［４］〜［１０］のいずれか一項に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［１３］本発明は、前記含フッ素単環芳香族化合物と、パラ−ベンゾキノンとのディールス・アルダー環化付加反応によって酸素原子が含まれる含フッ素多環芳香族化合物を合成する工程、及び前記酸素原子が含まれる含フッ素多環芳香族化合物を還元することによって含フッ素ペンタセン化合物を合成する工程、を有することを特徴とする前記［４］〜［１０］のいずれか一項に記載の含フッ素多環芳香族化合物の製造方法を提供する。
［１４］本発明は、前記［１１］〜［１３］のいずれか一項に記載の製造方法によって製造される含フッ素多環芳香族化合物を、有機半導体材料として用いることを特徴とする有機薄膜トランジスタの製造方法を提供する。
［１５］本発明は、前記［１１］〜［１３］のいずれか一項に記載の製造方法によって製造される含フッ素多環芳香族化合物を、電子輸送層、陰極側バッファ層、又は中間電極に接するバッファ層に含まれる電子移動材料として用いることを特徴とする太陽電池の製造方法を提供する。
［１６］本発明は、前記［１１］に記載の製造方法によって製造される含フッ素多環芳香族化合物を、電荷発生層に含まれる電荷発生材料として用いることを特徴とする電子写真感光体の製造方法を提供する。
［１７］本発明は、前記［１１］に記載の製造方法によって製造される含フッ素多環芳香族化合物を、発光層に含まれる発光材料として用いることを特徴とする有機発光素子の製造方法を提供する。 That is, the constitution of the present invention is as follows.
[1] The present invention has a conjugated polycyclic aromatic group having 3 or more rings, and at least one of aromatic groups located at both ends of the conjugated polycyclic aromatic group is nuclear-substituted with a perfluoroalkyl group. A fluorine-containing polycyclic aromatic compound
Provided is a fluorine-containing polycyclic aromatic compound represented by any one of the following formula (1), the following formula (2), the following formula (3), and the following formula (4).

[In the formula, M represents two hydrogen atoms, a divalent metal, or a trivalent or tetravalent metal or metalloid derivative, and X ₁ and X ₂ are each independently a perfluoroalkyl group, X ₃ and X ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group which may be fluorinated or perfluorinated, an alkyl group which is not fluorinated, or a phenyl group which is not fluorinated. Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following formula (1b), a substituent or It is an unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following (1b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. R ₁ , R ₂ , and R ₃ are each independently hydrogen, fluorine, chlorine, a non-fluorinated linear or branched alkyl group or alkoxy group, or a linear chain which may be fluorinated or perfluorinated. A branched or branched alkyl group or alkoxy group, an aryl group which may be fluorinated or perfluorinated. ]

[In the formula, A ₁ , A ₂ and A ₃ are an alkyl group, a phenyl group or a fluorine-containing alkyl group. ]

[In the formula, B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, a perfluoroalkyl group. , An alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group. ]
[2] In the present invention, the fluorine-containing polycyclic aromatic compound according to [1] is a compound represented by the general formula (1) or the general formula (2), and X ₁ and X ₂ is each independently any one perfluoroalkyl group selected from the group of —CF ₃ , —C ₄ F ₉ , —C ₆ F ₁₃ , —C ₈ F ₁₇ , and —C ₁₀ F _21. There is provided a fluorine-containing polycyclic aromatic compound characterized by being present.
[3] In the present invention, the fluorine-containing polycyclic aromatic compound according to [1] is a compound represented by the general formula (3) or the general formula (4), and the X ₁ and X ₂ is, _{independently, -CF 3, -C 4 F 9} , -C 6 F 13, is any perfluoroalkyl group -C _{8 F 17,} and _-C 10 _{F 21,} the _{X 3} And X ₄ are each independently a hydrogen atom or any one selected from the group of —CF ₃ , —C ₄ F ₉ , —C ₆ F ₁₃ , —C ₈ F ₁₇ , and —C ₁₀ F _21. Provided is a fluorine-containing polycyclic aromatic compound which is a fluoroalkyl group.
[4] The present invention is characterized by using a fluorinated monocyclic aromatic compound represented by the following formula (5) as a reaction intermediate in the synthesis of a fluorinated pentacene compound and a fluorinated naphthalocyanine compound. Provided is a method for producing a fluorinated polyaromatic compound.

[In the formula, X ₁ and X ₂ are each independently a fluorine atom or a fluorine-containing alkyl group, and Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, A substituent represented by the formula 1a), a phenyl group represented by the following formula (1b), a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following (1b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. ]

[In the formula, A ₁ , A ₂ and A ₃ are an alkyl group, a phenyl group or a fluorine-containing alkyl group. ]

[In the formula, B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, a perfluoroalkyl group. , An alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group. ]
[5] In the present invention, X ₁ and X ₂ are each independently a fluorine atom or a fluorine-containing alkyl group,
The Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, and the A ₁ , A ₂ and A ₃ are each independently an alkyl group or a perfluoroalkylalkyl group. 5a), or the above (5b), wherein each of B ₁ , B ₂ , B ₃ , B ₄ and B ₅ is independently a hydrogen atom, a fluorine atom, a chlorine atom or a perfluoroalkyl group. Is a phenyl group represented by
Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, and A ₁ , A ₂ and A ₃ are each independently an alkyl group or a perfluoroalkylalkyl group. Or a substituent represented by the formula (5a), or B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group; 5b) A phenyl group represented by the formula, which is a method for producing the fluorinated polycyclic aromatic compound according to the above [4].
[6] In the present invention, the fluorine-containing monocyclic aromatic compound is a compound represented by the following formula (6) or formula (7), in which bromine (Br) or iodine (I) is nuclear-substituted. A step of synthesizing a compound represented by the following formula (8) by introducing the substituents of the above X ₁ and X _{2 into} the position, and substitution of W ₁ and W ₂ of the compound represented by the following formula (8) In the group [4] or [5] above, the fluorine-containing polysiloxane is produced by a synthetic method comprising the step of brominating two hydrogen atoms bonded to carbons chemically bonded to the monocyclic aromatic ring. A method for producing a ring aromatic compound is provided.

[In the formula, Y ₁ , Y ₂ , X ₁ and X ₂ are the same substituents as described above, and W ₁ and W ₂ are each independently a methyl group, or one hydrogen atom of a methyl group is Z ₁ , Z ₂ is a substituted group. ]
[7] In the present invention, the fluorine-containing monocyclic aromatic compound has the substituent of X ₁ and X ₂ at the position where the bromine (Br) is nuclear-substituted, using the compound represented by the formula (6). The step of synthesizing the compound represented by the formula (8) by introducing the compound, and the _two compounds bonded to the carbon chemically bonded to the monocyclic aromatic ring in the substituents of W ₁ and W ₂ of the compound represented by the formula (8) The method for producing a fluorine-containing polycyclic aromatic compound according to the above [6], which is produced by a synthetic method having a step of brominating a hydrogen atom.
[8] In the present invention, the X ₁ and X ₂ are each independently a fluorine atom or a perfluoroalkyl group, and the fluorine-containing compound according to any one of the above [4] to [7]. A method for producing a polycyclic aromatic compound is provided.
[9] In the present invention, the Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom or a perfluoroalkyl group, and the production of the fluorine-containing polycyclic aromatic compound according to claim 8. Provide a way.
[10] The present invention provides the method for producing a fluorinated polycyclic aromatic compound according to the above [9], wherein Z ₁ and Z ₂ are hydrogen atoms.
[11] In the present invention, the fluorine-containing monocyclic aromatic compound is subjected to a Diels-Alder cycloaddition reaction with fumaronitrile or maleonitrile, followed by cyclized tetramerization or cyclotrimerization reaction. A method for producing a fluorine-containing polycyclic aromatic compound according to any one of the above [4] to [10], which comprises producing a fluorine naphthalocyanine compound.
[12] The present invention comprises the step of synthesizing a fluorine-containing polycyclic aromatic compound containing an oxygen atom by a Diels-Alder cycloaddition reaction between the fluorine-containing monocyclic aromatic compound and para-benzoquinone, and the oxygen. Any of the above-mentioned [4] to [10], characterized in that it comprises a step of silylethynylating a fluorine-containing polycyclic aromatic compound containing atoms and then reducing it to synthesize a fluorine-containing silylethynylpentacene compound. A method for producing the fluorine-containing polycyclic aromatic compound according to any one of items 1 to 3.
[13] The present invention comprises the step of synthesizing a fluorine-containing polycyclic aromatic compound containing an oxygen atom by a Diels-Alder cycloaddition reaction between the fluorine-containing monocyclic aromatic compound and para-benzoquinone, and the oxygen. The step of synthesizing a fluorine-containing pentacene compound by reducing a fluorine-containing polycyclic aromatic compound containing atoms, the fluorine-containing article according to any one of [4] to [10] above. A method for producing a polycyclic aromatic compound is provided.
[14] The present invention uses the fluorine-containing polycyclic aromatic compound produced by the production method according to any one of [11] to [13] as an organic semiconductor material. A method of manufacturing the same is provided.
[15] In the invention, the fluorine-containing polycyclic aromatic compound produced by the production method according to any one of the above [11] to [13] is used as an electron transport layer, a cathode side buffer layer, or an intermediate electrode. There is provided a method for manufacturing a solar cell, which is used as an electron transfer material contained in a buffer layer in contact with.
[16] The present invention relates to an electrophotographic photosensitive member characterized by using the fluorinated polycyclic aromatic compound produced by the production method described in [11] above as a charge generating material contained in a charge generating layer. A manufacturing method is provided.
[17] The present invention provides a method for producing an organic light emitting device, which comprises using the fluorinated polycyclic aromatic compound produced by the production method described in [11] above as a light emitting material contained in a light emitting layer. provide.

  According to the present invention, as a fluorine-containing polycyclic aromatic compound such as fluorine-containing pentacene and fluorine-containing naphthalocyanine, a function not obtained by a conventional fluorine-containing polycyclic aromatic compound is imparted, or electron mobility is improved or heat resistance is improved. It is possible to provide a novel fluorine-containing polycyclic aromatic compound having improved physical properties and characteristics such as improved properties and durability. Further, according to the production method of the present invention, not only can the fluorine-containing polycyclic aromatic compound of the present invention be easily synthesized with a small number of steps, but also at a desired bonding position in the molecular skeleton, a fluorine atom and various Since a fluorine-containing substituent can be introduced, it becomes possible to synthesize a compound which has been difficult to synthesize by a conventional method for producing a fluorine-containing polycyclic aromatic compound.

  The fluorine-containing monocyclic aromatic compound used as the reaction intermediate in the production method of the present invention is not only available as a custom-made product but also can be easily synthesized from a commercially available raw material, and thus has high versatility and availability. It is a raw material. Therefore, it can be used as a high-purity raw material at low cost in the method for producing a fluorinated polycyclic aromatic compound according to the present invention, and as a result, contributes to cost reduction of the fluorinated polycyclic aromatic compound.

  Further, the fluorine-containing polycyclic aromatic compound obtained by the production method of the present invention has high solubility not only in ordinary organic solvents but also in fluorine-based (fluorous) solvents, and therefore organic electronic materials and display materials. Also, it becomes possible to perform film formation necessary for forming an element or device in the field of polymer functional materials by a wet process such as coating, spraying and contacting. In addition to the wet process, the film can be formed not only by the conventional vacuum evaporation method, MBE method, vapor phase transport growth method, or other dry process, but also expands the scope of application in device or device formation. Can be planned.

It is sectional drawing which shows the basic layer structure of the organic thin-film transistor manufactured by this invention. FIG. 1 is a cross-sectional view showing a basic layer structure of a laminated function separation type electrophotographic photosensitive member manufactured by the present invention.

  In the present specification, the pentacene compound refers to a skeleton in which 6 or more carbon 6-membered rings are condensed, and includes a silylethynylated pentacene compound. The fluorinated pentacene compound refers to a compound in which at least one carbon atom forming the pentacene skeleton is bonded to a fluorine atom, an alkyl group containing a fluorine atom, or a perfluoroalkyl group.

  Further, the naphthalocyanine compound means a triphenylnaphthalocyanine compound and a tetraphenylnaphthalocyanine compound, and the fluorine-containing naphthalocyanine compound means that at least one of the carbon atoms forming the naphthalene skeleton is a fluorine atom or an alkyl group containing a fluorine atom. , A compound bonded to a perfluoroalkyl group or a substituted or unsubstituted aryl group.

  The fluorine-containing polycyclic aromatic compound of the present invention is a fluorine-containing pentacene compound and a fluorine-containing naphthalocyanine compound having a conjugated polycyclic aromatic group having three or more rings, and is located at both ends of the conjugated polycyclic aromatic group. Is a fluorine-containing polycyclic aromatic compound in which at least one of the aromatic groups is substituted with a perfluoroalkyl group. Further, as represented by any one of the following formulas (1), (2), (3) and (4), aromatic groups located at both ends of the conjugated polycyclic aromatic group. At least one of them is nuclear-substituted with two or more perfluoroalkyl groups, and at least two perfluoroalkyl groups are bonded to the ortho position of the aromatic group.

  As the fluorine-containing pentacene compound and the fluorine-containing naphthalocyanine compound, those in which at least one of the conjugated polycyclic aromatic groups is substituted with one or more fluorine atoms or perfluoroalkyl groups are already known or known. Further, a compound in which at least one of aromatic groups located at both ends of the conjugated polycyclic aromatic group is substituted with one perfluoroalkyl group as a nucleus is also known (for example, see Non-Patent Document 1 above). reference).

  On the other hand, in the fluorine-containing polycyclic aromatic compound of the present invention, at least one of the aromatic groups located at both ends of the conjugated polycyclic aromatic group is in the ortho position by two or more perfluoroalkyl groups. It has a structure that is nuclear-replaced. With such a structure, it is possible to impart a function, which is not obtained with a conventional fluorine-containing polycyclic aromatic compound, or to improve electron mobility, heat resistance and durability. Further, since the solubility is high in a fluorine-based (fluorous) solvent, the film formation required when forming an element or device in the field of organic electronic materials, display materials and polymer functional materials is performed by a wet process. Will be able to. Further, the type of perfluoroalkyl group, the number of substitutions, and the substitution position can be easily changed by appropriately selecting the raw material (fluorine-containing monocyclic aromatic compound) according to the physical properties and characteristics. Therefore, there is an advantage that the selection range of materials is widened for applications such as organic electronic materials.

  Hereinafter, the fluorine-containing polycyclic aromatic compound of the present invention will be described in detail. The fluorine-containing polycyclic aromatic compound of the present invention is specifically a fluorine-containing polycyclic aromatic compound represented by any of the following formulas (1), (2), (3) and (4). It is a compound.

In the above formulas (1), (2), (3), and (4), M is a derivative of two hydrogen atoms, a divalent metal, or a trivalent or tetravalent metal or metalloid. X ₁ and X ₂ are each independently a perfluoroalkyl group, and X ₃ and X ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl which may be fluorinated or perfluorinated. A group, a non-fluorinated alkyl group, or a non-fluorinated phenyl group. Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following formula (1b), a substituent or It is an unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following (1b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. R ₁ , R ₂ , and R ₃ are each independently hydrogen, fluorine, chlorine, a non-fluorinated linear or branched alkyl group or alkoxy group, or a fluorinated or perfluorinated linear group. Or, it is a branched alkyl group or alkoxy group, or an aryl group which may be fluorinated or perfluorinated.

前記（１ａ）式中、Ａ_１、Ａ_２及びＡ_３は、アルキル基、フェニル基、又は含フッ素アルキル基である。

In the formula (1a), A ₁ , A ₂ and A ₃ are an alkyl group, a phenyl group or a fluorine-containing alkyl group.

前記（１ｂ）式中、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４及びＢ_５は、それぞれ独立に水素原子、フッ素原子、塩素原子、第３級アルキル基、含フッ素第３級アルキル基、パーフルオロアルキル基、アルコキシ基、アシル基、エステル置換基、アミド置換基、又はフェニル基である。

In the formula (1b), B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, or a It is a fluoroalkyl group, an alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group.

The fluorine-containing polycyclic aromatic compound of the present invention is a cyclized trimer of triphenylnaphthalocyanine represented by the general formula (1) or a ring of tetraphenylnaphthalocyanine represented by the general formula (2). In the case of a fluorine-containing naphthalocyanine compound composed of a quaternary tetramer, X ₁ and X ₂ are each independently —CF ₃ , —C ₄ F ₉ , —C ₆ F ₁₃ , or —C ₈ F. ₁₇ and any one perfluoroalkyl group selected from the group of —C ₁₀ F ₂₁ . Thereby, in any of the organic semiconductor material, the electron transfer material, the charge generation material, and the light emitting material, the electron mobility, the heat resistance and the durability are improved, and the film-forming property when performing the wet process due to the high solubility in the solvent. Can be improved.

When the fluorine-containing polycyclic aromatic compound of the present invention is the fluorine-containing silylethynylpentacene compound represented by the general formula (3) or the fluorine-containing pentacene compound represented by the general formula (4), X ₁ and X ₂ are each independently a perfluoroalkyl group of any of —CF ₃ , —C ₄ F ₉ , —C ₆ F ₁₃ , —C ₈ F ₁₇ , and —C ₁₀ F ₂₁ ; Any one of the above X ₃ and X ₄ independently selected from the group consisting of a hydrogen atom, —CF ₃ , —C ₄ F ₉ , —C ₆ F ₁₃ , —C ₈ F ₁₇ , and —C ₁₀ F ₂₁ . It is one perfluoroalkyl group. Thereby, in the organic semiconductor material or the electron transfer material, electron mobility, heat resistance and durability can be improved, and film-forming property can be improved when performing a wet process due to high solubility in a solvent.

<Method for producing fluorinated polycyclic aromatic compound>
The method for producing the fluorine-containing polycyclic aromatic compound according to the present invention will be described below.

  In the production method of the present invention, when a fluorine-containing pentacene compound and a fluorine-containing naphthalocyanine compound are produced as the fluorine-containing polycyclic aromatic compound, a fluorine-containing monocyclic aromatic compound represented by the following formula (5) is used as a reaction intermediate. Use as a body.

［式中、Ｘ_１及びＸ_２は、それぞれ独立にフッ素原子又は含フッ素アルキル基であり、Ｙ_１及びＹ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（５ａ）式で表される置換基、下記（５ｂ）式で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。Ｚ_１及びＺ_２は、それぞれ独立に水素原子、フッ素原子、塩素原子、含フッ素アルキル基、下記（５ａ）式で表される置換基、下記（５ｂ）で表されるフェニル基、置換若しくは無置換の縮合多環芳香族基、又は置換若しくは無置換の芳香族複素環基である。］

［式中、Ａ_１、Ａ_２及びＡ_３は、アルキル基、フェニル基、又は含フッ素アルキル基である。］

［式中、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４及びＢ_５は、それぞれ独立に水素原子、フッ素原子、塩素原子、第３級アルキル基、含フッ素第３級アルキル基、パーフルオロアルキル基、アルコキシ基、アシル基、エステル置換基、アミド置換基、又はフェニル基である。］

[In the formula, X ₁ and X ₂ are each independently a fluorine atom or a fluorine-containing alkyl group, and Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, A substituent represented by the formula 5a), a phenyl group represented by the formula (5b) below, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (5a), a phenyl group represented by the following (5b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. ]

[In the formula, A ₁ , A ₂ and A ₃ are an alkyl group, a phenyl group or a fluorine-containing alkyl group. ]

[In the formula, B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, a perfluoroalkyl group. , An alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group. ]

  In the fluorine-containing monocyclic aromatic compound represented by the above formula (5), two dibromoalkyl groups are bonded to the monocyclic aromatic ring at the ortho position. By debrominating this compound, an orthoquinodimethane intermediate is generated, followed by a Diels-Alder addition reaction with an alkene, and at the same time forming an aromatic ring by dehydrobromination, the fluorine-containing pentacene compound according to the present invention and A fluorinated naphthalocyanine compound can be produced.

<Method for producing fluorine-containing naphthalocyanine compound>
The fluorine-containing naphthalocyanine compound is basically produced according to the following synthetic scheme 1 using the fluorine-containing monocyclic aromatic compound represented by the above formula (5) and fumaronitrile or maleonitrile. Synthetic Scheme 1 below is a fluorine-containing tetraphenyl compound of the fluorine-containing naphthalocyanine compound represented by the above formula (1), wherein M is two hydrogen atoms and is synthesized by a cyclization tetramerization reaction. A naphthalocyanine compound or a fluorine-containing naphthalocyanine compound represented by the above formula (2), wherein M is a metal or boron (B) and is synthesized by a cyclization trimerization reaction, Is a synthesis example of each of the above.
<Scheme 1>

In the above Scheme 1, the Diels-Alder addition reaction is performed by reducing sodium iodide (NaI) or the like in a polar aprotic solvent such as dimethylformamide (DMF), dimethylacetamide (DMA) or dimethylsulfoxide (DMSO). The naphthalene-2,3-dicarbonitrile (or 2,3-dicyanonaphthalene) represented by the formula (9) of the above scheme 1 can be obtained by heating with an agent at a temperature of 50 ° C. or higher for a predetermined time. Can be synthesized. When using the obtained naphthalene-2,3-dicarbonitrile, for example, when carrying out a cyclization tetramerization reaction, sodium sulfate and (CH ₃ ) _{3 in} a polar aprotic solvent such as DMF, DMA or DMSO. By adding a silyl compound such as SiNHSi (CH ₃ ) ₃ and heating the mixture at a temperature of 100 ° C. or higher for a predetermined time, a fluorine-containing naphthalocyanine compound (a compound represented by the formula (10) in the above scheme 1) is obtained. It can be manufactured.

  In the fluorine-containing naphthalocyanine compound represented by the above formula (1), M is a metal containing 2 or 3 instead of the compound containing 2 water atoms (the compound represented by the above formula (10)). Even if it is a derivative of a valent or tetravalent metal, it can be produced by a known synthesis method (see the above-mentioned Patent Document 6 or Journal of the Crystallographic Society of Japan, Vol 54, 2012, p345-351). For example, a fluorine-containing naphthalene-2,3-dicarbonitrile synthesized by using the fluorine-containing monocyclic aromatic compound represented by the formula (5) in the above scheme 1 (represented by the formula (9) in the scheme 3) Compound) is reacted with a metal or a metal derivative to carry out a cyclization tetramerization reaction. Examples of the metal or metal derivative include metals such as Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Rd, In, Sn, Pt, Pb, and the like. Examples thereof include halogen compounds, carboxylic acid compounds, sulfates, nitrates, carbonyl compounds, oxides and complexes.

  Further, by using the fluorine-containing naphthalene-2,3-dicarbonitrile represented by the above-mentioned scheme 1 (9), it is represented by the following formula (12) according to the synthesis method disclosed in Patent Document 6 above. A fluorine-containing 1,3-diiminobenzoindolidone compound may be synthesized. The fluorinated 1,3-diiminobenzoindolidone compound thus synthesized is reacted with a metal or a metal derivative in the same manner as in the case of the fluorinated naphthalene-2,3-dicarbonitrile to cyclize. By carrying out the tetramerization reaction, a fluorine-containing naphthalocyanine compound represented by the above formula (1) in which M is a derivative of two metals or a trivalent or tetravalent metal can be produced. Here, examples of the M include Cu, Zn, Ni, Pd, Ti, and V.

  Further, in the above Scheme 1, for example, when a compound containing boron (B) is synthesized by a cyclization trimerization reaction as M, a non-polar carbonization containing boron trichloride is performed in a solvent such as dichlorobenzene. Fluorine-containing triphenylnaphthalocyanine compound containing boron by adding hydrogen solution (eg heptane solution) and heating at 100 ° C. or higher for a predetermined time (compound represented by formula (11) in the above scheme 1) Can be manufactured.

  As shown in the above scheme 1, by using the fluorine-containing monocyclic aromatic compound represented by the above formula (5) as a reaction intermediate, the Diels-Alder addition reaction and the cyclization tetramerization or cyclization are basically performed. A fluorinated naphthalocyanine compound can be produced by a small synthesis scheme of two steps by the trimerization reaction. Further, unlike the tetraphenylnaphthalocyanine containing fluorine disclosed in Patent Document 6, at least one of the carbon atoms forming the naphthalene skeleton is not only a fluorine atom, but an alkyl group containing a fluorine atom, a perfluoroalkyl group. Compounds that bind to can be prepared. In particular, in order to easily and at low cost obtain a compound that undergoes nuclear substitution with two perfluoroalkyl groups at the ortho position, it is preferable to carry out the synthesis according to Scheme 1 above. As a result, it is possible to provide a compound suitable not only for improving heat resistance and solubility in an organic solvent, a fluorine-based (fluorous) solvent or a resin, but also for improving characteristics such as electron mobility and imparting a new function. it can.

<Method for producing fluorine-containing silylethylpentacene compound>
The fluorinated silylethylpentacene compound is basically produced according to the following synthetic scheme 2 using the fluorinated monocyclic aromatic compound represented by the above formula (5) and para-benzoquinone.
<Scheme 2>

［式中、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に水素、フッ素、塩素、フッ素化されていない直鎖状又は分岐状のアルキル基又はアルコキシ基、フッ素化又はパーフルオロ化されてもよい直鎖状又は分岐状のアルキル基又はアルコキシ基、フッ素化又はパーフルオロ化されてもよいアリール基である。］

[In the formula, R ₁ , R ₂ , and R ₃ are each independently hydrogen, fluorine, chlorine, a non-fluorinated linear or branched alkyl group or alkoxy group, or fluorinated or perfluorinated. Good linear or branched alkyl or alkoxy groups, optionally fluorinated or perfluorinated aryl groups. ]

  In the above scheme 2, the silylethynylation reaction can be carried out, for example, according to the method disclosed in Patent Document 4 and Japanese Patent Publication No. 2010-520241. Specifically, alkynyllithium prepared from a silylacetylene compound is added to the corresponding pentacenequinone (a compound represented by the formula (13) in Scheme 2) to carry out a silylethynylation reaction, followed by hydrogen iodide (HI). ) And a fluorinated silylethynylpentacene compound (a compound represented by the formula (3) in Scheme 2) can be synthesized by a reduction reaction with a reducing agent such as) and tin (II) chloride.

  As shown in the above scheme 2, by using the fluorine-containing monocyclic aromatic compound represented by the above formula (5) as a reaction intermediate, the Diels-Alder addition reaction, silylethynylation reaction and reduction reaction are basically performed. The fluorine-containing silylethynylpentacene compound can be produced by a small number of three-step synthetic scheme. Further, in the fluorine-containing silylethylpentacene compound synthesized according to the above scheme 2, it is necessary to use a fluorinating agent such as sulfur tetrafluoride and / or hydrogen fluoride described in Patent Document 1 during the synthesis. Since it does not exist, it is a highly convenient manufacturing method in terms of safety.

  Furthermore, in the production method of the present invention, at least one of the carbon atoms forming the pentacene skeleton can be formed according to the same synthetic scheme by only changing the chemical structure of the fluorine-containing monocyclic aromatic compound represented by the above formula (5). A fluorine-containing pentacene compound bonded to a fluorine atom, an alkyl group containing a fluorine atom, or a perfluoroalkyl group can be easily produced. On the other hand, in the synthetic methods disclosed in Patent Documents 1 to 2 or Patent Document 3, since the raw materials used and the synthetic method are limited, the substituent bonded to the carbon atom forming the pentacene skeleton is a fluorine atom or perfluoro. Limited to either alkyl group. As described above, the production method of the present invention can provide fluorine-containing pentacene compounds having various chemical structures, and thus imparts a function or electron transfer which has not been obtained by conventional fluorine-containing polycyclic aromatic compounds. It is possible to improve physical properties or characteristics such as improvement of the heat resistance and heat resistance and durability.

<Method for producing fluorine-containing pentacene compound>
The fluorinated pentacene compound is basically produced according to the following synthesis scheme 3 using the fluorinated monocyclic aromatic compound represented by the above formula (5) and para-benzoquinone (1,4-benzoquinone).
<Scheme 3>

In the above Scheme 3, the Diels-Alder addition reaction is carried out by reducing potassium iodide (KI) in a polar aprotic solvent such as dimethylformamide (DMF), dimethylacetamide (DMA) or dimethylsulfoxide (DMSO). It can be carried out using an agent. In this Diels-Alder addition reaction, the formation of an aromatic ring by the dehydrobromination reaction of the fluorine-containing monocyclic aromatic compound represented by the above formula (5) proceeds at the same time. In the reduction reaction, sodium borohydride (NaBH ₄ ) or lithium aluminum hydride (LiAlH ₄ ) is allowed to act, and subsequently tin (II) chloride (SnCl ₂ ) or its hydrate, hydrogen iodide ( HI), and a reducing agent such as an organometallic complex.

  As shown in Scheme 3 above, the use of the fluorine-containing monocyclic aromatic compound represented by the above formula (5) as a reaction intermediate basically reduces the number of steps to two, Diels-Alder addition reaction and reduction reaction. A fluorine-containing pentacene compound (a compound represented by the formula (4) in the above scheme 3) can be produced by the synthetic scheme. Further, the fluorine-containing pentacene synthesized according to the above Scheme 3 is the same as the fluorine-containing silylethynylpentacene compound synthesized according to the above Scheme 2, and sulfur tetrafluoride and / or fluorinated as a fluorinating agent during the synthesis. Since it is not necessary to use hydrogen or the like, it is a highly convenient manufacturing method in terms of safety.

<Fluorine-containing monocyclic aromatic compound and method for synthesizing the same>
Next, the fluorine-containing monocyclic aromatic compound represented by the above formula (5) will be described with reference to specific examples.

In the fluorine-containing monocyclic aromatic compound represented by the above formula (5), X ₁ and X ₂ are independently a fluorine atom or a fluorine-containing alkyl group, and the fluorine-containing alkyl group is a fluorine atom. An alkyl group having 1 to 12 carbon atoms containing at least one or more is mentioned. The fluorine-containing alkyl group includes a perfluoroalkyl group.

In the present invention, in addition to imparting solubility to an organic solvent, a fluorine-based (fluorous) solvent, or a resin, improvement of physical properties or characteristics such as improvement of electron mobility and improvement of heat resistance and durability is aimed at. In order to obtain the effect of the present invention of providing the above-mentioned fluorine polycyclic aromatic compound, it is preferable that X ₁ and X ₂ are fluorine or a perfluoroalkyl group. Furthermore, as the perfluoroalkyl group, a linear perfluoroalkyl group having 1 to 12 carbon atoms is preferable, and a linear perfluoroalkyl group having 1 to 10 carbon atoms is used in order to suppress a decrease in intermolecular interaction due to steric hindrance. Groups are more preferred. Specific examples of the linear perfluoroalkyl group having 1 to 10 carbon atoms are, for example, —CF ₃ , —C ₄ F ₉ , and —C ₆ F ₁₃ from the viewpoint that the material can be synthesized and obtained relatively easily. _{, -C 8 F 17, -C 10} F 21 , and the like. In the present invention, when synthesizing any of the compounds represented by the above formulas (1) to (4), at least X ₁ and X ₂ each independently have 1 to 12 carbon atoms, preferably 1 carbon atom. A fluorine-containing monocyclic aromatic compound which is a linear perfluoroalkyl group of 10 to 10 is used.

Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the formula (5a), a phenyl group represented by the formula (5b), a substituent or It is an unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. As Y ₁ and Y ₂ , linear or branched substitution in which at least one hydrogen atom is bonded to carbon bonded to the benzene ring, such as —CH ₃ , —CH ₂ —, and —CH <. Groups are not preferred. This is because these substituents not only inhibit the step of synthesizing the compound (5) described above, but also inhibit the production of an orthoquinodimethane intermediate by debromination thereof.

In the substituent represented by the above formula (5a), A ₁ , A ₂ , and A ₃ are each independently an alkyl group, a phenyl group, or a fluorine-containing alkyl group. The substituted or unsubstituted condensed polycyclic aromatic group has, for example, at least one atom in at least one ring member of a ring structure forming a skeleton such as a naphthyl group, anthracenyl group and pyrenyl group. A monovalent substituent (for example, a halogen-containing alkyl group, a fluorine-containing alkyl group including a perfluoroalkyl group, etc.) is substituted with a nucleus. The substituted or unsubstituted aromatic heterocyclic group means that at least one ring member of a ring structure (for example, thiophene, pyridine, etc.) having at least one of O, N, S and Se in the ring structure is 1 A monovalent substituent having one or more atoms (for example, a halogen-containing alkyl group, a fluorine-containing alkyl group including a perfluoroalkyl group, etc.) is substituted with a nucleus.

In the present invention, in addition to imparting solubility to an organic solvent, a fluorine-based (fluorous) solvent, or a resin, improvement of physical properties or characteristics such as improvement of electron mobility and improvement of heat resistance and durability is aimed at. From the standpoint that it is possible to provide the above-mentioned fluorine polycyclic aromatic compound, and that the material is relatively easy to synthesize and obtain, the above Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom. An atom, a perfluoroalkyl group, a substituent represented by the above (5a) in which A ₁ , A ₂ and A ₃ are each independently an alkyl group or a perfluoroalkylalkyl group, or the above B ₁ , B ₂ , B _3, B _4, and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group in which the is a phenyl group represented by (5b) good Arbitrariness.

Further, it is more preferable that Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom or a perfluoroalkyl group. Since the fluorine-containing monocyclic aromatic compound in which Y ₁ and Y ₂ have these substituents is easy to synthesize and obtain the material, not only can the raw material cost be reduced as compared with other compounds, but also It is easy to obtain a high-purity product. It is particularly preferable that the above Y ₁ and Y ₂ have the same substituent because the raw materials are more easily available.

For the same reason, Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, or A ₁ , A ₂ and A ₃ are each independently an alkyl group or a perfluoroalkyl group. The substituent represented by the above (5a) which is an alkyl group, or the above B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group. The phenyl group represented by the above (5b) is preferable, and the same substituent is particularly preferable from the viewpoint of easy availability of raw materials.

Furthermore, it is more preferable that Z ₁ and Z ₂ are hydrogen atoms. The above-mentioned fluorine-containing monocyclic aromatic compound in which Z ₁ and Z ₂ are hydrogen is easy to synthesize and obtain, so that a high-purity compound is easily obtained, and the raw material cost is reduced as compared with other compounds. Can be planned.

<Synthesis Method of Fluorine-Containing Monocyclic Aromatic Compound>
The fluorine-containing monocyclic aromatic compound represented by the above formula (5) is used as a basic raw material in the synthesis steps of the above Schemes 1 to 3, but in the present invention, a compound synthesized from another commercially available raw material is used. May be used. For example, a monocyclic aromatic compound represented by the following formula (6) or (7) can be used as a commercially available raw material, and can be synthesized by the following synthesis scheme 4. The monocyclic aromatic compound represented by the following formula (6) or (7) is a compound having a chemical structure in which two bromine (Br) or two iodine (I) are nuclear-substituted at the ortho position.
<Scheme 4>

As shown in Synthesis Scheme 4, the fluorine-containing monocyclic aromatic compound represented by the above formula (1) is the same as that of the monocyclic aromatic compound represented by the above formula (6) or (7). A step of synthesizing a compound represented by the above formula (8) by introducing the substituents of X ₁ and X ₂ at a position where Br) or iodine (I) is nuclear-substituted, and the above formula (8) And a step of brominating two hydrogen atoms bonded to carbons chemically bonded to the monocyclic aromatic ring in the substituents of W ₁ and W ₂ of the compound represented by.

When a perfluoro group (hereinafter, abbreviated as Rf-) is introduced as X ₁ and X ₂ in the above Scheme 4, for example, in the presence of copper powder in a polar aprotic solvent, the above formula (6) or It can be introduced by reacting the compound represented by the formula (7) with a compound such as Rf-I or Rf-Br. When introducing a fluorine atom as X ₁ and X ₂ , a compound represented by the above formula (6) or (7) is obtained by using a fluorinating agent such as sulfur tetrafluoride and / or hydrogen fluoride. May be fluorinated.

  Among the compounds represented by the above formulas (6) and (7), in the present invention, the compound represented by the above formula (8) is easily synthesized, and a high-purity raw material is easily available. It is preferable to use the compound represented by the above formula (6).

In Scheme 4, the bromination of W ₁ and W 2 can be performed, for example, by a compound such as N-bromosuccinimide (NBS) generally used as a bromine source in radical substitution and electrophilic addition reaction, and benzoyl peroxide (BPO). ) Or the like by reacting it with a peroxide to utilize the radical reaction mechanism. Here, after the reaction is carried out in the presence of a solvent in which only the reaction by-product produced by the bromination reaction is insoluble, such as carbon tetrachloride, the compound represented by the above formula (5) is obtained by a filtration fractionation method or the like. The isolation of

Representative examples of the fluorine-containing monocyclic aromatic compound represented by the above formula (5) are shown below, but the present invention is not limited to these compounds. In the compounds represented by the following (5-1) ~ (5-12), (F) Rf is a fluorine atom, or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C 8 F 17, And -C ₁₀ F ₂₁ each represent a perfluoroalkyl group, and C _{1 to} C ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group.

Further, the compounds represented by the above formulas (6), (7), and (8) used as raw materials for synthesizing the fluorine-containing monocyclic aromatic compound represented by the above formula (5) In the representative examples, W ₁ and W ₂ represented by the substituents are —CH ₃ , —C (F) H ₂ , —, corresponding to the compounds shown in [5-1] to [5-12] above. _{C (Rf) H 2, C} 1 ~C aryl group having ₅ to _{substituent, -C [C (CH 3)} 3] H 2, a -C (Cl) _{H 2.} Here, Rf is _{-CF 3, -C 4 F 9,} -C 6 F 13, -C 8 F 17, a perfluoroalkyl group having _-C 10 _{F 21.}

<Typical examples of fluorine-containing polycyclic aromatic compounds>
Next, typical examples of the fluorine-containing polycyclic aromatic compound produced by using the fluorine-containing monocyclic aromatic compound represented by the above formula (5) are shown below, but the present invention is not limited to these compounds. Not something.

First, typical examples of the fluorine-containing tetraphenylnaphthalocyanine compound represented by the above formula (1) produced according to the above scheme 1 are shown below. In the compound represented by [1-1] - [1-9] below, (F) Rf is a fluorine atom, or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C 8 F 17, And -C ₁₀ F ₂₁ each represent a perfluoroalkyl group, and C _{1 to} C ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group.

Further, in the structure of the fluorine-containing tetraphenylnaphthalocyanine compound represented by the above formula (1), a divalent, trivalent or tetravalent metal is bound as M in place of the hydrogen atom (H) which is bonded to nitrogen. Representative examples of such compounds are shown below. In the compound represented by [1-10] ~ [1-18] below, (F) Rf each independently represent a fluorine atom, or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C ₈ F ₁₇ and —C ₁₀ F ₂₁ each represent a perfluoroalkyl group, and C _{1 to} C ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group.

Further, typical examples of the fluorine-containing triphenylnaphthalocyanine compound represented by the above formula (2) are shown below. In the compound represented by [2-1] - [2-9] below, (F) Rf each independently represent a fluorine atom, or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C ₈ F _17, and indicates one of the perfluoroalkyl group _{-C 10 F 21, C 1 ~C} 5 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group.

  Furthermore, in the structure of the fluorine-containing triphenylnaphthalocyanine compound represented by the above formula (2), a hydrogen atom (H) bonded to nitrogen is replaced with a divalent, trivalent or tetravalent metal as M, or Representative examples of compounds to which tetravalent boron and the like are bound are shown below. In the case of a tetravalent element, it binds to another ligand (for example, halogen) in addition to the three nitrogens contained in the triphenylnaphthalocyanine compound, but in the representative example below, another ligand is used. Is omitted.

Next, typical examples of the fluorine-containing silylethynylpentacene compound represented by the above formula (3) produced according to the above scheme 2 are shown below. In the compound represented by [3-1] - [3-11] below, (F) Rf each independently represent a fluorine atom or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C 8 F _17, and indicates one of the perfluoroalkyl group _{-C 10 F 21, Rf (H} , F) are each _{independently, -CF 3, -C 4 F 9} , -C 6 F 13, -C ₈ F ₁₇ and a perfluoroalkyl group of —C ₁₀ F ₂₁ or a water atom or a fluorine atom. _Also, C 1 -C ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group. Further, R bonded to Si represents an alkyl group having 1 to 10 carbon atoms.

Next, typical examples of the fluorine-containing pentacene compound represented by the above formula (4) produced according to the above scheme 3 are shown below. In the compound represented by [4-1] - [4-12] below, Rf (F) are each independently a fluorine atom or _{-CF 3, -C 4 F 9,} -C 6 F 13, -C 8 F _17, and indicates one of the perfluoroalkyl group _{-C 10 F 21, Rf (H} , F) are each _{independently, -CF 3, -C 4 F 9} , -C 6 F 13, -C ₈ F ₁₇ and a perfluoroalkyl group of —C ₁₀ F ₂₁ or a water atom or a fluorine atom. . Further, C _{1 to} C ₅ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom or an alkyl group.

<Method for manufacturing organic thin film transistor>
The fluorine-containing polycyclic aromatic compound represented by the above formulas (1), (2), (3), and (4) produced by the present invention is used in an organic semiconductor layer constituting an organic thin film transistor. It can be used as an included organic semiconductor material. Therefore, a method of manufacturing the organic thin film transistor according to the present invention will be described.

  FIG. 1 is a sectional view showing a basic layer structure of an organic thin film transistor manufactured by the present invention. FIG. 1A shows a top-contact type organic thin film transistor, which has a substrate 1, a gate electrode 2, a gate insulating film 3, a source electrode 4, a drain electrode 5, and an organic semiconductor layer 6, and is on the organic semiconductor layer 6. In this structure, the source electrode 4 and the drain electrode 5 are arranged in the. FIG. 1B shows a bottom-contact type organic thin-film transistor, which has the same layer structure as the top-contact type, but is different in that the source electrode 4 and the drain electrode 5 are arranged under the organic semiconductor layer 6. Each of them has a structure of metal substrate-insulator-semiconductor, and the channel length and the channel width of the organic semiconductor are determined by the size of the gap between the source electrode 4 and the drain electrode 5 which are in contact with the organic semiconductor layer 6. Be done.

  In the organic thin film transistor shown in FIG. 1, carriers move through the channel in the organic semiconductor layer 6 formed between the source electrode 4 and the drain electrode 5. Here, by adjusting the voltage applied to the gate electrode 2, the movement of carriers through the channel formed in the organic semiconductor layer 6 can be controlled. In the organic thin-film transistor according to the present invention, the organic semiconductor layer contains any of the fluorine-containing polycyclic aromatic compounds represented by the above formulas (1), (2), (3), and (4). Therefore, the carriers moving in the organic semiconductor layer 6 are electrons, and the flow of electrons (current) moving in the organic semiconductor layer 6 is controlled by applying a positive voltage to the gate electrode. That is, the organic thin film transistor according to the present invention is an n-type organic thin film transistor.

  The general manufacturing method of the top contact type organic thin film transistor shown in FIG. 1A is that the gate electrode 2, the gate insulating film 3, the above formulas (1), (2), (3), and The organic semiconductor layer 6 containing any of the fluorine-containing polycyclic aromatic compounds represented by the formula (4), and the thin films of the source electrode 4 and the drain electrode 5 are sequentially laminated. On the other hand, in the general method for manufacturing the bottom contact type organic thin film transistor shown in FIG. 1B, the gate electrode 2 and the gate insulating film 3 are laminated on the substrate 1, and then the source electrode 4 and the drain electrode 5 are formed by a photo process. An organic semiconductor containing any of the fluorine-containing polycyclic aromatic compounds represented by the above formulas (1), (2), (3), and (4) after the thin film is formed by precision processing. By stacking the thin films of layer 6, an organic thin film transistor can be obtained.

  As the material of the substrate 1, inorganic materials such as glass, quartz, silicon, metals and ceramics, and organic materials such as plastics can be used. Here, when a conductive substance such as a metal is used as the material of the substrate 1, the substrate 1 also functions as a gate electrode, and thus another gate electrode having a function as the gate electrode 2 is formed on the substrate 1. Can be omitted. The organic thin film transistor according to the present invention is represented by the gate electrode 2, the gate insulating film 3, the source electrode 4, the drain electrode 5, and the above formulas (1), (2), (3), and (4). It is a MIS (metal-insulator-semiconductor) type thin film transistor including an organic semiconductor layer 6 containing any one of fluorine-containing polycyclic aromatic compounds. Since such a MIS type thin film transistor exhibits excellent characteristics of an n type organic thin film transistor and does not require a separate substrate, it can be easily manufactured at low cost. Further, when a plastic substrate is used as the material of the substrate 1, the entire organic thin film transistor including the plastic substrate has flexibility. Therefore, the organic thin film transistor according to the present invention can be used for driving circuits of flexible displays, ICs such as credit cards and the like. It can be used for various organic thin film devices such as cards and ID tags attached to products. However, the plastic material used for the plastic substrate is required to have excellent heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability and low moisture absorption. Examples of such plastic materials include polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyarylate, and polyimide.

  Examples of the material of the gate electrode 2 include metals such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, and calcium, and alloys thereof, and polysilicon, amorphous silicon, graphite, tin oxide. Examples include indium (ITO), zinc oxide, and conductive polymers. The gate electrode 2 is formed using the material of the gate electrode 2 by a known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, and a printing method.

Examples of the material of the gate insulating film 3 include SiO ₂ , Si ₃ N, SiON, Al ₂ O ₃ , Ta ₂ O ₅ , amorphous silicon, polyimide resin, polyvinylphenol resin, polyparaxylylene resin, and polymethylmethacrylate resin. The materials are listed. The gate insulating film 3 is formed by a known film forming method similar to that for the gate electrode 2 using one kind of material selected from the above materials, or two or more kinds selected from the above materials. The materials are mixed and formed by a known film forming method similar to that of the gate electrode 2.

  Examples of materials for the source electrode 4 and the drain electrode 5 include metals such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium, and calcium, alloys of these metals, and polysilicon and amorphous silicon. Materials include graphite, indium tin oxide, zinc oxide, and conductive polymers. The source electrode 4 and the drain electrode 5 are formed using the materials of the source electrode 4 and the drain electrode 5 (preferably simultaneously) by the same well-known film forming method as the gate electrode 2.

  The organic semiconductor layer (organic active layer) 6 uses any of the fluorine-containing polycyclic aromatic compounds represented by the above formulas (1), (2), (3), and (4). It is formed by a well-known or publicly known film forming method by a dry process such as a vacuum deposition method or an MBE method, or a wet process such as a printing method using a solution obtained by dissolving in an organic solvent or a fluorine-based solvent. In the present invention, since the wet process can be adopted, the manufacturing cost of the organic thin film transistor can be reduced.

  Furthermore, in order to improve the reliability and durability of the organic thin film transistor, a moisture permeation preventive layer (gas barrier) is formed on the surface of the substrate 1 on the same side as the gate electrode 2, the surface of the substrate 1 on the opposite side of the gate electrode 2, or both. Layer) is preferably provided. Further, by providing the substrate 1 with the moisture permeation preventive layer, it is possible to prevent moisture and / or oxygen in the air from entering the organic semiconductor layer. As a result, it is possible to prevent the life of the organic semiconductor layer from being sharply reduced. As a material for such a moisture permeation preventive layer, an inorganic or organic material can be used, but from the viewpoint of improving reliability and durability, it is preferable to use an inorganic material such as silicon nitride and silicon oxide. preferable. The moisture permeation preventive layer is formed by a known method such as a high frequency sputtering method.

  In the organic thin film transistor according to the present invention, the substrate 1 may be provided with a protective layer such as an organic or inorganic hard coat layer and an undercoat layer, if necessary.

<Method of manufacturing solar cell>
The fluorine-containing naphthalocyanine compounds represented by the above formulas (1) and (2), and the pentacene compounds represented by the formulas (3) and (4), which are produced by the present invention, constitute a solar cell. It can be applied as a material used for the layer. Therefore, a method for manufacturing a solar cell according to the present invention will be described.

The solar cell of the present invention has a structure in which organic thin films are laminated, and is not particularly limited as long as it has a structure including an organic layer corresponding to each function between a pair of electrodes. Specifically, a structure having the following element structure on a stable insulating substrate can be mentioned.
(1-1) Lower electrode / active layer (p layer) / active layer (n layer) / upper electrode (1-2) Lower electrode / buffer layer / active layer (p layer) / active layer (n layer) / upper Electrode (1-3) lower electrode / active layer (p layer) / active layer (n layer) / buffer layer / upper electrode (1-4) lower electrode / buffer layer / active layer (p layer) / active layer (n Layer) / buffer layer / upper electrode (1-5) lower electrode / buffer layer / active layer (p layer) / active layer (i layer or a mixing tank of p material and n material) / active layer (n layer) / buffer Layer / upper electrode (1-6) lower electrode / active layer (p layer) / active layer (n layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / active layer (n layer) / buffer Layer / upper electrode (1-7) lower electrode / buffer layer / active layer (p layer) / active layer (n layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / Layer (n layer) / buffer layer / upper electrode (1-8) lower electrode / buffer layer / active layer (p layer) / active layer (i layer, mixing tank of p material and n material) / active layer (n Layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / active layer (mixing tank of i layer or p material and n material) / active layer (n layer) / buffer layer / upper electrode

  Among the above device configurations, the buffer layer of the device configurations (1-2) to (1-8), particularly the buffer layer in contact with the cathode side buffer layer and / or the intermediate electrode, is manufactured according to the present invention (1). It is preferable to use any of the fluorine-containing polycyclic aromatic compounds represented by the formula, (2) formula, (3) formula, and (4) formula, and the device constitutions (1-3) to (1-8) It is more preferable to use the fluorinated polycyclic aromatic compound according to the present invention for the buffer layer, especially for the cathode side buffer layer and / or the buffer layer in contact with the intermediate electrode. Hereinafter, each component will be briefly described.

  The material of the lower electrode and the upper electrode is not particularly limited, and a known conductive material can be used. For example, a metal such as tin-doped indium oxide (ITO), gold (Au), osmium (Os), or palladium (Pd) can be used as the electrode connected to the active layer (p layer), and the active layer (n layer) is used. As an electrode to be connected with, a metal such as silver (Ag), aluminum (Al), indium (In), calcium (Ca), platinum (Pt), lithium (Li), or a binary metal system composed of these metals is used. Can be used. A metal having a high work function is preferable for the electrode connected to the p layer, and a metal or a metal-based material having a low work function is preferable for the electrode connected to the n layer. At least one surface of the organic solar cell is desirably sufficiently transparent, and the electrode formed on the transparent surface is formed by a method such as vapor deposition or sputtering so that a desired transparency can be secured.

The material used as the n-layer in the active layer is not particularly limited, but a compound having a function as an electron acceptor is preferable, and examples thereof include fullerene compounds such as C ₆₀ , carbon nanotubes, perylene compounds, polycyclic quinones and quinacridones. In the polymer system, C-poly (phenylene-vinylene), MEH-CN-PPV, a polymer containing a cyano group or a perfluoromethyl group, and a poly (fluorene) compound can be mentioned. In the case of an inorganic compound, an n-type inorganic semiconductor compound can be used. For example, doping semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CDSe, InP, Nb ₂ O ₅ , WO ₃ and Fe ₂ O ₃ , titanium dioxide (TiO ₂ ) and titanium monoxide (TiO ₂ ). ), Titanium oxides such as dititanium trioxide (Ti ₂ O ₃ ), conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO ₂ ), and one or more of them may be combined. Can be used.

  The electron donating material used as the p-layer of the active layer is not particularly limited, but it is necessary to exhibit an electron donating property, and a compound having a function as a hole acceptor is preferable. For example, N, N'-bis (3-tolyl) -N, N'-diphenylbenzidine (mTPD), N, N'-dinaphthyl-N, N'-diphenylbenzidine (NPD) and 4,4 ', 4'. Representative amine compounds such as'-tris (phenyl-3-tolylamino) triphanylamine (MTDATA), phthalocyanines such as phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc) and titanyl phthalocyanine (TiOPc). , Octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP) and the like, polyhexylthiophene (P3H) and methoxyethylhexyloxyphenylene vinylene (MEHPPV) and the like. Chain conjugated polymers such, as well as side chain type polymers such as represented by polyvinyl carbazole, and the like.

  The i-layer of the active layer may contain a material having properties intermediate between the electron-accepting material (n material) and the electron-donating material (p-material), or may contain an electron-accepting material and an electron-donating material. It may be a mixed layer containing and mixing.

The buffer layer, the upper electrode and the lower electrode of the organic thin-film solar cell is short-circuited, and is used by being stacked in order to prevent a decrease in the yield of cell production, and since the organic thin-film solar cell has a small total thickness, This is a particularly useful layer structure. The fluorine-containing naphthalocyanine compounds represented by the above formulas (1) and (2) and the fluorine-containing pentacene compounds represented by the above formulas (3) and (4) produced by the present invention are Since it has high transportability and a small energy barrier with the electrode, it is preferably used for the buffer layer, particularly for the cathode side. Besides, it can be used for a buffer layer in contact with the intermediate electrode. The fluorine-containing naphthalocyanine compound or the fluorine-containing pentacene compound according to the present invention may be used alone as a buffer layer for these, or may be used as a mixture with a known compound. Further, the layer structure of the same organic solar cell can be obtained by using the buffer layer containing the fluorine-containing naphthalocyanine compound or the fluorine-containing pentacene compound produced by the present invention and the buffer layer containing the known compound in combination. Known compounds include low molecular weight aromatic cyclic anhydrides, conductive polymers such as poly (3,4-ethylenedioxy) thiophene: polystyrenesulfonate and polyaniline: camphorsulfonic acid, and inorganic semiconductor compounds such as CdTe. , P-Si, SiC, GaAs, NiO ₂ , WO 3 and V ₂ O _{5 and the} like.

  The intermediate electrode is one of the layer structures adopted for separating the individual photoelectric conversion units of the stacked device by forming the electron-hole recombination zone. This layer serves to prevent the formation of an inverse heterojunction between the n-layer of the front photoelectric conversion unit (front cell) and the p-layer of the rear photoelectric conversion unit (back cell). The layer forming the intermediate electrode is made of any metal selected from Ag, Li, LiF, Al, Ti and Sn, and is usually formed with a thickness of 20 Å or less.

  Each layer constituting the solar cell of the present invention is generally formed by stacking on a substrate. The substrate used in the solar cell of the present invention preferably has high mechanical strength, heat resistance, and transparency. Examples of the substrate include a glass substrate and a transparent resin film.

  The formation of each layer constituting the solar cell of the present invention can be carried out by a known method adopted in the production of a known organic solar cell, for example, dry film formation such as vacuum deposition, sputtering, plasma and ion plating. Methods and wet film forming methods such as spin coating, dip coating, casting, roll coating, flow coating and inkjet can be applied. The fluorine-containing naphthalocyanine compounds represented by the above formulas (1) and (2), and the fluorine-containing pentacene compounds represented by the above formulas (3) and (4) produced by the present invention are in solution. When forming a buffer layer and the like by using a wet film formation method by coating, better film formation than before can be obtained, so that workability is improved especially when manufacturing a device with high definition and large area. Also, it is very effective in reducing the manufacturing cost.

  The film thickness of each layer is not particularly limited, but each layer is formed by adjusting the film thickness to an appropriate value. If the film thickness is too thick, the photoelectric conversion efficiency is lowered, and if it is too thin, pinholes and the like are observed and the desired function cannot be exhibited. The usual film thickness is adjusted in the range of 1 nm to 10 μm, but the range of 5 nm to 1 μm is particularly preferable.

  The solar cell obtained by the production method of the present invention is a resin or an oxide as necessary in order to improve the film-forming property in the organic thin film layer, prevent the occurrence of pinholes in the film, and increase the heat resistance and durability. Additives such as inhibitors, UV absorbers and plasticizers may be used.

<Method for manufacturing electrophotographic photoreceptor>
The fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) can be used as the charge generating material contained in the charge generating layer of the electrophotographic photoreceptor. Therefore, a method for manufacturing the electrophotographic photosensitive member according to the present invention will be described below.

  As the electrophotographic photosensitive member, many organic photosensitive members (OPC) using an organic photoconductive material have been studied from the viewpoints of low toxicity, wide selection of wavelength range, and cost reduction, and in recent years, Higher functionality and reliability such as printing durability, high-speed response, high gradation, and environmental resistance have been further advanced. OPCs are roughly classified into a negatively chargeable laminated function separation type and a positively chargeable single layer separation type. The layer structure is shown in FIG.

  As shown in FIG. 2, the stacked function separation type OPC has a conductive base 7, an undercoat layer 8, a charge generation layer 9, and a charge transport layer 10 as a basic layer structure. Further, there is a case where a PCT in which the charge generation layer 9 is provided directly on the conductive substrate 7 without forming the undercoat layer 8 is manufactured. The function of the negatively-charged stacked function separation type OPC is as described below.

  In the multi-layer photosensitive member that is negatively charged in the dark, light is absorbed by the charge generating material contained in the charge generating layer 9, and hole and electron charge carriers are generated. The generated electrons are injected into the electrode of the conductive substrate 7, which is an electrode, and the holes are injected into the charge transport layer 10. The holes move in the charge transport layer 10 and partially neutralize the surface charges on the negatively charged photoreceptor, so that the other portions remain in the negatively charged state. For example, a negatively charged toner is attached to the neutralized portion, or a positively charged toner is attached to the negatively charged portion to print an image, and further, fixing is performed by heating or light to obtain a desired image. It is formed. The electrophotographic photoreceptor according to the present invention can be manufactured by using the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) as the charge generating material contained in the charge generating layer 9.

  The method for forming the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) as the charge generation layer 9 in the present invention is (i) using the fluorine-containing naphthalocyanine compound in an organic solvent. After dissolving or dispersing, a method of coating and drying on the conductive substrate 7 or the undercoat layer 8 to form a film, (ii) Dispersing or dissolving the fluorine-containing naphthalocyanine compound and the resin binder in an organic solvent, and then conducting. Method of forming a film by coating and drying on the organic substrate 7 or the undercoat layer 8, or (iii) an organic solvent in which the fluorine-containing naphthalocyanine compound, a resin binder, and another organic photoconductive substance are added as minor components And the like, and then coating and drying on the conductive substrate 7 or the undercoat layer 8. The fluorine-containing naphthalocyanine compound is combined with another charge generating material such as an azo pigment, a perylene pigment, an anthrone pigment, a metal-free phthalocyanine pigment, and a phthalocyanine pigment containing a metal such as Al, In, V, Mg or Ti. You may use it together.

  Examples of the resin binder used at this time include polyvinyl alcohol, polyarylate, polycarbonate, polyamide, polyurethane, polyester, polyvinyl acetate, ethyl cellulose and the like, and one or more of these can be used.

  An aluminum-based substrate is generally used as the conductive substrate 7 in the present invention. Examples of the aluminum-based substrate include an aluminum plate, an aluminum cylinder, an aluminum foil, and a plastic film on which a thin film or foil of a conductive metal such as aluminum is provided.

  The undercoat layer 8 is provided when improvement in blocking property of OPC and higher environmental stability are required, and, for example, the resin exemplified as the resin binder is used as the undercoat layer depending on the characteristics. be able to.

  Examples of the charge transport material used to form the charge transport layer 10 include poly-N-vinylcarbazole, polyvinylanthracene, carbazoles, fluorenes, hydrazones, triazoles, arylamines, quinones, oxazoles, and polysilanes. However, the present invention is not limited to these compounds. These compounds can be used alone or in combination of two or more. In the present invention, the charge transport layer 10 can be formed by the same method as the method for forming the charge generation layer 9 described above, and a resin binder, an organic solvent and the like can be appropriately selected and used.

<Method of manufacturing organic light emitting device>
Further, the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) can be applied as a light emitting material contained in a light emitting layer of an organic light emitting device. Therefore, a method for manufacturing an organic light emitting device according to the present invention will be described below.

  The organic light emitting device is a device in which a single layer or a multilayer organic thin film is laminated between an anode and a cathode. In the case of a single organic light emitting device, a light emitting layer is provided between an anode and a cathode, and the light emitting layer contains a light emitting material, and further, a light emitting material, holes injected from the anode or electrons injected from the cathode are emitted as the light emitting material. A hole transport material or an electron transport material is contained for the purpose of transporting to. The light-emitting element used here has a single material having at least one of hole transporting ability and electron transporting ability in addition to the light emitting ability, or is used as a mixture of compounds having respective properties. Useful for. The fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) produced by the present invention is used as a light emitting material having an electron transporting property, or as an electron transporting material contained together with the light emitting material in a light emitting layer. used.

Examples of the multilayer organic light emitting device include a structure in which the following multilayer structure is laminated on a substrate.
(2-1) Anode / hole transport layer / light emitting layer / cathode (2-2) Anode / light emitting layer / electron transport layer / cathode (2-3) Anode / hole transport layer / light emitting layer / electron transport layer / Cathode (2-4) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (2-5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (2-6) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  Further, not limited to the above configuration, a layer in which a hole transport layer component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided as necessary. Further, between the electron transport layer and the light emitting layer, to a layer (hole blocking layer) that prevents holes or excitons (exciton) from escaping to the cathode side, or a light emitting layer in an excited state, or light emission in an excited state. A layer (anti-quenching layer) for preventing or suppressing both energy transition and electron transfer from a layer to an adjacent layer may be inserted.

  In these multilayer organic light-emitting device configurations, the fluorinated naphthalocyanine compound represented by the above formula (1) or (2) produced by the present invention is used as the light emitting material contained in the light emitting layer.

  In addition to the above-described structure, the organic light-emitting device of the present invention can be provided with a protective layer (sealing layer) for blocking contact with oxygen, moisture and the like so as to minimize the influence of the external environment. .. The protective layer can be formed using any of a thermoplastic resin such as an epoxy resin, an acrylic resin, a polyester resin, a polycarbonate resin, or a fluororesin, a thermosetting resin, or a photocurable resin. In addition, the organic light emitting device of the present invention can be protected from the external environment by encapsulating the device in an inert material such as paraffin, silicone oil, or fluorocarbon.

  Hereinafter, the configuration of the organic light-emitting device of the present invention will be described in detail by taking as an example a configuration in which the (2-3) anode, hole transport layer, light-emitting layer, electron transport layer, and cathode are sequentially provided on a substrate. To do.

  The substrate is not particularly limited as long as it is used in a conventional organic light emitting device, and examples thereof include a substrate made of a material such as glass such as quartz glass and a transparent plastic. Alternatively, an opaque substrate such as a metal substrate or a ceramic substrate may be used.

  As the anode, one having a large work function is preferable, and examples thereof include simple metals such as gold, platinum, nickel, palladium, cobalt, selenium, and vanadium, or alloys thereof, oxides, zinc oxide, indium tin oxide (ITO). ), And metal oxides such as zinc indium oxide. Further, a conductive polymer material such as polyaniline, polypyrrole, polythiophene, etc. can also be used. The anode can be formed of these materials on the substrate by a method such as vapor deposition, sputtering, and coating. The film thickness of the anode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  As the hole transporting material used for the hole transporting layer, known materials which have been conventionally used as a charge injecting and transporting material for holes in photoconductive materials and well-known hole transporting layers for organic light emitting devices are used. Any material can be selected and used. Examples of the hole-transporting material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, N, N′-di (m-tolyl) -N. , N'-diphenyl-4,4'-diaminobiphenyl (TPD), N, N'-di (1-naphthyl) -N, N'-diphenyl-4,4'-diaminobiphenyl (α-NPD) and other triaryls Examples thereof include amine derivatives, polyphenylene vinylene derivatives, and polythiophene derivatives. Further, a hole-transporting polymer such as polyvinylcarbazole, (fanylmethyl) polysilane, and polyaniline can also be used. As the hole transporting polymer, a polymer obtained by doping the above low molecular weight hole transporting material into a polymer such as polystyrene or polycarbonate may be used.

  As the light emitting material used in the light emitting layer, at least the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) produced by the present invention is used. May be used in combination with a known luminescent material material. Examples of the known light emitting material include acridone derivatives, quinacridone derivatives, coumarin derivatives, pyran derivatives, oxazone derivatives, benzoxazone derivatives, benzothiazole derivatives, benzimidazole derivatives, condensed polycyclic aromatic hydrocarbons and their derivatives, triarylamine derivatives. , An organic metal derivative (for example, an organic metal complex of aluminum or iridium), and the like, and they are used alone or in a mixture of two or more. Further, as the light emitting material, a material containing a dopant material in a host material, for example, a polycarbazole doped with an iridium metal complex or a charge transporting host material containing a phosphorescent platinum complex can be used.

As the electron transporting material used in the electron transporting layer, conventionally known compounds can be used. Examples of the known compound include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq ₃ ), 2- (4-biphenylyl) -5- (4-t-butylphenyl)- Azole such as 1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ) Examples include compounds and phenanthroline derivatives. Moreover, you may use the fluorine-containing pentacene compound represented by said Formula (3) and (4) manufactured by this invention. These electron-transporting materials are used alone or as a mixture of a plurality of materials, depending on the characteristics of the organic light emitting device.

  The cathode preferably has a small work function, and examples thereof include a single metal or a plurality of alloys such as lithium, sodium, potassium, cesium, calcium, magnesium, aluminum, indium, silver, lead, tin, and chromium. Be done. Alternatively, a metal oxide such as indium tin oxide (ITO) may be used. The cathode can be produced by forming a thin film of these materials by a method such as vapor deposition or sputtering. The thickness of the cathode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  In the organic light emitting device according to the present invention, the light emitting layer containing the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) and the layer containing another organic compound are generally vacuum vapor deposition methods. Alternatively, it is dissolved in an applicable organic solvent to form a solution, and the solution is formed into a thin film by a coating method such as spin coating, dip coating, or roll toe-toll method. Since the fluorine-containing naphthalocyanine compound represented by the above formula (1) or (2) can obtain a good film-forming property in the film formation by the solution coating method, a device with high definition and large area can be obtained. A great effect can be achieved in improving workability and manufacturing cost at the time of manufacturing. Examples of the organic solvent used include hydrocarbon solvents, ketone solvents, halogen solvents, ester solvents, alcohol solvents, ether solvents, aprotic solvents, perfluoro solvents, water and the like. These organic solvents may be used alone or as a plurality of mixed solvents.

  The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited as long as it is a thickness generally adopted in a conventional organic light emitting device, but is usually 1 to 1000 nm. Is adjusted to

  Hereinafter, the method for producing the fluorinated polycyclic aromatic compound will be described with reference to specific examples, but the present invention is not limited to these examples.

[Example 1]
Synthesis of 4,5-bis (perfluorohexyl) -o-xylene

Copper powder (10.8 g, 170 mmol) dried at 150 ° C. and 0.1 mmHg for 30 minutes was placed in a 100 mL three-necked flask, and 4,5-dibromo-o-xylene (4.50 g, 17.0 mmol) and C ₆ F ₁₃ I ( 22.7 g, 17.0 mmol) and anhydrous DMSO (45 mL) were added, and the mixture was stirred at 110 ° C for 22 hr under an argon atmosphere. After water was added to the reaction mixture, it was filtered through Celite using chloroform. The aqueous layer of the filtrate was extracted 3 times with chloroform, the organic layer was washed 5 times with water to remove DMSO, and the organic layer was dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the mixture was concentrated with a rotary evaporator to obtain 4,5-bis (perfluorohexyl) -o-xylene as a yellow liquid (12.2 g, 16.5 mmol, yield 97%). When the NMR measurement of the obtained product was performed, the results were as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.50 (s, 2H), 2.39 (s, 6H).
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ = -81.02 (t, J = 9.68, 6F), -103.31 (s, 4F), -118.34 (s, 4F), -122.12 (s, 4F), 122.91 (s, 4F), 126.23 (s, 4F).

[Example 2]
Synthesis of 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene

In a 100 mL three-necked flask, 4,5-bis (perfluorohexyl) -o-xylene (6.0 g, 8.1 mmol), N-bromosuccinimide (NBS) (5.8 g, 3.2 mmol), benzoyl peroxide (BPO) ( 0.20 g, 0.081 mmol) and dry carbon tetrachloride (45 mL) were added, and the mixture was refluxed for 24 hours. The reaction solution was cooled to room temperature, NBS (1.5 g, 2.0 mmol) and BPO (0.049 g, 0.020 mmol) were added, and the mixture was refluxed for 24 hours again. The reaction solution was cooled to room temperature, NBS (1.5 g, 2.0 mmol) and BPO (0.049 g, 0.020 mmol) were added, and the mixture was refluxed for 24 hours. The reaction solution was cooled to room temperature, NBS (1.5 g, 2.0 mmol) and BPO (0.049 g, 0.020 mmol) were added, and the mixture was refluxed for 24 hours. The reaction solution was cooled to room temperature, NBS (1.5 g, 2.02 mmol) and BPO (0.049 g, 0.020 mmol) were added, and the mixture was refluxed for 4 hours. At this point, disappearance of the raw materials and formation of the desired product were confirmed by silica gel thin layer chromatography (TLC). The reaction solution was cooled to 0 ° C., the generated succinimide was filtered off, and then concentrated by a rotary evaporator to obtain 7.1 g of a yellow solid. From ¹ H and ¹⁹ F NMR analysis of this solid, 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene and 4,5-bis (perfluorohexyl) -1-dibromomethyl- It was a mixture of 2-bromomethylbenzene, and the molar ratio was confirmed to be 8: 1. The ¹⁹ F NMR yield of 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene was estimated to be 88%. When the NMR measurement of the reaction product was performed, the results were as follows.

4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.08 (s, 2H), 7.10 (s, 2H).
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ = -81.02 (t, J = 9.51, 6F), -103.93 (s, 4F), -118.11 (s, 4F), -122.03 (s, 4F),- 122.87 (s, 4F), -126.28 (s, 4F).

4,5-bis (perfluorohexyl) -1-dibromomethyl-2-bromomethylbenzene
¹ H NMR (400 MHz, CDCl ₃ ): δ = 8.31 (s, 1H), 7.70 (s, 1H), 7.03 (s, 1H), 4.60 (s, 2H)
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ = -81.02 (t, J = 9.51, 6F), -103.93 (s, 4F), -118.11 (s, 4F), -122.03 (s, 4F),- 122.87 (s, 4F), -126.28 (s, 4F).

[Example 3]
Synthesis of 2,3,9,10-tetrakis (perfluorohexyl) pentacene-6,13-dione

  In a 100 mL three-necked flask, a mixture of 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene and 4,5-bis (perfluorohexyl) -1-dibromomethyl-2-bromomethylbenzene. (2.0 g, molar ratio 8: 1), 1,4-benzoquinone (0.082 g, 0.76 mmol), potassium iodide (3.1 g, 19 mmol) and anhydrous DMF (45 mL) were added, and the mixture was heated at 110 ° C under an argon atmosphere. It was stirred for 20 hours. The reaction mixture was cooled to room temperature, 150 mL of a saturated aqueous solution of sodium hydrogen sulfite was added, and the precipitated solid was suction filtered. The obtained solid was washed with water (100 mL × 2) and acetone (50 mL × 2), dissolved in 1H, 1H-decafluoropentane, and washed 3 times with water to remove DMF, and the organic layer was removed. It was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solution was concentrated with a rotary evaporator to give 2,3,9,10-tetrakis (perfluorohexyl) pentacene-6,13-dione as a brown solid 1.0 g (0.67 mmol, yield 73%). Obtained. When the product was subjected to NMR measurement, the results were as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 9.18 (s, 4H), 8.63 (s, 4H).
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ = -80.78 (t, J = 9.16, 6F), -103.17 (s, 4F), -118.12 (s, 4F), -121.93 (s, 4F),- 122.70 (s, 4F), -126.08 (s, 4F).

[Example 4]
Synthesis of 6,13-bis (triisopropylsilylethynyl) -2,3,9,10-tetrakis (perfluorohexyl) pentacene

  To a solution of triisopropylsilylacetylene (0.12 mL, 0.55 mmol) in THF (15 mL) was added n-butyllithium hexane solution (1.6 M, 0.29 mL, 0.46 mmol) under argon atmosphere at 0 ° C, and the mixture was added at 30 ° C at 0 ° C. Stir for minutes. 6,13-Bis (triisopropylsilylethynyl) -2,3,9,10-tetrakis (perfluorohexyl) pentacene (0.16 g, 0.10 mmol) was added, and the mixture was stirred at room temperature for 16 hours. The reaction solution was concentrated with a rotary evaporator, excess triisopropylsilylacetylene was removed by column chromatography (silica gel, hexane), and the solution eluted with ethyl acetate was concentrated with a rotary evaporator to obtain a mixture containing an intermediate diol. Obtained. This was dissolved in degassed THF (10 mL) and hydrochloric acid (6 M, 10 mL), tin (II) chloride dihydrate (0.45 g, 2.0 mmol) was added, and the mixture was refluxed for 3 hours under shading. The reaction mixture was extracted with hexane (100 mL), and the organic layer was dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the residue was purified by column chromatography (silica gel, hexane) and concentrated by a rotary evaporator to obtain 0.026 g (0.014 mmol, yield 13%) of the target pentacene derivative as a blue solid. When the product was subjected to NMR measurement, the results were as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 9.52 (s, 4H), 8.41 (s, 4H), 1.05-1.48 (m, 42 H).
¹⁹ F NMR (376 MHz, CDCl ₃ ): δ = -80.74 (t, J = 9.51, 6F), -103.14 (s, 4F), -118.09 (s, 4F), -121.89 (s, 4F),- 122.62 (s, 4F), -126.03 (s, 4F).

[Example 5]
Synthesis of 6,7-bis (tridecafluorohexyl) -2,3-dicyanonaphthalene

Under an argon atmosphere, 4,5-bis (tridecafluorohexyl) -1,2-bis (dibromomethyl) benzene (9.0 g, 8.5 mmol) in anhydrous DMA (140 mL) was treated with fumaronitrile (1.1 g, 15 mg). mmol) and sodium iodide (3.6 g, 24 mmol) were added, and the mixture was stirred at 75 ° C for 20 hr. The reaction was stopped by adding a saturated aqueous sodium hydrogen sulfite solution (100 mL), and the filtered solid was dissolved in 3M ^TM Novec ^TM 7100 and washed 5 times with distilled water (50 mL). The organic layer was dried over anhydrous sodium sulfate, the sodium sulfate was filtered off, and the crude product obtained by concentrating on a rotary evaporator was purified by column chromatography (silica gel, hexane: dichloromethane = 1: 1) to give an orange-colored product. The desired product was obtained as a solid (3.0 g, 3.7 mmol, 43%).

[Example 6]
Synthesis of hexakis (perfluoroalkyl) naphthalocyanine

  Under an argon atmosphere, a mixture of 6,7-bis (tridecafluorohexyl) -2,3-dicyanonaphthalene (0.33 g, 0.41 mmol) and dry DMF (0.03 mL, 0.33 mmol) was added to ammonium sulfate (5 mg, 0.04 mmol). mmol) and 1,1,1,3,3,3-hexamethyldisilazane (0.18 mL, 0.85 mmol) were added, and the mixture was heated at 150 ° C. for 24 hours. After cooling to room temperature, the produced solid was filtered and washed with methanol and water once to obtain the desired product as a black solid (0.26 g, 0.08 mmol, yield 20%).

MS (MALDI-FT-ICR): m / z 3259 (M ⁺ ).
UV-vis: λ _max = 762 nm (ε 9.5 × 10 ³ ).

[Example 7]
Synthesis of 4,5-bis (perfluorobutyl) -o-xylene

80℃、0.1 mmHgで３０分間乾燥させた銅粉（43 g, 0.68 mol）を300mL三ツ口フラスコに入れ、4,5-ジブロモ-o-キシレン(18 g, 68 mmol) 、C₄F₉I (34 g, 0.20 mol)、無水DMSO (180 mL) を加え、アルゴン雰囲気下80 ℃で22時間攪拌した。反応混合物に水を加えた後、クロロホルムを用いてセライトろ過を行った。ろ液の水層をクロロホルムで３回抽出し、有機層を水で５回洗浄することでDMSOを除去し、有機層を無水硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ別した後、ロータリーエバポレーターで濃縮し、4,5-ビス(パーフルオロブチル)-o-キシレンを黄色液体として35 g（65 mmol、収率95％）得た。得られた生成物のNMR測定を行ったところ、結果は以下の通りであった。

Copper powder (43 g, 0.68 mol) dried at 80 ° C. and 0.1 mmHg for 30 minutes was placed in a 300 mL three-necked flask, and 4,5-dibromo-o-xylene (18 g, 68 mmol) and C ₄ F ₉ I ( 34 g, 0.20 mol) and anhydrous DMSO (180 mL) were added, and the mixture was stirred at 80 ° C for 22 hr under an argon atmosphere. After water was added to the reaction mixture, it was filtered through Celite using chloroform. The aqueous layer of the filtrate was extracted 3 times with chloroform, the organic layer was washed 5 times with water to remove DMSO, and the organic layer was dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the mixture was concentrated with a rotary evaporator to obtain 35 g (65 mmol, yield 95%) of 4,5-bis (perfluorobutyl) -o-xylene as a yellow liquid. When the NMR measurement of the obtained product was performed, the results were as follows.

¹ H NMR (400 MHz, CDCl3): δ 7.50 (s, 2H), 2.39 (s, 6H).
¹⁹ F NMR (376 MHz, CDCl3): δ -81.06 (t, J = 9.7 Hz, 6F), -103.36 (s, 4F), -119.20 (s, 4F), -126.16 (s, 4F).

[Example 8]
Synthesis of 4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene

In a 500 mL three-necked flask, 4,5-bis (perfluorobutyl) -o-xylene (35 g, 65 mmol) obtained in Example 7, N-bromosuccinimide (NBS) (46 g, 0.26 mol), Benzoyl peroxide (BPO) (3.1 g, 13 mmol) and dry carbon tetrachloride (360 mL) were added, and the mixture was refluxed for 24 hours. The reaction solution was cooled to room temperature, NBS (12 g, 65 mmol) and BPO (0.78 g, 3.3 mmol) were added, and the mixture was refluxed for 24 hours again. The reaction solution was cooled to room temperature, NBS (12 g, 65 mmol) and BPO (0.78 g, 3.3 mmol) were added, and the mixture was refluxed for 24 hours. At this point, disappearance of the raw materials and formation of the desired product were confirmed by silica gel thin layer chromatography (TLC). The reaction solution was cooled to 0 ° C., the generated succinimide was filtered off and then concentrated by a rotary evaporator to obtain 59 g of a yellow solid. From ¹ H and ¹⁹ F NMR analysis of this solid, 4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene and 4,5-bis (perfluorobutyl) -1-dibromomethyl- It was a mixture of 2-bromomethylbenzene and the molar ratio was confirmed to be 33: 1. The ¹⁹ F NMR yield of 4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene was estimated to be 97%. When the NMR measurement of the reaction product was performed, the results were as follows.

4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene
¹ H NMR (400 MHz, CDCl3): δ 8.09 (s, 2H), 7.07 (s, 2H).
¹⁹ F NMR (376 MHz, CDCl3): δ -80.91 (t, J = 9.9 Hz, 6F), -103.94 (s, 4F), -118.90 (s, 4F), -125.99 (s, 4F).

4,5-bis (perfluorobutyl) -1-dibromomethyl-2-bromomethylbenzene
¹ H NMR (400 MHz, CDCl3): δ 8.31 (s, 1H), 7.70 (s, 1H), 7.03 (s, 1H), 4.60 (s, 2H)
¹⁹ F NMR (376 MHz, CDCl3): δ -80.91 (t, J = 9.9 Hz, 6F), -103.94 (s, 4F), -118.90 (s, 4F), -125.99 (s, 4F).

[Example 9]
Synthesis of 6,7-bis (perfluorobutyl) -2,3-dicyanonaphthalene

  4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene obtained in Example 8 and 4,5-bis (perfluorobutyl) -1- (dibromomethyl) -2-bromo Mixture of methylbenzene (2.5 g, 4,5-bis (perfluorobutyl) -1,2-bis (dibromomethyl) benzene: 2.8 mmol, 4,5-bis (perfluorobutyl) -1- (dibromomethyl)) -2-Bromomethylbenzene: 0.096 mmol) in dimethylformamide (25 mL), fumaronitrile (0.39 g, 5.0 mmol) and sodium iodide (1.2 g, 8.2 mmol) were added, and the mixture was added under argon atmosphere at 75 ° C for 20 Heated for hours. After cooling to room temperature, saturated aqueous sodium hydrogen sulfite solution (25 ml) was added to stop the reaction, and the precipitated solid was filtered off. This solid was dissolved in HCFC-225 and washed 5 times with distilled water. The organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated with a rotary evaporator. The obtained crude product was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2) to obtain 0.90 g (1.5 mmol, 50%) of the title compound as a colorless solid.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.58 (s, 2H), 8.46 (s, 2H).
¹⁹ F NMR (376 MHz, CDCl3): δ -80.91 (t, J = 9.9 Hz, 6F), -103.94 (s, 4F), -118.90 (s, 4F), -125.99 (s, 4F).

[Example 10]
Synthesis of Subnaphthalocyanine Having Perfluoroalkyl Group (C ₄ F ₉ )

  A 20 mL Schlenk tube was charged with a solution of 6,7-bis (perfluorobutyl) -2,3-dicyanonaphthalene (0.14 g, 0.23 mmol) obtained in Example 9 in o-dichlorobenzene (6 mL), Boron trichloride (1.0 M heptane solution, 0.15 mL, 0.15 mmol) was added, and the mixture was heated at 150 ° C for 1 hr under an argon atmosphere, and then heated at 180 ° C for 23 hr. The mixture was cooled to room temperature, the insoluble matter was filtered off, and the filtrate was concentrated. The obtained crude product was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2) to obtain 0.12 g (0.064 mmol, 85%) of the title compound as a black purple solid.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.64 (s, 6H), 8.83 (s, 6H).
¹⁹ F NMR (376 MHz, CDCl3): δ -80.91 (t, J = 9.9 Hz, 18F), -103.94 (s, 12F), -118.90 (s, 12F), -125.99 (s, 12F).

  The thermal stability of the fluorine-containing subnaphthalocyanine (triphenylnaphthalocyanine) compound obtained in this Example was measured by the method of the prior art (K. Shirai et al., Tertahedron, Vol. 74, p. 4220-4225). ) And the following fluorine-containing triphenylnaphthalocyanine compound disclosed in (4).

  The thermal stability was measured by using a thermogravimetric analyzer (TGA; Thermo Plus EVO differential scanning calorimeter manufactured by Rigaku Co., Ltd.) from room temperature to about 500 ° C. at a temperature rising rate of 10 ° C./min. The temperature Td (5%) when the amount was reduced by 5% compared to the initial stage was evaluated. The higher Td (5%) means the better thermal stability.

  As a result of TGA measurement, the Td (5%) of this example was 271 ° C, whereas the Td (5%) of the prior art compound was 221 ° C. Thus, in the fluorine-containing triphenylnaphthalocyanine compound, thermal stability is improved by introducing a perfluorobutyl group in place of the fluorine atom into the aromatic group located at the end of the conjugated polycyclic aromatic group. It turns out that it can be improved.

  In addition, the wavelength dependence of the light absorption of the compound of this example was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation: UV-2550), and the wavelength showing the maximum absorption was 647 nm. This wavelength shows almost no difference from the wavelength (646 nm) at which the compound according to the prior art shows the maximum absorption. Therefore, the conjugated polycyclic aromatic compound has an optical characteristic that the basic skeleton of the triphenylnaphthalocyanine compound has. It was confirmed that the substituents that are nuclear-substituted by the aromatic groups located at the ends of the groups have almost no effect even if the type is changed.

[Example 11]
2,3-bis (perfluorohexyl) pentacene-6,13-dione

    Obtained by synthesizing 4,5-bis (perfluorohexyl) -o-xylene in place of 4,5-bis (perfluorobutyl) -o-xylene in the synthesis method of Examples 7 and 8. A mixture of 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene and 4,5-bis (perfluorohexyl) -1- (dibromomethyl) -2-bromomethylbenzene (2.0 g, 4,5-bis (perfluorohexyl) -1,2-bis (dibromomethyl) benzene: 1.7 mmol, 4,5-bis (perfluorobutyl) -1- (dibromomethyl) -2-bromomethylbenzene : 0.2 mmol) in dimethylformamide (55 mL), anthracene-1,4-one (0.55 g, 2.7 mmol) and potassium iodide (4.5 g, 27 mmol) were added, and the mixture was heated at 110 ° C under argon atmosphere at 20 Heated for hours. After cooling to room temperature, saturated aqueous sodium hydrogen sulfite solution (55 ml) was added to stop the reaction, and the precipitated solid was separated by filtration. The solid was washed with a small amount of diethyl ether and acetone to obtain 0.90 g (0.95 mmol, 50%) of the title compound as a light brown solid.

¹ H NMR (400 MHz, CDCl3): δ 9.14 (s, 4H), 9.00 (s, 4H), 8.59 (s, 4H), 8.16 (q, J = 3.2 Hz, 4H). 7.77 (q, J = 3.1 Hz, 4H).
¹⁹ F NMR (376 MHz, CDCl3): δ-80.72 (t, J = 10.2 Hz, 6F), -102.91 (s, 4F), -117.77 (s, 4F), -121.86 (s, 4F), -122.66 (s, 4F), -126.03 (s, 4F).
¹³ C NMR and HRMS could not be recorded due to poor solubility.

[Example 12]
6,13-bis [(triisopropylsilyl) ethynyl] -2,3-bis (perfluorohexyl) pentacene

  Under an argon atmosphere, n-butyllithium (1.6 M hexane solution, 0.50 mL, 0.80 mmol) was added to a solution of (triisopropylsilyl) acetylene (0.20 mL, 0.92 mmol) in tetrahydrofuran (30 mL), and the mixture was stirred at 0 ° C. After stirring for 0.5 hours, 2,3-bis (perfluorohexyl) pentacene-6,13-dione (0.16 g, 0.18 mmol) obtained in Example 11 was added, and the mixture was stirred at room temperature for 16 hours. The residue obtained by concentrating the mixture was separated by column chromatography (silica gel, hexane to ethyl acetate) to obtain a crude product containing an intermediate diol. To a solution of this crude product in tetrahydrofuran (10 mL) was added hydrochloric acid (6M, 10 mL) and tin (II) chloride dihydrate (6.8 g, 36 mmol), and the mixture was heated at 66 ° C for 3 hours under an argon atmosphere. Heated. After cooling to room temperature, the insoluble matter was filtered off, and the filtrate was washed 5 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the crude product obtained by concentrating the filtrate was purified by column chromatography (silica gel, hexane) to give the title compound as a blue solid in an amount of 0.084 g (0.070 g). mmol, 39%) was obtained.

¹ H NMR (400 MHz, CDCl3): δ 9.46 (s, 2H), 9.35 (s, 2H), 8.37 (s, 2H), 8.01 (q, J = 3.2 Hz, 2H). 7.48 (q, J = 3.5 Hz, 2H), 1.35-1.46 (m, 42 H).
¹⁹ F NMR (376 MHz, CDCl3): δ-80.74 (t, J = 10.2 Hz, 6F), -103.05 (s, 4F), -118.14 (s, 4F), -121.93 (s, 4F), -122.64 (s, 4F), -126.05 (s, 4F).
¹³ C {1H} NMR (100 MHz, CDCl3): 134.2, 133.0, 131.6, 129.4, 129.3, 128.7, 126.8, 126.7, 119.6, 109.1, 103.8, 18.9, 11.6.
¹³ C NMR signals corresponding to the C6F13 groups could not be observed.
HRMS (MALDI +) m / z calcd for C56H52F26Si2 1274.3192, found: 1274.3173 ([M] +).

  The fluorine-containing silylethynylpentacene obtained in this Example, the fluorine-containing silylethynylpentacene obtained in Example 4 and the prior art (Z. Bao et al., Macoromolecules, 2008, Volume 41, p. 6977). ), The following fluorine-free triphenylnaphthalocyanine compound was measured for wavelength dependence of light absorption using an ultraviolet-visible spectrophotometer (UV-2550 manufactured by Shimadzu Corporation).

  As a result of measurement with an ultraviolet-visible spectrophotometer, the wavelengths exhibiting maximum absorption were 648 nm, 656 nm, and 668 nm in the compound of Example 4, the compound of this example, and the compound of the prior art, respectively. Thus, by introducing a nuclear-substituted perfluorohexyl group at one end and both ends of the aromatic group located at the end of the conjugated polycyclic aromatic group, the bonding position and number of the perfluorohexyl group to be introduced Depending on the above, the spectral characteristics of the compound can be changed within a desired range. In the present Example and Example 4, a perfluorohexyl group was exemplified as the perfluoroalkyl group. However, the number of substitutions and the substitution position of the perfluoroalkyl group, including the type of the perfluoroalkyl group, are further examined to optimize the chemical structure. As a result, not only the spectral characteristics of the fluorine-containing polycyclic aromatic compound but also the electron mobility can be changed within a desired range, so that the range of material selection can be expanded for applications such as organic electronic materials.

  As described above, according to the present invention, as a fluorine-containing polycyclic aromatic compound of fluorine-containing pentacene and fluorine-containing naphthalocyanine, imparting a function not obtained in the conventional fluorine-containing polycyclic aromatic compound, or to a solvent It is possible to provide a novel fluorine-containing polycyclic aromatic compound having improved physical properties or characteristics such as improved solubility, improved electron mobility, improved heat resistance and durability. Further, the fluorine-containing polycyclic aromatic compound of the present invention can be easily synthesized by the production method of the present invention with a small number of steps. The fluorine-containing polycyclic aromatic compound of the present invention is excellent in various properties such as heat resistance or solvent resistance, has high solubility in a fluorine-based solvent, and can be used even under high temperature, non-aqueous or special solvent environments. Therefore, when the organic thin film transistor, the solar cell, the electrophotographic photosensitive member, and the organic light emitting element are applied, the applicable range thereof can be expanded more than ever. In addition, since fluorine-containing pentacene and naphthalocyanine can be easily produced to have compounds having various chemical structures, which were difficult to synthesize by the conventional methods, by adding a new function to various fields. Since it can be expected to be applied, its usefulness is extremely high.

1 ... Substrate, 2 ... Gate electrode, 3 ... Gate insulating film, 4 ... Source electrode, 5 ... Drain electrode, 6 ... Organic semiconductor layer, 7 ... Conductive substrate , 8 ... undercoat layer, 9 ... charge generation layer, 10 ... charge transport layer.

Claims (17)

A fluorine-containing polycyclic aromatic compound having a conjugated polycyclic aromatic group having three or more rings, wherein at least one of the aromatic groups located at both ends of the conjugated polycyclic aromatic group is nucleus-substituted with a perfluoroalkyl group. A family compound,
A fluorine-containing polycyclic aromatic compound represented by any of the following formula (1), the following formula (2), the following formula (3), and the following formula (4).

[In the formula, M represents two hydrogen atoms, a divalent metal, or a trivalent or tetravalent metal or metalloid derivative, and X ₁ and X ₂ are each independently a perfluoroalkyl group, X ₃ and X ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group which may be fluorinated or perfluorinated, an alkyl group which is not fluorinated, or a phenyl group which is not fluorinated. Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following formula (1b), a substituent or It is an unsubstituted condensed polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following (1b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. R ₁ , R ₂ , and R ₃ are each independently hydrogen, fluorine, chlorine, a non-fluorinated linear or branched alkyl group or alkoxy group, or a fluorinated or perfluorinated linear group. Or, it is a branched alkyl group or alkoxy group, or an aryl group which may be fluorinated or perfluorinated. ]

[In the formula, A ₁ , A ₂ and A ₃ are an alkyl group, a phenyl group or a fluorine-containing alkyl group. ]

[In the formula, B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, a perfluoroalkyl group. , An alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group. ] The fluorine-containing polycyclic aromatic compound according to claim 1 is a compound represented by the general formula (1) or the general formula (2), and the X ₁ and X ₂ are each independently, _{-CF 3, -C 4 F 9,} -C 6 F 13, fluorine, which is a one of a perfluoroalkyl group selected from the group consisting of -C _{8 F 17,} and _-C 10 _{F 21} Polycyclic aromatic compounds. The fluorine-containing polycyclic aromatic compound according to claim 1 is a compound represented by the general formula (3) or the general formula (4), and X ₁ and X ₂ are each independently, _{-CF 3, -C 4 F 9,} -C 6 F 13, is any perfluoroalkyl group -C _{8 F 17,} and _-C 10 _{F 21,} the _{X 3} and _{X 4} are each independently and wherein the hydrogen atom or _{-CF 3, -C 4 F 9,} -C 6 F 13, is any one perfluoroalkyl group selected from the group consisting of -C _{8 F 17,} and _-C 10 _{F 21} Fluorine-containing polycyclic aromatic compound. A fluorine-containing polycyclic aromatic compound characterized by using a fluorine-containing monocyclic aromatic compound represented by the following formula (5) as a reaction intermediate in the synthesis of a fluorine-containing pentacene compound and a fluorine-containing naphthalocyanine compound. Production method.

[In the formula, X ₁ and X ₂ are each independently a fluorine atom or a fluorine-containing alkyl group, and Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, A substituent represented by the formula 5a), a phenyl group represented by the formula (5b) below, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aromatic heterocyclic group. Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a fluorine-containing alkyl group, a substituent represented by the following formula (1a), a phenyl group represented by the following (5b), a substituted or non-substituted one. It is a substituted fused polycyclic aromatic group or a substituted or unsubstituted aromatic heterocyclic group. ]

[In the formula, A ₁ , A ₂ and A ₃ are each independently an alkyl group, a phenyl group or a fluorine-containing alkyl group. ]

[In the formula, B ₁ , B ₂ , B ₃ , B ₄ and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a fluorine-containing tertiary alkyl group, a perfluoroalkyl group. , An alkoxy group, an acyl group, an ester substituent, an amide substituent, or a phenyl group. ] X ₁ and X ₂ are each independently a fluorine atom or a fluorine-containing alkyl group,
The Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a perfluoroalkyl group, and the A ₁ , A ₂ and A ₃ are each independently an alkyl group or a perfluoroalkylalkyl group. 5a), or B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group. Is a phenyl group,
Z ₁ and Z ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a tertiary alkyl group, a perfluoroalkyl group, and each of A ₁ , A ₂ and A ₃ is an alkyl group or perfluoro. The substituent represented by the formula (5a), which is an alkylalkyl group, or B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group. The method for producing a fluorinated polycyclic aromatic compound according to claim 4, wherein the phenyl group is represented by the formula (5b). The fluorine-containing monocyclic aromatic compound is a compound represented by the following formula (6) or formula (7), and the bromine (Br) or iodine (I) is nuclear-substituted at the position X ₁ and X. a step of synthesizing a compound represented by the following expression (8) by introducing _two substituents, and a monocyclic aromatic ring in the substituents W ₁ and W ₂ of the compound represented by the following formula (8) The method for producing a fluorine-containing polycyclic aromatic compound according to claim 4 or 5, wherein the method is produced by a synthetic method including a step of brominating two hydrogen atoms bonded to carbon to be chemically bonded.

[In the formula, Y ₁ , Y ₂ , X ₁ and X ₂ are the same substituents as described above, and W ₁ and W ₂ are each independently a methyl group, or one hydrogen atom of a methyl group is Z ₁ , Z ₂ is a substituted group. ] The fluorine-containing monocyclic aromatic compound is a compound represented by the formula (6), and by introducing the substituents of X ₁ and X ₂ at the position where bromine (Br) is nuclear-substituted, A step of synthesizing the compound represented by the formula (8), and two hydrogens bonded to carbons chemically bonded to the monocyclic aromatic ring in the substituents of W ₁ and W ₂ of the compound represented by the formula (8). The method for producing a fluorinated polycyclic aromatic compound according to claim 6, which is produced by a synthetic method having a step of brominating atoms. The method for producing a fluorine-containing polycyclic aromatic compound according to any one of claims 4 to 7, wherein X ₁ and X ₂ are each independently a fluorine atom or a perfluoroalkyl group. The method for producing a fluorinated polycyclic aromatic compound according to claim 8, wherein Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom or a perfluoroalkyl group. The method for producing a fluorinated polycyclic aromatic compound according to claim 9, wherein Z ₁ and Z ₂ are hydrogen atoms.   A fluorine-containing naphthalocyanine compound is produced by carrying out a Diels-Alder cycloaddition reaction of the above-mentioned fluorine-containing monocyclic aromatic compound and fumaronitrile or maleonitrile, and then by carrying out a reaction of cyclotetramerization or cyclotrimerization. The method for producing a fluorinated polycyclic aromatic compound according to any one of claims 4 to 10, wherein   A step of synthesizing a fluorine-containing polycyclic aromatic compound containing an oxygen atom by a Diels-Alder cycloaddition reaction of the fluorine-containing monocyclic aromatic compound and para-benzoquinone, and a fluorine-containing polycyclic compound containing the oxygen atom. The step of synthesizing a fluorine-containing silylethynylpentacene compound by silylethynylating a ring aromatic compound and then reducing the ring aromatic compound, The fluorine-containing polycycle according to any one of claims 4 to 10. Method for producing aromatic compound.   A step of synthesizing a fluorine-containing polycyclic aromatic compound containing an oxygen atom by a Diels-Alder cycloaddition reaction of the fluorine-containing monocyclic aromatic compound and para-benzoquinone, and a fluorine-containing polycyclic compound containing the oxygen atom. The method for producing a fluorine-containing polycyclic aromatic compound according to any one of claims 4 to 10, comprising a step of synthesizing a fluorine-containing pentacene compound by reducing the ring aromatic compound.   A method for producing an organic thin film transistor, which comprises using the fluorine-containing polycyclic aromatic compound produced by the production method according to any one of claims 11 to 13 as an organic semiconductor material.   An electron transfer material containing the fluorine-containing polycyclic aromatic compound produced by the production method according to any one of claims 11 to 13 in an electron transport layer, a cathode side buffer layer, or a buffer layer in contact with an intermediate electrode. A method for manufacturing a solar cell, which is used as   A method for producing an electrophotographic photosensitive member, comprising using the fluorine-containing polycyclic aromatic compound produced by the production method according to claim 11 as a charge generating material contained in a charge generating layer.   A method for producing an organic light emitting device, comprising using the fluorine-containing polycyclic aromatic compound produced by the production method according to claim 11 as a light emitting material contained in a light emitting layer.

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