JP6004848B2 - Polymer, organic thin film and organic thin film element using the polymer - Google Patents

Description

  The present invention relates to a polymer, an organic thin film using the polymer, and an organic thin film element including the same.

  Thin films containing organic materials having charge (electron or hole) transport properties are expected to be applied to organic thin film elements such as organic thin film transistors, organic thin film solar cells, and optical sensors. From polymers that can form such thin films, Various organic p-type semiconductor materials (showing hole transport properties) and organic n-type semiconductor materials (showing electron transport properties) have been studied.

  As an organic p-type semiconductor material made of a polymer, poly (3-alkylthiophene) is known (see Patent Document 1).

  On the other hand, as an organic thin film solar cell which is one embodiment of the organic thin film element, it is described that a composition containing an organic p-type semiconductor material made of a donor polymer and an acceptor fullerene derivative is used for the organic thin film solar cell. (See Patent Document 2).

US Pat. No. 6,107,117 US Pat. No. 5,331,183

  However, it has been difficult to say that the organic p-type semiconductor material made of the conventional polymer has sufficient hole transportability.

  Then, an object of this invention is to provide the polymer which has the outstanding hole transportability. Furthermore, an object of this invention is to provide the organic thin film element provided with this organic thin film containing this polymer, and this organic thin film.

［式中、
Ｘ^１及びＸ^２は、それぞれ独立に、酸素原子、硫黄原子又は＝Ｃ（Ａ）_２で表される基（Ａは、水素原子、ハロゲン原子又は置換基を有していてもよい１価の基を示し、二つのＡは互いに同一でも異なっていてもよい。）を示す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、直鎖状、分岐状若しくは環状の炭素数１〜３０のアルキル基、直鎖状、分岐状若しくは環状の炭素数１〜３０のアルキル基を含む１価の非アルキル基、置換基を有していてもよい炭素数６〜６０のアリール基又は置換基を有していてもよい炭素数２〜６０の１価の複素環基を示す。また、Ｒ^１及びＲ^２は互いに結合して、これらが結合している環と縮合する炭化水素環又は複素環を形成していてもよく、該炭化水素環及び該複素環は置換基を有していてもよい。
Ａｒ^１は、置換基を有していてもよい炭素数６〜６０の４価の芳香族炭化水素基又は置換基を有していてもよい炭素数４〜６０の４価の複素環基を示す。
Ｙは、炭素原子、ケイ素原子、ゲルマニウム原子、チタン原子又はスズ原子を示す。
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子、ハロゲン原子、直鎖状、分岐状若しくは環状の炭素数１〜３０のアルキル基、直鎖状、分岐状若しくは環状の炭素数１〜３０のアルキル基を含む１価の非アルキル基、置換基を有していてもよい炭素数６〜６０のアリール基又は置換基を有していてもよい炭素数２〜６０の１価の複素環基を示す。
Ａｒ^２及びＡｒ^３は、それぞれ独立に、置換基を有していてもよい炭素数６〜６０の３価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜６０の３価の複素環基を示す。
なお、式（１）において、Ｒ^１及びＲ^２が結合している２つの炭素の間の結合は二重結合として記載されているが、Ｒ^１及びＲ^２が互いに結合して環を形成し、該環内に共役（交互の単結合及び二重結合）を形成している場合には、式（１）中の当該二重結合は該共役におけるπ電子が非局在化した結合を意味する。このことは、Ａｒ^１が結合している２つの炭素の間の結合についても同様である。］ The present invention provides a polymer having at least two structural units represented by formula (1) and having at least one structural unit represented by formula (2).

[Where:
X ¹ and X ² are each independently an oxygen atom, a sulfur atom or a group represented by ═C (A) ₂ (A is a monovalent optionally having a hydrogen atom, a halogen atom or a substituent. And two A's may be the same or different from each other.
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic carbon group having 1 to 30 carbon atoms. A monovalent non-alkyl group containing an alkyl group, an aryl group having 6 to 60 carbon atoms which may have a substituent, or a monovalent heterocyclic group having 2 to 60 carbon atoms which may have a substituent Indicates. R ¹ and R ² may be bonded to each other to form a hydrocarbon ring or a heterocyclic ring condensed with the ring to which they are bonded, and the hydrocarbon ring and the heterocyclic ring have a substituent. You may do it.
Ar ¹ represents an optionally substituted tetravalent aromatic hydrocarbon group having 6 to 60 carbon atoms or an optionally substituted tetravalent heterocyclic group having 4 to 60 carbon atoms. Show.
Y represents a carbon atom, a silicon atom, a germanium atom, a titanium atom or a tin atom.
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic carbon group having 1 to 30 carbon atoms. A monovalent non-alkyl group containing an alkyl group, an aryl group having 6 to 60 carbon atoms which may have a substituent, or a monovalent heterocyclic group having 2 to 60 carbon atoms which may have a substituent Indicates.
Ar ² and Ar ³ are each independently a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent or a carbon number having 3 to 60 which may have a substituent. A trivalent heterocyclic group is shown.
In Formula (1), the bond between the two carbons to which R ¹ and R ² are bonded is described as a double bond, but R ¹ and R ² are bonded to each other to form a ring. When a conjugation (alternate single and double bonds) is formed in the ring, the double bond in formula (1) means a bond in which π electrons in the conjugation are delocalized. To do. The same applies to the bond between the two carbons to which Ar ¹ is bonded. ]

  Such a polymer has a small ionization potential (a shallow HOMO (maximum occupied orbit)) and an excellent hole transport property.

  Further, in a preferred embodiment, the polymer of the present invention has excellent solubility in an organic solvent such as chloroform. The polymer of the present invention having such properties is excellent in handleability because an organic thin film element can be formed on a flexible substrate by a printing method.

  The present invention also provides an organic thin film containing the polymer of the present invention. Since the organic thin film of the present invention contains the polymer of the present invention, it exhibits excellent hole transportability, and in a preferred embodiment, it can be easily formed by a printing method.

  The present invention further provides an organic thin film element comprising the organic thin film of the present invention. As the organic thin film element, an organic thin film transistor and an organic thin film solar cell are suitable. Such an organic thin film element includes the organic thin film of the present invention, and since this organic thin film has excellent hole transport properties, it efficiently transports charges injected from the electrodes and charges generated by light absorption. be able to. Further, since this organic thin film has a narrow HOMO-LUMO (lowest empty orbit) gap, it can efficiently absorb light having a long wavelength. Therefore, the organic thin film element of the present invention can exhibit excellent performance, the organic thin film transistor has high hole mobility, and the organic thin film solar cell has high open-end voltage and photoelectric conversion efficiency.

  According to the present invention, a polymer having excellent hole transportability can be provided. Moreover, in preferable embodiment of this invention, the polymer which is excellent also in the solubility to an organic solvent can be provided. Furthermore, according to the present invention, an organic thin film that includes such a polymer of the present invention and exhibits excellent hole transportability, and an organic thin film element that can exhibit excellent performance by including such an organic thin film, In particular, an organic thin film transistor and an organic thin film solar cell can be provided.

It is a schematic cross section of the organic thin-film transistor which concerns on 1st Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 2nd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 3rd Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 4th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 5th Embodiment. It is a schematic cross section of the organic thin-film transistor concerning 6th Embodiment. It is a schematic cross section of the organic thin-film transistor which concerns on 7th Embodiment. It is a schematic cross section of the solar cell which concerns on suitable embodiment. It is a schematic cross section of the photosensor concerning a 1st embodiment. It is a schematic cross section of the optical sensor which concerns on 2nd Embodiment. It is a schematic cross section of the photosensor concerning a 3rd embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Polymer]
First, the polymer of the present invention will be described. The polymer of the present invention has at least two structural units represented by the formula (1) and at least one structural unit represented by the formula (2). Here, the “structural unit” of the polymer means a structural unit constituting the main chain of the polymer. The “polymer” includes both those usually classified as oligomers or polymers.

Hereinafter, the suitable structure of the structural unit represented by Formula (1) is demonstrated. First, in formula (1), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom or a group represented by ═C (A) ₂ . A each independently represents a hydrogen atom, a halogen atom or a monovalent group which may have a substituent.

When X ¹ or X ² has a group represented by ═C (A) ₂ , LUMO can be further lowered. Therefore, at least one of the two A is preferably an electron-attracting group, More preferably, each of the two A is an electron withdrawing group. The electron withdrawing group is preferably a cyano group, a nitro group, a formyl group, an alkanoyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or a halogen atom, more preferably a cyano group, a nitro group or a halogen atom, and a cyano group. Is more preferable. As the alkyl group of the alkanoyl group containing the alkyl group in the structure and the alkyl group of the alkoxycarbonyl group, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is still more preferable.

X ¹ and X ² are preferably an oxygen atom or a group represented by ═C (A) ₂ , and more preferably an oxygen atom because LUMO can be further reduced.

In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic group. A monovalent non-alkyl group containing an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 60 carbon atoms which may have a substituent, or an aryl group having 2 to 60 carbon atoms which may have a substituent. A heterocyclic group is shown. A part of carbon atoms in the alkyl group may be substituted with an oxygen atom, a sulfur atom, S═O, S (═O) ₂ or N—R (where R is a hydrogen atom, a halogen atom or a substituent). And a part or all of the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. R ¹ and R ² may be bonded to each other to form a hydrocarbon ring or a heterocyclic ring condensed with the ring to which they are bonded, and the hydrocarbon ring and the heterocyclic ring have a substituent. You may do it.

In R ¹ and R ² , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, in this specification, the same atom is illustrated also about the halogen atom mentioned later.

In R ¹ and R ² , the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms is preferably a linear, branched or cyclic alkyl group having 3 to 24 carbon atoms, and has 6 carbon atoms. More preferred is a linear or branched alkyl group of ˜20. However, a linear alkyl group is preferable for improving the intermolecular arrangement, while a branched alkyl group is preferable for increasing the solubility in an organic solvent, and these have desired properties. Can be selected. In addition, it is more preferable that R ¹ and R ² are the same group because the production of the polymer becomes easy.

  Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 3-methylbutyl group, pentyl group, hexyl group, 2-ethylhexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, 3,7-dimethyloctyl group, and 3,7,11-trimethyldodecyl group. In these alkyl groups, some or all of the hydrogen atoms may be substituted with halogen atoms, and the halogen atom to be substituted is preferably a fluorine atom.

  The monovalent non-alkyl group containing a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms is a group containing an alkyl group and an atom other than a carbon atom, and a group containing an alkyl group and an unsaturated bond. Say. Specific examples thereof include an alkoxy group, an alkylthio group, an alkyl-alkenyl group, an alkyl-alkynyl group, an alkylaryl group, an alkoxyaryl group, an alkylthioaryl group, an alkoxycarbonyl group, an alkylthiocarbonyl group, an alkylsilyl group, and an alkylamino group. Can be mentioned. Of these, an alkoxy group and an alkylthio group are preferable, and an alkylthio group is more preferable. In addition, as an alkyl group contained in groups other than the alkyl group containing a linear, branched or cyclic C1-C30 alkyl group, the thing similar to the above-mentioned alkyl group can be illustrated.

Examples of the aryl group having 6 to 60 carbon atoms which may have a substituent in R ¹ and R ² include a phenyl group, a phenyl group having an alkoxy group having 1 to 12 carbon atoms, and a carbon number of 1 to 12 carbon atoms. And a phenyl group, a 1-naphthyl group, and a 2-naphthyl group having an alkyl group. Among them, an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group having an alkoxy group having 1 to 12 carbon atoms and a phenyl group having an alkyl group having 1 to 12 carbon atoms are more preferable.

Examples of the heterocyclic group having 2 to 60 carbon atoms that may have a substituent in R ¹ and R ² include a thienyl group, a thienyl group having an alkyl group having 1 to 12 carbon atoms, a pyrrolyl group, and furyl. Group, a pyridyl group, and a pyridyl group having an alkyl group having 1 to 12 carbon atoms. Among these, a heterocyclic group having 3 to 20 carbon atoms is preferable, and a thienyl group, a thienyl group having an alkyl group having 1 to 12 carbon atoms, a pyridyl group, and a pyridyl group having an alkyl group having 1 to 12 carbon atoms are more preferable. The heterocyclic group refers to a group in which at least one atom constituting the ring is a heteroatom in an organic group having a cyclic structure, and the heterocyclic group is an aromatic heterocyclic group. Is preferred.

In the case where R ¹ and R ² are not bonded to each other to form a ring, at least one of R ¹ and R ² , preferably each independently, are both linear, branched or cyclic carbon number 1 to 30 alkyl groups, linear, branched or cyclic fluoroalkyl groups having 1 to 30 carbon atoms, linear, branched or cyclic alkoxy groups having 1 to 30 carbon atoms, linear, branched or cyclic It is preferably a fluoroalkoxy group having 1 to 30 carbon atoms, a linear, branched or cyclic alkylthio group having 1 to 30 carbon atoms or a fluoroalkylthio group having 1 to 30 carbon atoms. More preferably a linear alkyl group having 3 to 24 carbon atoms, a linear or branched fluoroalkyl group having 3 to 24 carbon atoms, or a linear or branched alkoxy group having 3 to 24 carbon atoms. State Further, a branched alkyl group having 6 to 20 carbon atoms or a linear or branched fluoroalkyl group having 6 to 20 carbon atoms is more preferable. By using R ¹ and R ² as these groups, solubility in an organic solvent is improved.

In addition, when R ¹ and R ² are bonded to each other to form a ring, the ring is a hydrocarbon ring that may have a substituent or a heterocyclic ring that may have a substituent. May be. From the viewpoint of improving the solubility in an organic solvent, the ring formed by bonding R ¹ and R ² to each other is preferably a hydrocarbon ring having a substituent or a heterocyclic ring having a substituent. The hydrocarbon ring that may have a substituent is preferably an aromatic hydrocarbon ring, and the heterocyclic ring that may have a substituent is preferably an aromatic heterocyclic ring. The substituent, preferably a same groups as the preferred groups as R ¹ and R ² when R ¹ and R ² described above do not form a ring together. By using these groups as substituents, solubility in organic solvents is improved.

  Examples of the hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, a perylene ring, and a fluorene ring, and a benzene ring is preferable.

  Examples of the heterocyclic ring include a thiophene ring, a thienothiophene ring, a furan ring, a pyrrole ring, and a pyridine ring, and a thiophene ring and a thienothiophene ring are preferable.

In Formula (1), Ar ¹ is an optionally substituted tetravalent aromatic hydrocarbon group having 6 to 60 carbon atoms or 4 having 4 to 60 carbon atoms which may have a substituent. A valent heterocyclic group is shown.

In Ar ¹ , the optionally substituted tetravalent aromatic hydrocarbon group having 6 to 60 carbon atoms refers to an aromatic hydrocarbon compound having 6 to 60 carbon atoms that may have a substituent. The tetravalent group remove | excluding four hydrogen atoms on the aromatic ring in is shown. The aromatic hydrocarbon compound may be a single ring or a condensed ring. Among these, since superior solubility is obtained and production is easy, a condensed ring in which a single ring or 5 or less rings are condensed is preferable, and a condensed ring in which a single ring or two rings are condensed is preferable. More preferred is a single ring.

  Examples of the aromatic hydrocarbon compound include benzene, naphthalene, anthracene, fluorene, pyrene, and perylene. Of these, benzene or naphthalene is preferable, and benzene is more preferable.

  Examples of the substituent in the tetravalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent include a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, and carbon. An aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkanoyl group having 1 to 12 carbon atoms, an aryloxy group having 6 to 60 carbon atoms, a heterocyclic group having 2 to 60 carbon atoms, an amino group, and a nitro group Group and cyano group. Examples of the saturated hydrocarbon group as a substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and examples of the unsaturated hydrocarbon group include a vinyl group and 1-propenyl. Group, allyl group, propargyl group, isopropenyl group, 1-butenyl group and 2-butenyl group. In addition, as the aryl group as a substituent, phenyl group, naphthyl group, alkoxy group as methoxy group, ethoxy group, propoxy group, alkanoyl group as methanoyl group, ethanoyl group, propanoyl group, propenoyl group, benzoyl group The aryloxy group is a phenyloxy group or a phenyloxy group having an alkyl group having 1 to 12 carbon atoms, and the heterocyclic group is, for example, a thienyl group or an alkyl group having 1 to 12 carbon atoms. Group, pyrrolyl group, furyl group, pyridyl group.

  The tetravalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent refers to four on the heterocyclic ring in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. A tetravalent group excluding a hydrogen atom is shown. The heterocyclic compound may be a monocyclic ring or a condensed ring, and the heterocyclic compound is preferably an aromatic heterocyclic compound. Among these, since excellent solubility is obtained and production is easy, a condensed ring in which a single ring or 5 or less rings are condensed is preferable, and a condensed ring in which a single ring or two rings are condensed is more preferable. Preferably, a single ring is more preferable.

  Examples of the heterocyclic compound include pyridine, thiophene, thienothiophene, dithienothiophene, benzothiophene, benzodithiophene, dibenzothiophene, pyrrole, quinoline, and indole. Of these, thiophene, thienothiophene or pyridine is preferable, and thiophene is more preferable.

  Examples of the substituent in the tetravalent heterocyclic group having 4 to 60 carbon atoms which may have a substituent include a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, and 6 to 60 carbon atoms. Aryl group, C 1-12 alkoxy group, C 1-12 alkanoyl group, C 6-60 aryloxy group, C 2-60 heterocyclic group, amino group, nitro group, cyano group Is mentioned. Examples of these substituents include the same groups as described above.

Ar ¹ is preferably a tetravalent group excluding four hydrogen atoms on the aromatic ring in benzene or thiophene.

In the polymer according to this embodiment, the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (3).

In formula (3), X ¹ , X ² , R ¹ and R ² have the same meanings as described above, and Z ¹ represents a group represented by formula (i), a group represented by formula (ii), and a formula A group represented by (iii), a group represented by formula (iv), a group represented by formula (v), a group represented by formula (vi), a group represented by formula (vii), a formula A group represented by (viii) or a group represented by formula (ix) is shown. When Z ¹ is a group represented by the formula (i), (ii) or (ix), the group represented by the formula (3) has a furan ring, thiophene ring or pyrrole ring structure, respectively. Since these rings, particularly thiophene rings, exhibit suitable electrical properties, a polymer having these rings can exhibit various electrical characteristics.
In Formula (3), the bond between the two carbons to which R ¹ and R ² are bonded is described as a double bond, but R ¹ and R ² are bonded to each other to form a ring. When a conjugation (alternate single and double bonds) is formed in the ring, the double bond in formula (3) means a bond in which π electrons in the conjugation are delocalized. To do.

In formulas (vii), (viii) and (ix), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a monovalent group optionally having a hydrogen atom, a halogen atom or a substituent. R ¹¹ and R ¹² may be bonded to each other to form a ring. In addition, the group represented by the formula (viii) may be horizontally reversed.

As the monovalent group in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , for example, a linear or branched chain group (here, the chain group refers to a group having no cyclic structure) .) A monovalent cyclic group (herein, the cyclic group represents a group having a cyclic structure. This cyclic structure may be a monocyclic ring or a condensed ring, may be a carbocyclic ring or a heterocyclic ring, and may be saturated) May be unsaturated.). The monovalent group may be an electron donating group or an electron withdrawing group.

As the substituent which the monovalent group in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may have, a substituent composed of 20 or less carbon atoms is preferred, and a substituent composed of 17 or less carbon atoms Groups are more preferred. Examples of the substituent include a group having an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms in its structure (for example, an alkoxy group, an alkylamino group, or an alkoxycarbonyl group), and 6 to 6 carbon atoms. Examples include 20 aryl groups, halogen atoms, nitro groups, and cyano groups.

  The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. In these groups, some or all of the hydrogen atoms may be substituted with halogen atoms, and the halogen atom to be substituted is preferably a fluorine atom. The alkyl group in which part or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms is preferably a linear or branched fluoroalkyl group having 1 to 10 carbon atoms.

  Examples of the alkyl group as the substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, A decyl group is mentioned. Examples of the alkyl group in a group containing an alkyl group in its structure (for example, an alkoxy group, an alkylamino group, and an alkoxycarbonyl group) include the same groups as described above.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and more preferably a hydrogen atom, an alkyl group or an aryl group.

The structural unit represented by the formula (1) is also preferably a structural unit represented by the formula (4).

In formula (4), X ¹ , X ² and Ar ¹ are as defined above,
Z ² is a group represented by the following formula (xi), a group represented by the formula (xii), a group represented by the formula (xiii), a group represented by the formula (xiv), or the formula (xv) A group represented by formula (xvi), a group represented by formula (xvii), a group represented by formula (xviii) or a group represented by formula (xix).
R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, or a monovalent group that may have a substituent.
In addition, in Formula (4), although the coupling | bonding between two carbons which Ar < ¹ > has couple | bonded is described as a double bond, conjugation in the ring of Ar < ¹ > (alternate single bond and double bond) Is formed, the double bond in formula (4) means a bond in which π electrons in the conjugate are delocalized.

In formula (xvii), formula (xviii), and formula (xix), R ²¹ , R ²² , R ^23, and R ²⁴ each independently represent a hydrogen atom, a halogen atom, or a monovalent group that may have a substituent. R ²¹ and R ²² may be bonded to each other to form a ring. Further, the group represented by the formula (xviii) may be horizontally reversed.

In the formula (4), when the group represented by Z ² is a group represented by the formula (xi), (xii), (xiii), (xiv), (xv) or (xvi), R ^At least one of ⁵ and R ⁶ is preferably a group similar to the group suitable as R ¹ and R ² described above. On the other hand, when the group represented by Z ² is a group represented by the formula (xvii), (xviii) or (xix), R ⁵ , R ^{6 and the} formula (xvii), (xviii) or (xix) It is preferable that at least one of the substituents (R ²¹ , R ²² , R ^23, or R ²⁴ ) in the group represented by (1) is a group similar to the groups suitable as R ¹ and R ² described above. By satisfying these conditions, the solubility of the polymer in the organic solvent becomes better.

Z ² is a group represented by any of formulas (xi) to (xix) and represented by any one of formulas (xi), (xii), (xiii), (xvii), (xviii), and (xix). The group represented by formula (xii) and (xvii) is more preferable, and the group represented by formula (xvii) is still more preferable. In the case of a group represented by the formula (xvii), at least one of R ²¹ and R ²² , preferably both independently, are each an alkyl group having 1 to 25 carbon atoms, a fluoroalkyl group having 1 to 25 carbon atoms, a carbon number It is preferably an alkoxy group having 1 to 25 carbon atoms, a fluoroalkoxy group having 1 to 25 carbon atoms, an alkylthio group having 1 to 25 carbon atoms, or a fluoroalkylthio group having 1 to 25 carbon atoms, and an alkyl group having 1 to 25 carbon atoms or A C1-C25 fluoroalkyl group is more preferable, a C6-C20 alkyl group or a C6-C20 fluoroalkyl group is still more preferable, and a C6-C12 alkyl group is especially preferable. These alkyl groups and the alkyl group of the group containing the alkyl group in the structure may be linear, branched or cyclic. By using these groups, the solubility of the polymer in an organic solvent is improved.

In formula (4), the monovalent group which may have a substituent in R ⁵ and R ⁶ includes an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, and 1 carbon atom. Examples thereof include an -18 alkoxy group, a C1-C18 fluoroalkoxy group, a C1-C18 alkylthio group, or a C1-C18 fluoroalkylthio group.

It is preferable that the structural unit represented by Formula (1), Formula (3), and Formula (4) is a structural unit represented by Formula (5).

In formula (5), X ¹ , X ² , R ⁵ , R ⁶ , Z ¹ and Z ² are as defined above.

In the formula (5), when the group represented by Z ² is a group represented by the formula (xi), (xii), (xiii), (xiv), (xv) or (xvi), R ^At least one of ⁵ and R ⁶ is preferably a group similar to the group suitable as R ¹ and R ² described above. On the other hand, when the group represented by Z ² is a group represented by the formula (xvii), (xviii) or (xix), R ⁵ , R ^{6 and the} formula (xvii), (xviii) or (xix) It is preferable that at least one of the substituents (R ²¹ , R ²² , R ^23, or R ²⁴ ) in the group represented by (1) is a group similar to the groups suitable as R ¹ and R ² described above. By satisfying these conditions, the solubility of the polymer in the organic solvent is improved.

Z ² is a group represented by any of formulas (xi) to (xix) and represented by any one of formulas (xi), (xii), (xiii), (xvii), (xviii), and (xix). The group represented by formula (xii) and (xvii) is more preferable, and the group represented by formula (xvii) is still more preferable. In the case of a group represented by the formula (xvii), at least one of R ²¹ and R ²² , preferably both independently, are each an alkyl group having 1 to 25 carbon atoms, a fluoroalkyl group having 1 to 25 carbon atoms, a carbon number It is preferably an alkoxy group having 1 to 25 carbon atoms, a fluoroalkoxy group having 1 to 25 carbon atoms, an alkylthio group having 1 to 25 carbon atoms, or a fluoroalkylthio group having 1 to 25 carbon atoms, and an alkyl group having 1 to 25 carbon atoms or A C1-C25 fluoroalkyl group is more preferable, a C6-C20 alkyl group or a C6-C20 fluoroalkyl group is still more preferable, and a C6-C12 alkyl group is especially preferable. These alkyl groups and the alkyl group of the group containing the alkyl group in the structure may be linear, branched or cyclic. By using these groups, the solubility of the polymer in an organic solvent is improved.

In formula (5), the monovalent group which may have a substituent in R ⁵ and R ⁶ includes an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, and 1 carbon atom. Examples thereof include an -18 alkoxy group, a C1-C18 fluoroalkoxy group, a C1-C18 alkylthio group, or a C1-C18 fluoroalkylthio group.

  Examples of the structural unit represented by Formula (1), Formula (3), Formula (4), and Formula (5) include structural units represented by the following chemical formulas.

  Next, the suitable structure of the structural unit represented by Formula (2) is demonstrated. First, in formula (2), Y represents a carbon atom, a silicon atom, a germanium atom, a titanium atom or a tin atom, preferably a silicon atom, a germanium atom, a titanium atom or a tin atom, and more preferably a silicon atom or a germanium atom. A silicon atom is particularly preferable. When Y is a silicon atom, the group represented by Formula (2) has a silole ring structure. Since a silole ring exhibits suitable electrical properties, a polymer having a silole ring can exhibit various electrical characteristics.

In formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic group. A monovalent non-alkyl group containing an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 60 carbon atoms which may have a substituent, or an aryl group having 2 to 60 carbon atoms which may have a substituent. A monovalent heterocyclic group is shown.

Specific examples of R ³ and R ⁴ include the groups exemplified for R ¹ and R ² above. As R ³ and R ⁴ , the solubility in a solvent is high, and therefore a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a linear, branched or cyclic carbon group having 1 to 30 carbon atoms. A monovalent non-alkyl group containing the above alkyl group is preferred. As the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 3 to 24 carbon atoms is preferable, and a linear or branched alkyl group having 6 to 20 carbon atoms or A branched alkyl group is more preferred. However, a linear alkyl group is preferable for improving the intermolecular arrangement, while a branched alkyl group is preferable for increasing the solubility in an organic solvent, and these have desired properties. Can be selected. In addition, it is more preferable that R ³ and R ⁴ are the same group because the production of the polymer becomes easy.

In Formula (2), Ar ² and Ar ³ may each independently have a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a substituent that may have a substituent. A trivalent heterocyclic group having 3 to 60 carbon atoms is shown. The trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent is an aromatic ring in an aromatic hydrocarbon compound having 6 to 60 carbon atoms which may have a substituent. The trivalent group remove | excluding three hydrogen atoms of is shown. The trivalent heterocyclic group having 3 to 60 carbon atoms which may have a substituent refers to three of the heterocyclic rings in the heterocyclic compound having 3 to 60 carbon atoms which may have a substituent. A trivalent group excluding a hydrogen atom is shown, and the heterocyclic group is preferably an aromatic heterocyclic group. Specific examples of these aromatic hydrocarbon compounds and heterocyclic compounds include the aromatic hydrocarbon compounds and heterocyclic compounds exemplified in the above Ar ¹ section.

In the polymer according to the present embodiment, the structural unit represented by the formula (2) is preferably a structural unit represented by the formula (6).

In formula (6), Y, R ³ and R ⁴ have the same meanings as described above. W ³ and W ⁴ are each independently represented by a group represented by —C (R ′) ═ (R ′ represents a hydrogen atom, a halogen atom or a monovalent group) or —N═. Indicates a group. Incidentally, the W ³ and W ⁴ are the same, since the production of the polymer is facilitated, and more preferred.

It is preferable that both W ³ and W ⁴ are a group represented by —C (R ′) ═ or a group represented by —N═. A polymer in which W ³ and W ⁴ are groups represented by —N═ has higher electron acceptability than a polymer not containing a nitrogen atom, and as a result, the LUMO of the polymer can be adjusted. it can.

In Formula (6), Z ³ and Z ⁴ are each independently a group represented by the following Formula (xxi), a group represented by Formula (xxii), a group represented by Formula (xxiii), a formula A group represented by (xxiv), a group represented by formula (xxv), a group represented by formula (xxvi), a group represented by formula (xxvii), a group or a formula represented by formula (xxviii) It is a group represented by (xxix), and any one of groups represented by formulas (xxii) and (xxvii) is preferable, and a group represented by formula (xxii) is particularly preferable. When W ³ and W ⁴ are —C (R ′) = and Z ³ or Z ⁴ is a group represented by the formula (xxi), (xxii) or (xxix), the formula (6) Each group to be formed has a furan ring, thiophene ring or pyrrole ring structure. Since these rings, particularly thiophene rings, exhibit suitable electrical properties, a polymer having these rings can exhibit various electrical characteristics. Incidentally, when Z ³ and Z ⁴ are the same, since the production of the polymer is facilitated, and more preferred.

In the formulas (xxvii), (xxviii) and (xxix), R ³¹ , R ³² , R ³³ and R ³⁴ each independently represents a monovalent group optionally having a hydrogen atom, a halogen atom or a substituent. R ³¹ and R ³² may be bonded to each other to form a ring. Further, the group represented by the formula (xxviii) may be horizontally reversed.

Examples of the monovalent group represented by R ³¹ , R ³² , R ³³ and R ³⁴ include the same groups as the monovalent group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ .

As a structural unit represented by Formula (2) and Formula (6), the structural unit represented by the following chemical formula can be illustrated.

The polymer according to this embodiment may further have a structural unit represented by the formula (7). This widens the range in which solubility or mechanical, thermal or electronic properties can be changed. The structural unit represented by the formula (7) is different from the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2).

In formula (7), Ar ⁴ represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent heterocyclic group which may have a substituent. The divalent aromatic hydrocarbon group which may have a substituent is a divalent group excluding two hydrogen atoms on the aromatic ring in the aromatic hydrocarbon compound which may have a substituent. Indicates. The divalent heterocyclic group which may have a substituent refers to a divalent group excluding two hydrogen atoms on the heterocyclic ring in the heterocyclic compound which may have a substituent, The heterocyclic group is preferably an aromatic heterocyclic group. Specific examples of the aromatic hydrocarbon compound and the heterocyclic compound include the aromatic hydrocarbon compound and the heterocyclic compound exemplified in the above Ar ¹ section.

In the polymer according to this embodiment, the structural unit represented by the formula (7) is preferably a structural unit represented by the formula (8).

In formula (8), R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ⁷ and R ⁸ may be bonded to each other to form a ring. Specific examples of R ⁷ and R ⁸ include the groups exemplified for R ¹ and R ² above. R ⁷ and R ⁸ are a monovalent group including a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. Non-alkyl groups are preferred, hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 30 carbon atoms are more preferred, hydrogen atoms, straight-chain or branched alkyl groups having 6 to 20 carbon atoms are more preferred. Further preferred.
However, a linear alkyl group is preferable for improving the intermolecular arrangement, while a branched alkyl group is preferable for increasing the solubility in an organic solvent, and these have desired properties. Can be selected. In addition, it is more preferable that R ⁷ and R ⁸ are the same group because the production of the polymer becomes easy.

In formula (8), Z ⁵ is a group represented by formula (xxxi), a group represented by formula (xxxii), a group represented by formula (xxxiii), a group represented by formula (xxxiv), A group represented by formula (xxxv), a group represented by formula (xxxvi), a group represented by formula (xxxvii), a group represented by formula (xxxviii) or a group represented by formula (xxxix) Yes, and is preferably a group represented by the formula (xxxii). When Z ⁵ is a group represented by the formula (xxxi), (xxxii) or (xxxix), the group represented by the formula (8) has a furan ring, thiophene ring or pyrrole ring structure, respectively. Since these rings, particularly thiophene rings, exhibit suitable electrical properties, a polymer having these rings can exhibit various electrical characteristics.

In formulas (xxxvii), (xxxviii) and (xxxix), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent group optionally having a substituent. R ⁴¹ and R ⁴² may be bonded to each other to form a ring. Further, the group represented by the formula (xxxviii) may be horizontally reversed.

Examples of the monovalent group in R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ include the same groups as the monovalent group in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ .

  Among the polymers according to this embodiment, those having a structure in which the formulas (1) and (2) are alternately arranged are preferable because the hole transport property is improved. As such a structure, what has a structural unit represented by Formula (11) is preferable.

In the formula (11), X ¹ , X ² , Y, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are as defined above. s and t each independently represent an integer of 0 to 6, and an integer of 0 to 2 is preferable. When there are a plurality of Ar ^{4 s} , they may be the same or different. Incidentally, if a plurality of Ar ⁴ are the same, since the production of the polymer is facilitated, and more preferred.

In the polymer according to this embodiment, the structural unit represented by the formula (11) is more preferably a structural unit represented by the formula (12).

In the formula (12), X ¹ , X ² , Y, R ¹ , R ² , R ³ , R ⁴ , R ⁷ , R ⁸ , W ³ , W ⁴ , Z ¹ , Z ³ , Z ⁴ , Z ⁵ , s and t are as defined above, and when there are a plurality of R ⁷ , R ⁸ and Z ⁵ , they may be the same or different. In addition, since several manufacture of a polymer becomes easy when several R < ⁷ >, R < ⁸ > and Z < ⁵ > are respectively the same, it is preferable.

In the polymer according to this embodiment, the structural unit represented by the formula (12) is more preferably a structural unit represented by the formula (13).

In the formula (13), X ¹ , X ² , Y, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , W ³ , W ⁴ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , s, and t are as defined above, and when there are a plurality of R ⁷ , R ^8, and Z ⁵ , they may be the same or different. In addition, since several manufacture of a polymer becomes easy when several R < ⁷ >, R < ⁸ > and Z < ⁵ > are respectively the same, it is preferable.

  In the polymer according to the present embodiment, in addition to the structural unit represented by the above formula (11), the structural unit represented by the above formula (12), or the structural unit represented by the above (13), the above ( The structural unit represented by 7) or the structural unit represented by (8) above may be included.

As a polymer which concerns on this embodiment, what has a structure represented by Formula (14)-(26) is preferable. In addition, each code | symbol in Formula (14)-(26) is respectively synonymous with the same code | symbol demonstrated above, respectively. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a monovalent group. k and k ′ each independently represent an integer of 1 to 6. Specific examples of R ⁹ and R ¹⁰ include the groups exemplified for R ⁷ and R ⁸ above. A plurality of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different. In addition, since manufacture of a polymer becomes easy when several R < ⁷ >, R <^8> , R < ⁹ > and R < ¹⁰ > are respectively the same, it is preferable.

  Examples of the terminal group of the polymer include a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an alkanoyl group, an amino group, an aryl group, and a monovalent heterocyclic group (one of hydrogen atoms bonded to these groups). Part or all may be substituted with a fluorine atom), a group having an α-fluoroketone structure, other electron-donating groups and electron-withdrawing groups. Of these, an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are preferable. The terminal group preferably has a conjugated bond continuous with the conjugated structure of the main chain. Examples of such a terminal group include an aryl group bonded to the main chain via a carbon-carbon bond and a monovalent heterocyclic group.

  Furthermore, a polymerization active group is also mentioned as a terminal group of a polymer. When it has a polymerization active group as a terminal group, the polymer can also be used as a precursor for obtaining a higher molecular weight polymer. When used as such a precursor, the polymer preferably has two polymerization active groups in the molecule.

Polymerization active groups include halogen atoms, carboxyl groups, alkoxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, arylalkylsulfonyl groups, alkylstannyl groups, arylstannyl groups, arylalkylstannyl groups, boric acid ester residues , Sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid residue (group represented by —B (OH) ₂ ), formyl group, and vinyl group. Of these, a halogen atom, an alkylstannyl group, and a borate ester residue are preferable. Here, the boric acid ester residue is a monovalent group having a structure in which one of the bonds of the boron atom in the boric acid ester is replaced with a bond, for example, the following formulas (100) to (103 ) Is represented.

  Among the above reactive groups, the alkyl group in the alkylsulfonyl group, arylalkylsulfonyl group, alkylstannyl group, and arylalkylstannyl group, which is a group containing an alkyl group in its structure, has 1 to 12 carbon atoms. Alkyl groups having 1 to 6 carbon atoms are more preferable. In addition, as the aryl group in the arylsulfonyl group, arylalkylsulfonyl group, arylstannyl group, arylalkylstannyl group, which is a group containing an aryl group in its structure, an aryl group having 6 to 20 carbon atoms is preferable, More preferred are aryl groups having 6 to 10 carbon atoms.

  In addition, when the polymer of the present invention is used as an organic thin film, if the polymerization active group remains as a terminal group, the element characteristics and durability when an organic thin film element is formed may be reduced. The active group may be substituted with a stable group.

  As the polymer of the present invention, those having the structures represented by the following general formulas (27) to (37) are particularly suitable because they can achieve both higher hole transportability and excellent solubility in a solvent. is there.

In the above formulas (27) to (37), R ⁰ and R ⁰⁰ each independently represent the above-described terminal group, and an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group is preferable. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are as defined above, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^When there are a plurality of ⁹ and R ^{10 s} , they may be the same or different. J and j ′ represent an integer of 1 to 6, and p represents an integer of 1 or more. p can be appropriately selected depending on the method of forming the organic thin film using the polymer. That is, if the polymer has sublimation properties, it can be formed into an organic thin film using a vapor phase growth method such as a vacuum evaporation method. In this case, p is preferably 2 to 10, 5 is more preferable. On the other hand, when forming an organic thin film by the method of apply | coating the solution which melt | dissolved the polymer in the organic solvent, 3-500 are preferable, 6-300 are more preferable, and 20-200 are still more preferable.

And since the polymer mentioned above has the favorable uniformity of a film | membrane when an organic thin film is formed by application | coating, it is preferable in the number average molecular weight of polystyrene conversion being 1 * 10 < ³ > -1 * 10 < ⁸ >. It is more preferable that it is * 10 < ³ > -1 * 10 < ⁶ >, and it is still more preferable that it is 4 * 10 < ³ > -1 * 10 < ⁵ >.

[Method for producing polymer]
Next, the manufacturing method of the polymer of embodiment mentioned above is demonstrated. The polymer may be produced by any method, but is preferably produced by the production method described below.

That is, the polymer according to this embodiment includes a monomer compound represented by the following formula (1-m), the following formula (3-m), the following formula (4-m), or the following formula (5-m); A monomer compound represented by the following formula (2-m) or the following formula (6-m), and a monomer compound represented by the following formula (7-m) or the following formula (8-m) as necessary. It is preferable to produce by reacting. In this case, V ¹ and V ² in one monomer compound react with V ¹ or V ² in another monomer compound, respectively, to form a bond, and a polymer is formed by continuously generating such a reaction. . The monomer compounds represented by formula (1-m), formula (3-m), formula (4-m), or formula (5-m) are represented by formula (1), formula (3), formula ( 4) corresponds to the structural unit represented by formula (5), and the monomer compound represented by formula (2-m) or formula (6-m) corresponds to formula (2) or formula (6), respectively. The monomer compound represented by the formula (7-m) or the formula (8-m) corresponds to the structural unit represented by the formula (7) or the formula (8), respectively.

  In addition, the polymer according to the present embodiment can be produced by further reacting the synthetic intermediate after obtaining the synthetic intermediate by reacting the monomer compound as a raw material. As the synthetic intermediate, a compound represented by the following formula (11-m), the following formula (12-m) or the formula (13-m) is preferable.

Formulas (1-m), (2-m), (3-m), (4-m), (5-m), (6-m), (7-m), (8-m), ( 11-m), (12-m) and (13-m), X ¹ , X ² , Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , W ³ , W ⁴ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , s and t are as defined above, and R ⁷ , R ⁸ , When there are a plurality of Ar ⁴ and Z ⁵ , they may be the same or different. In addition, since manufacture of a polymer becomes easy when several R < ⁷ >, R < ⁸ >, Ar < ⁴ > and Z < ⁵ > are the same, it is preferable.
V ¹ and V ² each independently represent a polymerization reactive group. Examples of the polymerization reactive group include a hydrogen atom, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an arylalkylsulfonyl group, an alkylstannyl group, an arylstannyl group, an arylalkylstannyl group, a boric acid ester residue, Examples include sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid residue, formyl group, and vinyl group.

Since the monomer compound is easily synthesized and easily reacted, V ¹ and V ² are each independently a halogen atom, alkylsulfonyl group, arylsulfonyl group, arylalkylsulfonyl group, alkylstannyl group, boron Acid ester residues and boric acid residues are preferred. When the polymerization reactive group is any of these groups, the reaction between the monomer compounds is likely to occur, which is advantageous in terms of synthesis.

Examples of the polymer production method include a method using Wittig reaction, a method using Heck reaction, a method using Horner-Wadsworth-Emmons reaction, a method using Knoevenagel reaction, a method using Suzuki coupling reaction, and a Grignard reaction. A method using a Stille reaction, a method using a Ni (0) catalyst, a method using an oxidizing agent such as FeCl _{3, a} method using an electrochemical oxidation reaction, or decomposition of an intermediate compound having an appropriate leaving group The method by is mentioned.

  Among these, a method using a Wittig reaction, a method using a Heck reaction, a method using a Horner-Wadsworth-Emmons reaction, a method using a Knoevenagel reaction, a method using a Suzuki coupling reaction, a method using a Grignard reaction, and a Stille reaction are used. The method and the method using a Ni (0) catalyst are preferable because the structure of the polymer can be easily controlled. Furthermore, a method using a Suzuki coupling reaction, a method using a Grignard reaction, a method using a Stille reaction, and a method using a Ni (0) catalyst are more preferable because the raw materials are easily available and the reaction operation is simple.

  The above formulas (1-m), (2-m), (3-m), (4-m), (5-m), (6-m), (7-m), (8-m), The monomer compounds represented by (11-m), (12-m) and (13-m) are dissolved in an organic solvent as necessary, and an alkali or a suitable catalyst is used, and the melting point of the organic solvent. The reaction can be conducted at a boiling point or higher.

  The organic solvent used in the reaction varies depending on the monomer compound used and the type of reaction, but it is preferable that deoxygenation treatment is sufficiently performed in order to suppress side reactions. Examples of the organic solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, and chloropentane. Halogenated saturated hydrocarbons such as bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane; halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; methanol, ethanol, propanol, isopropanol, butanol, tert Alcohols such as butyl alcohol; carboxylic acids such as formic acid, acetic acid, propionic acid; dimethyl ether, diethyl ether, methyl-tert-butyl ether Le, tetrahydrofuran, tetrahydropyran, dioxane and the like can be mentioned. In place of the organic solvent, inorganic acids such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, and nitric acid may be used.

  When an alkali or an appropriate catalyst is added, these may be selected according to the reaction to be generated. As the alkali or catalyst, those which are sufficiently dissolved in the solvent used for the reaction are preferable.

  The reaction is preferably allowed to proceed under an inert atmosphere. Furthermore, similarly, during the reaction, it is preferable to perform a dehydration treatment (however, this is not the case in the case of a two-phase reaction with water such as a Suzuki coupling reaction).

  After the reaction, the polymer can be obtained, for example, by performing usual post-treatment such as extraction with an organic solvent after stopping the reaction with water, and then distilling off the solvent. Isolation and purification of the obtained polymer can be performed by a method such as fractionation by chromatography or recrystallization.

  In addition, when the polymer is used as a material for an organic thin film element, its purity may affect the element characteristics. Therefore, each monomer compound before the reaction was purified by a method such as distillation, sublimation purification, and recrystallization. It is preferable to react (polymerize) later. After the synthesis of the polymer, it is preferable to carry out a purification treatment such as reprecipitation and fractionation by chromatography. In order to increase the purity and obtain good device characteristics, it is preferable to further purify the polymer obtained by the above-described production method by a method such as distillation, sublimation purification, and recrystallization.

  In the above example, the structural unit represented by the formula (1), the formula (3), the formula (4), or the formula (5), the structural unit represented by the formula (2) or the formula (6), and an arbitrary unit The method for producing a polymer having a structural unit represented by formula (7) or formula (8) has been described as an example, but a polymer having a structural unit other than these may be selected appropriately from monomer compounds. Can be produced in the same manner as in the above reaction.

[Composition]
Next, the composition according to a preferred embodiment will be described. The composition according to this embodiment includes the polymer of the preferred embodiment described above.

  The composition may include one type of the polymer according to this embodiment alone, or may include a combination of two or more types. Moreover, a composition can change a component suitably according to the use. Hereinafter, the composition for organic thin film production which can use suitably the polymer concerning this embodiment is explained.

  The composition for producing an organic thin film enhances the electron transport property or hole transport property of the organic thin film, so that it is a low-molecular compound or a polymer compound (hereinafter referred to as “electron transport material”) having an electron transport property, and a hole transport property. A low molecular compound or a high molecular compound (hereinafter referred to as “hole transporting material”) having a mixture is preferably contained.

  A well-known material can be used as the hole transporting material. Specific examples thereof include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, polysilanes having aromatic amines in side chains or main chains. Examples thereof include siloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

As the electron transporting material, known materials can be used. Specific examples thereof include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, metal complexes of diphenoquinone derivatives, or 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerenes and derivatives thereof such as C _60.

  When the composition for organic thin film production contains a hole transporting material and / or an electron transporting material, the content can be appropriately adjusted according to the desired properties. For example, the polymer 100 according to this embodiment is used. It is preferable in it being 1-1000 mass parts with respect to a mass part, and it is more preferable in it being 10-300 mass parts.

The composition for producing an organic thin film may contain a charge generating material in order to generate a charge by light absorbed in the organic thin film. As the charge generation material, known materials can be used. Specific examples thereof include azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone compounds and derivatives thereof, squarylium compounds. and its derivatives, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes and derivatives thereof such as C _60.

  The content in the case where the composition for producing an organic thin film contains a charge generation material can be appropriately adjusted according to desired properties, but for example, 1 to 100 parts by mass of the polymer according to this embodiment. 1000 parts by mass is preferable, and 10 to 300 parts by mass is more preferable.

  The composition for producing an organic thin film may contain other materials necessary for developing various functions. Other materials include, for example, a sensitizer for sensitizing the function of generating charge by absorbed light, a stabilizer for increasing stability, and a UV absorber for absorbing ultraviolet (UV) light. Etc.

  Since the composition for organic thin film manufacture can improve mechanical characteristics, it may contain polymer materials other than the polymer which concerns on this embodiment as a polymer binder. As the polymer binder, those not extremely disturbing the electron transport property or hole transport property are preferable, and those having no strong absorption against visible light are preferably used.

  Examples of such a polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. Examples include derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The composition for producing an organic thin film can be dissolved in a solvent and used as a solution in order to facilitate film formation. Any solvent may be used as long as it dissolves the polymer according to the present embodiment, an electron transporting material, a hole transporting material, a charge generation material, and a polymer binder mixed therewith. For example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene; carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Halogenated saturated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane; Halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; tetrahydrofuran, tetrahydro Examples include ether solvents such as pyran. Although the polymer which concerns on this embodiment is based also on the structure and molecular weight, 0.1 mass% or more can be normally melt | dissolved in these solvents. The upper limit of the amount of the polymer dissolved in the solvent is not particularly limited, but can be, for example, 10% by mass or less.

[Organic thin film]
Next, an organic thin film according to a preferred embodiment will be described. The organic thin film which concerns on this embodiment contains the polymer of suitable embodiment mentioned above, or the composition for organic thin film manufacture of suitable embodiment mentioned above.

  The organic thin film preferably has a thickness of 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  Examples of the method for producing an organic thin film according to the present embodiment include, in addition to the polymer according to the present embodiment, an electron transport material, a hole transport material, a charge generation material, and a polymer binder, which are mixed as necessary. And a method of forming a film using the obtained solution. Moreover, when the polymer which concerns on this embodiment has sublimability, a thin film can also be formed by a vacuum evaporation method.

  Examples of film forming methods using a solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing. Application methods such as flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating can be used. Of these, spin coating, flexographic printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred.

  The step of manufacturing the organic thin film may include a step of orienting the polymer according to the present embodiment. By orienting the polymer by this step, the main chain molecules or the side chain molecules are aligned in one direction, so that the electron mobility or hole mobility by the organic thin film is improved.

  As a method for aligning the polymer according to this embodiment, a method known as a liquid crystal alignment method can be used. Among these, the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are more preferable.

  Further, the step of manufacturing the organic thin film may include a step of performing an annealing process after the film formation. By this step, the film quality of the organic thin film is improved, for example, the interaction between the polymers according to this embodiment is promoted, and the electron mobility or hole mobility is further improved. The annealing temperature is preferably a temperature between 50 ° C. and the vicinity of the glass transition temperature (Tg) of the polymer according to the present embodiment, and more preferably a temperature between (Tg−30 ° C.) and Tg. The annealing time is preferably 1 minute to 10 hours, and more preferably 10 minutes to 1 hour. The atmosphere for the annealing treatment is preferably in a vacuum or in an inert gas atmosphere such as nitrogen gas.

  Since the organic thin film according to this embodiment has charge transportability (particularly excellent hole transportability), by controlling the transport of charges injected from the electrodes or charges generated by light absorption, organic thin film transistors, organic It can be used for various organic thin film elements such as thin film solar cells and optical sensors. When using an organic thin film for these organic thin film elements, it is more preferable to use the organic thin film by orienting it because of high charge transportability.

[Organic thin film element]
The organic thin film according to the preferred embodiment described above has excellent charge transportability (particularly, excellent hole transportability) because it includes the polymer according to the present embodiment. Therefore, this organic thin film can efficiently transport charges injected from electrodes or the like or generated by light absorption, and can be applied to various electric elements (organic thin film elements) using the organic thin film. . Hereinafter, examples of organic thin film elements will be described.

(Organic thin film transistor)
First, an organic thin film transistor according to a preferred embodiment will be described. The organic thin film transistor includes a source electrode and a drain electrode, an active layer (ie, an organic thin film layer) including a polymer according to the present embodiment that is a current path between them, and a gate electrode that controls the amount of current passing through the current path. Any structure can be used. Examples of the organic thin film transistor include a field effect type and an electrostatic induction type.

  The field effect organic thin film transistor includes a source electrode and a drain electrode, an active layer that is a current path between them, a polymer according to the present embodiment, a gate electrode that controls the amount of current passing through the current path, and an active layer and a gate. It is preferable to provide an insulating layer disposed between the electrodes. In particular, it is preferable that the source electrode and the drain electrode are provided in contact with the active layer containing the polymer according to this embodiment, and further, the gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween.

  The static induction organic thin film transistor has a source electrode and a drain electrode, an active layer that becomes a current path between them, and contains a polymer according to the present embodiment, and a gate electrode that controls an amount of current passing through the current path, The gate electrode is preferably provided in the active layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the active layer are preferably provided in contact with the active layer containing the polymer according to the present embodiment. As the structure of the gate electrode, any structure may be used as long as a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. .

  FIG. 1 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a first embodiment. An organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 between the source electrode 5 and the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 formed between the source electrode 5 and the drain electrode 6. A gate electrode 4 is provided.

  FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment. An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5 and a predetermined electrode. Of the drain electrode 6 formed on the active layer 2 with an interval of, the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer 3 between the source electrode 5 and the drain electrode 6. A gate electrode 4 is provided on the insulating layer 3 so as to cover the region.

  FIG. 3 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a third embodiment. The organic thin film transistor 120 shown in FIG. 3 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval, and a source electrode. 5 and the drain electrode 6 so as to partially cover the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below. A gate electrode 4 formed on the insulating layer 3 is provided so as to partially cover each region of the insulating layer 3 that is present.

  FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment. 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A part of the source electrode 5 and the drain electrode 6 and a part of the source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined interval so as to partially cover the region of the insulating layer 3 formed on The active layer 2 is formed on the insulating layer 3 so as to cover it.

  FIG. 5 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fifth embodiment. An organic thin film transistor 140 shown in FIG. 5 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. A source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3 formed on the active layer 2 and an active layer 2 formed on the insulating layer 3 so as to partially cover the source electrode 5. And a drain electrode 6 formed on the insulating layer 3 with a predetermined distance from the source electrode 5 so as to partially cover the region of the active layer 2 formed below the gate electrode 4. .

  FIG. 6 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a sixth embodiment. An organic thin film transistor 150 shown in FIG. 6 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom. The active layer 2 is formed on the insulating layer 3 so as to partially cover the region of the active layer 2 formed under the active layer 2 and the gate electrode 4 formed below. The source electrode 5 and the drain electrode 6 formed on the insulating layer 3 with a predetermined distance from the source electrode 5 so as to partially cover the region of the active layer 2 where the gate electrode 4 is formed below. It is to be prepared.

  FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (static induction organic thin film transistor) according to a seventh embodiment. The organic thin film transistor 160 shown in FIG. 7 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality on the active layer 2 with a predetermined interval. The formed gate electrode 4 and the active layer 2a formed on the active layer 2 so as to cover the gate electrode 4 (the material constituting the active layer 2a may be the same as or different from that of the active layer 2). And a drain electrode 6 formed on the active layer 2a.

  In the organic thin film transistor according to the first to seventh embodiments, the active layer 2 and / or the active layer 2a contains the polymer according to the present embodiment, and the current path between the source electrode 5 and the drain electrode 6 (Channel). The gate electrode 4 controls the amount of current passing through the current path (channel) in the active layer 2 and / or the active layer 2a by applying a voltage.

  Such a field effect type organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069. The electrostatic induction organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-2004-006476.

  As the substrate 1, it is sufficient that the characteristics as an organic thin film transistor are not hindered, and a glass substrate, a flexible film substrate, or a plastic substrate can be used.

  When forming the active layer 2, it is preferable to use a compound soluble in an organic solvent because it is advantageous in production. In that case, the organic thin film used as the active layer 2 can be formed by applying the organic thin film manufacturing method described above.

As the insulating layer 3 in contact with the active layer 2, any material having high electrical insulation may be used, and a known material can be used. For _{example, SiOx, SiNx, Ta 2 O} 5, polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass and photoresists. Since the voltage can be lowered, a material having a high dielectric constant is preferable.

When the active layer 2 is formed on the insulating layer 3, the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification. Examples of the surface treatment agent include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane. Prior to the treatment with the surface treatment agent, the surface of the insulating layer can be treated with ozone UV or O ₂ plasma.

  Moreover, it is preferable to form a protective film on the organic thin film transistor after the organic thin film transistor is manufactured in order to protect the element. Thereby, an organic thin-film transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic thin-film transistor can be suppressed. Moreover, the influence from the outside in the process of forming the display device driven with an organic thin-film transistor on an organic thin-film transistor with a protective film can be reduced.

  Examples of the method for forming the protective film include a method of covering with a UV curable resin, a thermosetting resin, or an inorganic SiONx film. In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  An organic thin film transistor array can be formed by integrating a plurality of organic thin film transistors, and can also be used as a backplane of a flat panel display.

(Organic thin film solar cell)
Next, application of the preferred embodiment to an organic thin film solar cell will be described. FIG. 8 is a schematic cross-sectional view of an organic thin-film solar cell according to a preferred embodiment. An organic thin film solar cell 200 shown in FIG. 8 includes an organic material containing a substrate 1, a first electrode 7a formed on the substrate 1, and a polymer according to the present embodiment formed on the first electrode 7a. An active layer 2 made of a thin film and a second electrode 7b formed on the active layer 2 are provided.

  In the organic thin film solar cell according to the present embodiment, a transparent or translucent electrode is used for at least one of the first electrode 7a and the second electrode 7b. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In order to obtain a high open circuit voltage, each electrode is preferably selected so that the difference in work function is large. In the active layer 2, a charge generating agent, a sensitizer and the like can be added and used in order to increase the photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  The operation mechanism of the organic thin film solar cell will be described. Light energy incident from a transparent or translucent electrode is absorbed by the acceptor compound and / or donor compound, and excitons in which electrons and holes are combined are generated. When the generated excitons move and reach the heterojunction interface where the acceptor compound and the donor compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO and LUMO energy of each compound at the interface. Generates a charge that can move independently. The generated electrons can be taken out as electrical energy (current) by moving to the cathode and the generated holes to the anode.

  Considering such an operating mechanism, in order to obtain an organic thin film solar cell with high photoelectric conversion efficiency, an acceptor compound and / or a donor having an absorption region capable of efficiently absorbing a spectrum of desired incident light. It is important that organic thin-film solar cells contain many heterojunction interfaces in order to efficiently separate excitons, and that materials that have charge transportability to quickly transport generated charges to the electrode are important in order to efficiently separate excitons. is there.

  In the organic thin film solar cell of the present invention, an additional layer may be provided between at least one of the first electrode 7a and the second electrode 7b and the active layer 2 in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer that separates the electrode from the organic layer.

  Specifically, in the organic thin film solar cell 200 shown in FIG. 8, the organic layer having a buffer layer between the active layer 2 containing the acceptor compound and the donor compound and one or both of the pair of electrodes. Thin film solar cells are preferred.

  An organic thin film solar cell can be operated as a solar cell by generating a photovoltaic force between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells. The polymer of the present invention functions as a donor compound because it has excellent hole transport properties.

(Optical sensor)
Next, application of the organic thin film according to the present embodiment to an optical sensor will be described. FIG. 9 is a schematic cross-sectional view of the photosensor according to the first embodiment. An optical sensor 300 shown in FIG. 9 includes a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing the polymer according to the present embodiment formed on the first electrode 7a. An active layer 2, a charge generation layer 8 formed on the active layer 2, and a second electrode 7 b formed on the charge generation layer 8.

  FIG. 10 is a schematic cross-sectional view of an optical sensor according to the second embodiment. An optical sensor 310 illustrated in FIG. 10 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8. The active layer 2 which consists of an organic thin film containing the polymer which concerns on this embodiment and the 2nd electrode 7b formed on the active layer 2 are provided.

  FIG. 11 is a schematic cross-sectional view of an optical sensor according to the third embodiment. An optical sensor 320 shown in FIG. 11 includes a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing a polymer according to the present embodiment formed on the first electrode 7a. And the second electrode 7 b formed on the active layer 2.

  In the optical sensor according to the first to third embodiments, a transparent or translucent electrode is used for at least one of the first electrode 7a and the second electrode 7b. The charge generation layer 8 is a layer that absorbs light and generates charges. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used. In the active layer 2, a carrier generating agent, a sensitizer and the like can be added and used in order to increase the photosensitivity. As the substrate 1, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example at all.

  In the following examples, for example, a compound represented by Formula A will be referred to as “Compound A”, and the compounds represented by Formulas B to P will be similarly represented.

[Measurement conditions]
First, conditions for each measurement performed in an experiment described later will be described. The nuclear magnetic resonance (NMR) spectrum was measured using a product name JMN-270 (400 MHz at the time of ¹ H measurement) manufactured by JEOL (JEOL Ltd.). Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm. The coupling constant (J) is shown in hertz, and the abbreviations s, d, t, q, m, and br are singlet, doublet, triplet, quadruple, respectively. Represents a line, a multiplet, and a broad line. Reaction under microwave irradiation was performed by Initiator ^™ Ver. Manufactured by Biotage AB. 2.5 was used and the output was 400 W and 2.45 GHz.

As silica gel in the column chromatography, trade name Silicagel 60N (40-50 μm) manufactured by Kanto Chemical Co., Ltd. was used. All chemical substances are reagent grade and purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd., Sigma Aldrich Japan Co., Ltd. or Daikin Chemicals Co., Ltd.
In the purification of the compound by gel permeation chromatography (GPC), GPC system CO-8020 (manufactured by Tosoh Corporation) was used.

  The polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using Hitachi High-Technologies Hitachi High Performance Liquid Chromatograph System (L-2420 / L-2130) and GPC packed column (shodex K-803L). ) And measured. The molecular weight distribution (PDI) was determined from the relational expression of Mw / Mn.

The absorption spectrum was measured using a magnetic spectrophotometer (UV-3100PC: manufactured by Shimadzu Corporation) under the condition of a slit width of 1 mm. The absorption spectrum of the solution was measured using a quartz cell having a cell width of 1 cm by preparing a polymer in a 1 × 10 ⁻⁶ mol / L chlorobenzene solution. The absorption spectrum of the thin film was obtained by forming a polymer thin film on a quartz substrate. The wavelength that becomes the peak of the absorption spectrum was λmax, and the optical gap energy (Eg) was determined from the relational expression of Eg (eV) = 1240 / λc (nm) from the absorption edge wavelength (λc) of the thin film absorption spectrum.

<Synthesis of Compound C>
Under a nitrogen atmosphere, compound A (1 g, 3.03 mmol), thionyl chloride (SOCl ₂ ) (2.16 g, 18.2 mmol), dimethylformamide (DMF) (catalytic amount) were placed in a reaction vessel, Stir for hours. After the SOCl ₂ was distilled off under reduced pressure, it was dissolved in dichloromethane (10 mL), aluminum chloride (AlCl ₃ ) and compound B were sequentially added at 0 ° C. and stirred for 2 hours. Washed with water and extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off, and vacuum dried. Separation and purification by silica gel column chromatography (hexane: ethyl acetate = 20: 1) gave a yellow solid (compound C) (yield: 1.06 g, yield: 65%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.06 (s, 2H), 2.75 (t, 4H), 1.69-1.61 (m, 4H), 1.45 1.24 (m, 12H), 0.91 (t, 6H).

Example 1
<Synthesis of Polymer E>
Compound D was synthesized by the method described in the literature (J. Hou et al. J. Am. Chem. Soc., 2008, 130, 16144.). In a test tube with a lid, compound C (108 mg, 0.2 mmol), compound D (150 mg, 0.2 mmol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) (3.6 mg, 0 .004 mmol), tri-o-tolylphosphine (4.8 mg, 0.016 mmol) and chlorobenzene (2 mL) were added, and the reaction was carried out under irradiation with microwave (200 ° C., 30 minutes) after argon substitution. The solvent was distilled off under reduced pressure, followed by separation and purification by silica gel column chromatography (solvent chloroform). Furthermore, methanol, hexane and chloroform were separated and purified by Soxhlet in this order to obtain a deep blue solid (polymer E) (yield: 120 mg, yield: 75%).
Mn = 19500 PDI = 1.46 λ _max = 610 nm
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.18 (br, 2H), 7.94 (br, 2H), 2.80 (br, 4H), 1.80-0.70 ( br, 56H).

<Synthesis of Compound G>
Under a nitrogen atmosphere, compound A (1 g, 3.03 mmol), thionyl chloride (SOCl ₂ ) (2.16 g, 18.2 mmol), dimethylformamide (DMF) (catalytic amount) were placed in a reaction vessel, Stir for hours. After the SOCl ₂ was distilled off under reduced pressure, it was dissolved in dichloromethane (10 mL), and aluminum chloride (AlCl ₃ ) and compound F were sequentially added at 0 ° C., followed by stirring for 2 hours. Washed with water and extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off, and vacuum dried. Separation and purification by silica gel column chromatography (hexane: ethyl acetate = 20: 1) gave a yellow solid (Compound G). (Yield: 1.12 g, yield: 76%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.04 (s, 2H), 2.74 (t, 4H), 1.66 to 1.55 (m, 4H), 1.47− 1.38 (m, 4H), 0.94 (t, 6H).

Example 2
<Synthesis of Polymer H>
Put compound G, compound D, (Pd ₂ (dba) ₃ ), tri-o-tolylphosphine, and chlorobenzene into a test tube with a lid, and replace with argon, then react under irradiation with microwave (200 ° C., 30 minutes). Do. The solvent is distilled off under reduced pressure, followed by separation and purification by silica gel column chromatography (solvent chloroform). Further, separation, purification with Soxhlet in the order of methanol, hexane and chloroform yields polymer H.

<Synthesis of Compound J>
Under a nitrogen atmosphere, Compound A (1 g, 3.03 mmol), SOCl ₂ (2.16 g, 18.2 mmol), and DMF (catalytic amount) were placed in a reaction vessel, and the mixture was stirred at 70 ° C. for 1 hour. After the SOCl ₂ was distilled off under reduced pressure, it was dissolved in dichloromethane (10 mL), and AlCl ₃ and Compound I were sequentially added at 0 ° C., followed by stirring for 2 hours. Washed with water and extracted with chloroform. The organic layer was dried over sodium sulfate, the solvent was distilled off, and vacuum dried. Separation and purification by silica gel column chromatography (hexane: ethyl acetate = 20: 1) gave yellow solid J (yield: 1.30 g, yield: 71%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 4.35 (s, 4H), 1.79-1.74 (m, 4H), 1.4-1.2 (m, 20H), 0.89 (t, 6H).

Example 3
<Synthesis of Polymer K>
Compound J, compound D, Pd ₂ (dba) ₃ , tri-o-tolylphosphine, and chlorobenzene are placed in a test tube with a lid, and after replacing with argon, the reaction is carried out under microwave (200 ° C., 30 minutes) irradiation. After separation and purification by column chromatography (solvent chloroform), separation and purification are further performed by Soxhlet in the order of methanol, hexane and chloroform to obtain a polymer K.

Example 4
<Synthesis of Polymer M>
Compound L is synthesized by the method described in the literature (C J. Kudla, D Dolfen, K J. Schottler, JM Koenen, D Breusov, SAllard, U Scherf. Macromolecules, 2010, 43, 7864-7867).
Compound G, compound L, Pd ₂ (dba) ₃ , tri-o-tolylphosphine, and chlorobenzene are placed in a test tube with a lid, and after replacing with argon, the reaction is performed under irradiation with microwave (200 ° C., 30 minutes). After separation and purification by column chromatography (solvent chloroform), further separation and purification by methanol, hexane and chloroform in the order of Soxhlet yields polymer M.

Example 5
<Synthesis of Polymer N>
Compound C, compound L, Pd ₂ (dba) ₃ , tri-o-tolylphosphine, and chlorobenzene are placed in a test tube with a lid, and after replacing with argon, the reaction is carried out under microwave (200 ° C., 30 minutes) irradiation. After separation and purification by column chromatography (solvent chloroform), separation and purification are further performed by Soxhlet in the order of methanol, hexane and chloroform to obtain a polymer N.

Example 6
<Synthesis of Polymer O>
Compound J, compound L, Pd ₂ (dba) ₃ , tri-o-tolylphosphine, and chlorobenzene are placed in a test tube with a lid, and after replacing with argon, the reaction is carried out under microwave (200 ° C., 30 minutes) irradiation. After separation and purification by column chromatography (solvent chloroform), separation and purification are further performed by Soxhlet in the order of methanol, hexane and chloroform to obtain a polymer O.

Example 7
<Preparation of Organic Thin Film Element 1 and Evaluation of Solar Cell Characteristics>
Suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (Baytron (registered trademark) PAI4083 manufactured by Stark Vitec Co., Ltd.) on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering. Was filtered through a 0.2 μm membrane filter, a thin film was formed with a thickness of 44 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Next, polymer E synthesized in Example 1 and fullerene C70PCBM (phenyl C71-butyric acid methyl ester, manufactured by Frontier Carbon Co.) (weight ratio of polymer E / C70PCBM = 1/2) ) And dissolved in orthodichlorobenzene (the total weight of the polymer E and C70PCBM is 2.0% by weight) to prepare a coating solution. The coating solution was applied onto the substrate by spin coating to deposit an organic thin film containing the polymer E (film thickness: about 100 nm). The thus prepared organic thin film had a light absorption terminal wavelength of 770 nm. Then, calcium was vapor-deposited with a thickness of 8 nm on the organic thin film by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm. The shape of the obtained organic thin film element 1 was a regular square of 2 mm × 2 mm. The obtained organic thin film element 1 is irradiated with constant light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.), and the generated current and voltage are measured. The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined. Jsc (short circuit current density) = 11.36 mA / cm ² , Voc (open-circuit voltage) = 0.90 V, ff (fill factor) = 0.48, photoelectric conversion efficiency (η) = 4.9% Good solar cell characteristics were obtained.

Example 8
<Preparation of organic thin film element 2 and evaluation of transistor characteristics>
A substrate in which a 300 nm silicon oxide film was formed as an insulating film by thermal oxidation on the surface of a heavily doped p-type silicon substrate as a gate electrode was prepared. On this substrate, a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 μm were formed by a lift-off method. The substrate with electrodes was ultrasonically cleaned with acetone for 10 minutes and then with isopropyl alcohol for 10 minutes, and then the surface was cleaned by irradiation with ozone UV for 20 minutes. A toluene-diluted solution (β-PTS / toluene: 0.2 mL / 10 mL) of β-phenyltrichlorosilane (β-PTS) (Shin-Etsu Chemical LP-1990) was dropped on the surface-cleaned substrate with electrodes, and then spinned. The substrate surface was SAM-treated by spinning with a coater. Further, toluene was dropped and spin-coated to wash away excess β-PTS, and a surface-treated substrate with an electrode was produced. When the polymer E synthesized in Example 1 was dissolved in chloroform at a concentration of 0.5% by mass, it was confirmed that the polymer E was completely dissolved in chloroform and could be dissolved in an organic solvent. It was. This solution was applied onto the surface-treated substrate by spin coating at a rotation speed of 1500 rpm for 1 minute and dried to deposit an organic thin film of polymer E (film thickness: about 100 nm). Thereafter, annealing treatment was performed at 170 ° C. for 30 minutes in a nitrogen atmosphere to obtain an organic thin film element 2. Using a semiconductor parameter analyzer (trade name “4200-SCS” manufactured by Keithley), while changing the gate voltage Vg and the source-drain voltage Vsd in the range of +20 to −40 V in a vacuum, When the organic transistor characteristics were measured, good drain current (Id) -gate voltage (Vg) characteristics of a p-type semiconductor were obtained. The mobility at this time was 7.9 × 10 ⁻⁴ cm ² / Vs, the threshold voltage was −1.7 V, the on / off ratio was about 10 ⁶ , and both were good. From this, it was confirmed that the organic thin film element 2 functions effectively as a p-type organic transistor. From this, it was confirmed that the polymer E has an excellent hole transport property and can be used as an organic p-type semiconductor.

Comparative Example 1
<Preparation of organic thin film element C1 and evaluation of solar cell characteristics>
Organic thin film element C1 was produced under the same conditions as in Example 7 except that poly (3-hexylthiophene) (P3HT: manufactured by Aldrich) was used instead of polymer E. In addition, the film thickness of the organic thin film containing P3HT was 115 nm, and the light absorption terminal wavelength of the organic thin film was 660 nm. The obtained organic thin film element C1 is irradiated with constant light using a solar simulator in the same manner as in Example 7, and the generated current and voltage are measured to measure photoelectric conversion efficiency, short-circuit current density, open-end voltage, fill factor. Asked. Jsc (short circuit current density) = 4.09 mA / cm ² , Voc (open circuit voltage) = 0.67 V, ff (fill factor) = 0.44, photoelectric conversion efficiency (η) = 1.2% The characteristics were lower than those of the organic thin film element 1 of Example 7.

Comparative Example 2
<Preparation of Organic Thin Film Element C2 and Evaluation of Solar Cell Characteristics>
Instead of polymer E, poly [2,6- (4,4'-bis (2-ethylhexyl) dithieno [3,2-b: 2 ', 3'-d] silole) -alt-4,7 (2 , 1,3-benzothiadiazole)] (PSBTBT: manufactured by Luminescence Technology Corporation: LT-S951), an organic thin film element C2 was fabricated under the same conditions as in Example 7. The film thickness of the organic thin film containing PSBTBT was 111 nm, and the light absorption terminal wavelength of the organic thin film was 860 nm. The obtained organic thin film element C2 is irradiated with constant light using a solar simulator in the same manner as in Example 7, and the generated current and voltage are measured to measure photoelectric conversion efficiency, short-circuit current density, open-end voltage, fill factor. Asked. Jsc (short circuit current density) = 9.61 mA / cm ² , Voc (open-circuit voltage) = 0.66 V, ff (fill factor (curve factor)) = 0.42, photoelectric conversion efficiency (η) = 2.7% The characteristics were lower than those of the organic thin film element 1 of Example 7.

<Synthesis of Compound Q>
Under a nitrogen atmosphere, Compound A (1 g, 3.03 mmol), SOCl ₂ (2.16 g, 18.2 mmol), and DMF (catalytic amount) were placed in a reaction vessel, and the mixture was stirred at 70 ° C. for 1 hour. The SOCl ₂ was distilled off under reduced pressure and then dissolved in dichloromethane (10 ml) at 0 ° C. by the method described in AlCl ₃ and G. barbarella, L. Favaretto, A. Bongini. J. Org. Chem. 1998, 63, 5497. The synthesized compound P (1.15 g, 4.55 mmol) was added in order and stirred for 2 hours. Separation and purification by silica gel column chromatography (hexane: ethyl acetate = 20: 1) gave Compound Q as a yellow solid (yield: 1.23 g, yield: 74%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 3.32 (t, 4H), 1.75-1.69 (m, 4H), 1.43-1.31 (m, 12H), 0.89 (t, 6H).

Example 9
<Synthesis of Polymer R>
In a test tube with a lid, Compound Q (190 mg, 0.35 mmol) and Compound D (260 mg, 0.35 mmol), Pd ₂ (dba) ₃ (7 mg, 2% mol), tri-o-tolylphosphine (9 mg, 8%) mol) and toluene (8 ml, 0.05 M) were added, and after substitution with argon, the reaction was carried out at 120 ° C. for 2 days. After reprecipitation, separation and purification were performed with Soxhlet in the order of methanol, hexane, and chloroform to obtain a polymer R as a black solid (yield: 240 mg, yield: 80%).
Mn = 19.8 kg / mol PDI = 1.51
λ _max = 581 nm (in solution)
λ _max = 599 nm (in film)
Eg = 1.72 eV
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.78 (br, 2H), 3.47 (br, 4H), 1.80 (Br, 4H), 1.52 (Br, 4H) , 1.39-1.25 (br, 30H), 1.94-0.81 (br, 18H).

Example 10
<Preparation of organic thin film element 3 and evaluation of solar cell characteristics>
Suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (Baytron (registered trademark) PAI4083 manufactured by Stark Vitec Co., Ltd.) on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering. Was filtered through a 0.2 μm membrane filter, a thin film was formed with a thickness of 44 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Next, polymer R and C70PCBM (phenyl C71-butyric acid methyl ester, synthesized by Frontier Carbon Co.) synthesized in Example 9 (weight ratio of polymer R / C70PCBM = 1/2) Were dissolved in orthodichlorobenzene (the total weight of the polymer E and C70PCBM was 2.0% by weight) to prepare a coating solution. The coating solution was applied onto the substrate by spin coating to deposit an organic thin film containing the polymer R (film thickness of about 80 nm). Then, Al was vapor-deposited with a thickness of 100 nm on the organic thin film by a vacuum vapor deposition machine. The shape of the obtained organic thin film element 3 was a regular square of 3 mm × 3 mm. The obtained organic thin film element 3 is irradiated with constant light using a solar simulator (trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.), and the generated current and voltage are measured. The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined. Jsc (short-circuit current density) = 7.71 mA / cm ² , Voc (open-circuit voltage) = 0.98 V, ff (fill factor (curve factor)) = 0.43, photoelectric conversion efficiency (η) = 3.2% Good solar cell characteristics were obtained.

Example 11
<Preparation of Organic Thin Film Element 4 and Evaluation of Solar Cell Characteristics>
In the same manner as in Example 10, using C60PCBM (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co.) instead of C70PCBM, Polymer R and C60PCBM (Polymer R / C60PCBM) An organic thin film element 4 having an organic thin film containing a weight ratio = 1/2) was produced. The obtained organic thin film element 4 is irradiated with constant light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.), and the generated current and voltage are measured. The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined. Jsc (short-circuit current density) = 6.01 mA / cm ² , Voc (open-circuit voltage) = 0.98 V, ff (fill factor) = 0.46, photoelectric conversion efficiency (η) = 2.70% Good solar cell characteristics were obtained.

<Synthesis of Compound T>
Compound 300 (2.00 g, 4.97 mmol) and dehydrated THF (80 mL) were placed in a 300 mL flask in which the internal gas was replaced with argon to obtain a uniform solution. The obtained THF solution was kept cooled to -78 ° C., and 1.6 M n-butyllithium hexane solution (7.76 mL, 12.4 mmol) was added dropwise over 10 minutes. After the addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Thereafter, the reaction solution was cooled again to −78 ° C., and tributyltin chloride (4.45 g, 13.7 mmol) was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, water (100 mL) was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer which is an ethyl acetate solution was dried with sodium sulfate, the organic layer was filtered, and then the solvent component of the filtrate was distilled off with an evaporator. The obtained oily substance was purified by a silica gel column using hexane as a developing solvent. The silica gel column used was a silica gel that was previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane. After purification, compound T was obtained (yield: 3.30 g, yield: 68%).

Example 12
<Synthesis of Polymer U>
In a 100 mL flask in which the internal gas was replaced with argon, compound T (125.0 mg, 0.127 mmol), compound C (68.5 mg, 0.127 mmol), tris (2-tolyl) phosphine (3.5 mg,. 011 mmol) and dehydrated toluene (5 mL) were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes. Tris (dibenzylideneacetone) dipalladium (1.74 mg, 0.0019 mmol) was added to the toluene solution, and the mixture was stirred at 105 ° C. for 6 hours. Phenyl bromide (100 mg) was added to the reaction solution, and further stirred at 105 ° C. for 3 hours. did. Thereafter, the reaction solution was cooled to room temperature and poured into a mixed solution of methanol (200 mL) and concentrated hydrochloric acid (20 mL). The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in o-dichlorobenzene (7 mL), sodium diethyldithiocarbamate (0.11 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with water (50 mL), then twice with 3 wt% aqueous acetic acid (50 mL), and finally twice with water (50 mL). The obtained solution was poured into methanol to precipitate a polymer. The polymer was collected by filtration and dried, and the obtained polymer was dissolved again in 7 mL of o-dichlorobenzene and purified with an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was collected by filtration and dried to obtain a polymer U (23 mg).

<Synthesis of Compound W>
Compound V (1.00 g, 1.59 mmol) and dehydrated THF (20 mL) were placed in a 300 mL flask in which the internal gas was replaced with argon to obtain a uniform solution. The obtained THF solution was cooled to -78 ° C., and a 2.6 M n-butyllithium hexane solution (2.45 mL, 6.38 mmol) was added dropwise over 10 minutes. After the addition, the reaction solution was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Thereafter, the reaction solution was cooled again to −78 ° C., and tributyltin chloride (2.34 g, 7.18 mmol) was added to the reaction solution. After the addition, the reaction solution was stirred at −78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 3 hours. Thereafter, water (100 mL) was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract an organic layer containing the reaction product. The organic layer which is an ethyl acetate solution was dried with sodium sulfate, and after filtering the organic layer, the solvent component of the filtrate was distilled off with an evaporator. The obtained oily substance was purified with a column using silica gel (Wakogel 100C18 manufactured by Wako Pure Chemical Industries) with octadecylsilyl group bonded to the surface. As a developing solvent, a mixed solution of acetonitrile and tetrahydrofuran was used. After purification, compound W was obtained (yield: 1.14 g, yield: 59%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 6.89 (s, 2H), 1.79 (t, 4H), 0.85-1.75 (m, 116H).

<Synthesis of Compound X>
Under a nitrogen stream atmosphere, Compound A (3.0 g, 9.1 mmol), toluene (150 mL) and N, N-dimethylformamide (1 drop) were charged at room temperature into a 200 mL three-necked flask equipped with a Dimroth, and oxalyl chloride ( 3.18 mL, 36 mmol) was added dropwise, and the mixture was heated to reflux for 1 hour. After refluxing, the reaction solution was cooled to room temperature, concentrated with an evaporator, dehydrated dichloromethane (100 mL) was added, and the mixture was cooled to 0 ° C. Aluminum chloride (5.33 g) was slowly added to the dichloromethane solution and stirred at 0 ° C. for 30 minutes. To the reaction solution, a solution of 1,2-diethylbenzene (1.49 g) in dichloromethane (20 mL) was slowly added dropwise with a syringe, stirred at 0 ° C. for 1 hour, then warmed to room temperature, and further stirred for 2 hours. Thereafter, water was added, the aqueous layer was neutralized with an aqueous sodium hydrogen carbonate solution, the organic layer was extracted with chloroform, and the organic layer was washed three times with water (50 mL). The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography, and then compound X was obtained by recrystallization (yield: 2.32 g, yield: 54%).
¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.09 (s, 2H), 2.80 (q, 4H), 1.31 (t, 6H).

Example 13
<Synthesis of Polymer Y>
Compound 100 (200 mg, 0.166 mmol), compound X (71.0 mg, 0.166 mmol), tris (2-tolyl) phosphine (4.5 mg, 0.015 mmol) was added to a 100 mL flask whose internal gas was replaced with argon. And dehydrated toluene (30 mL) was added to make a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Tris (dibenzylideneacetone) dipalladium (2.3 mg, 0.0025 mmol) was added to the toluene solution and stirred at 105 ° C. for 6 hours. Phenyl bromide (100 mg) was added to the reaction solution, and further stirred at 105 ° C. for 3 hours. did. Thereafter, the reaction solution was cooled to room temperature and poured into a mixed solution of methanol (200 mL) and concentrated hydrochloric acid (20 mL). The precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in o-dichlorobenzene (7 mL), sodium diethyldithiocarbamate (0.11 g) and water (2.0 mL) were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with water (50 mL), then twice with 3 wt% aqueous acetic acid (50 mL), and finally twice with water (50 mL). The obtained solution was poured into methanol to precipitate a polymer. The polymer was collected by filtration and dried. The obtained polymer was dissolved again in o-dichlorobenzene (7 mL) and purified with an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was collected by filtration and dried to obtain a polymer Y (135 mg).

Example 14
<Preparation of organic thin film element 5 and evaluation of transistor characteristics>
An organic thin film element 5 was produced under the same conditions as in Example 8 except that the polymer Y was used instead of the polymer E. The film thickness of the organic thin film containing the polymer Y was 50 nm. The obtained organic thin film element 5 was subjected to a semiconductor parameter analyzer (trade name “4200-SCS” manufactured by Keithley, Inc.) in the same manner as in Example 8, and the gate voltage Vg and the source-drain voltage Vsd were +20 in vacuum. The organic transistor characteristics of the organic thin film element 2 were measured while changing in the range of -40V. The mobility was 2.8 × 10 ⁻⁴ cm ² / Vs, the threshold voltage was 13.3 V, and the on / off ratio was about 10 ⁴ , both of which were good. From this, it was confirmed that the organic thin film element 5 functions effectively as a p-type organic transistor. From this, it was confirmed that the polymer Y has an excellent hole transport property and can be used as an organic p-type semiconductor.

  DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Active layer, 2a ... Active layer, 3 ... Insulating layer, 4 ... Gate electrode, 5 ... Source electrode, 6 ... Drain electrode, 7a ... 1st electrode, 7b ... 2nd electrode, 8 ... Charge generation layer, 100 ... organic thin film transistor according to the first embodiment, 110 ... organic thin film transistor according to the second embodiment, 120 ... organic thin film transistor according to the third embodiment, 130 ... organic thin film transistor according to the fourth embodiment, 140 ... Organic thin film transistor according to fifth embodiment, 150... Organic thin film transistor according to sixth embodiment, 160. Organic thin film transistor according to seventh embodiment, 200... Organic thin film solar cell according to embodiment, 300. Optical sensor 310... Optical sensor according to the second embodiment, 320... Optical sensor according to the third embodiment.

Claims (7)

A polymer having at least two structural units represented by formula ( 3 ) and having at least one structural unit represented by formula ( 6 ).

[Where:
X ¹ and ^{X 2} represents an acid MotoHara child.
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic carbon group having 1 to 30 carbon atoms. A monovalent non-alkyl group containing an alkyl group, an aryl group having 6 to 60 carbon atoms which may have a substituent, or a monovalent heterocyclic group having 2 to 60 carbon atoms which may have a substituent Indicates. R ¹ and R ² may be bonded to each other to form a hydrocarbon ring or a heterocyclic ring condensed with the ring to which they are bonded, and the hydrocarbon ring and the heterocyclic ring have a substituent. You may do it.
Z ¹ represents a group represented by the formula (ii).
Y represents a carbon atom, a silicon atom, a germanium atom, a titanium atom or a tin atom.
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic carbon group having 1 to 30 carbon atoms. A monovalent non-alkyl group containing an alkyl group, an aryl group having 6 to 60 carbon atoms which may have a substituent, or a monovalent heterocyclic group having 2 to 60 carbon atoms which may have a substituent Indicates.
W ³ and W ⁴ are each independently a group represented by —C (R ′) ═ (R ′ represents a hydrogen atom, a halogen atom or a monovalent group) or —N═. Indicates a group.
Z ³ and Z ⁴ represent a group represented by the formula (ii). ]

Further comprising a structural unit represented by Formula (7) The polymer according to claim 1.

[Where:
Ar ⁴ represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent heterocyclic group which may have a substituent. ] The polymer of Claim 1 or 2 which has a structural unit represented by Formula (12).

[Where:
X ¹ , X ² , Y, R ¹ , R ² , R ³ , R ⁴ , W ³ , W ⁴ , Z ¹ , Z ³ and Z ⁴ are as defined above.
R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom or a monovalent group, and R ⁷ and R ⁸ may be bonded to each other to form a ring.
Z ⁵ is a group represented by the formula (xxxi), a group represented by the formula (xxxii), a group represented by the formula (xxxiii), a group represented by the formula (xxxiv), or a group represented by the formula (xxxv). A group represented by formula (xxxvi), a group represented by formula (xxxvii), a group represented by formula (xxxviii), or a group represented by formula (xxxix).
s and t each independently represent an integer of 0 to 6.
When there are a plurality of R ⁷ , R ⁸ and Z ⁵ , they may be the same or different. ]

[Where:
R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent group which may have a substituent, and R ⁴¹ and R ⁴² are bonded to each other. A ring may be formed. ] The organic thin film containing the polymer as described in any one of Claims 1-3 . An organic thin film element provided with the organic thin film of Claim 4 . An organic thin-film transistor provided with the organic thin film of Claim 4 . An organic thin film solar cell comprising the organic thin film according to claim 4 .

Images