WO2017212961A1 - Boron-containing polymer and use thereof - Google Patents

Boron-containing polymer and use thereof Download PDF

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Publication number
WO2017212961A1
WO2017212961A1 PCT/JP2017/019845 JP2017019845W WO2017212961A1 WO 2017212961 A1 WO2017212961 A1 WO 2017212961A1 JP 2017019845 W JP2017019845 W JP 2017019845W WO 2017212961 A1 WO2017212961 A1 WO 2017212961A1
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boron
containing polymer
polymer compound
nitrogen
ring
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PCT/JP2017/019845
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French (fr)
Japanese (ja)
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武士 大前
英樹 羽田
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綜研化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions

Definitions

  • the present invention relates to a boron-containing polymer compound and its use.
  • the polymer organic semiconductor has an advantage that an excellent film quality can be easily obtained upon application and the device characteristics are easily stabilized. It is known that in order to make the high molecular organic semiconductor more mobile, it is desirable that a unit structure having a large ⁇ -conjugated area is introduced and that the high molecular weight semiconductor be a higher molecular weight body.
  • Non-Patent Document 1 it is disclosed in Non-Patent Document 1 that the LUMO / HOMO level is deepened by introducing a boron-nitrogen coordination bond structure, and it is disclosed in Patent Document 1 that the organic semiconductor performance can be improved. ing.
  • a polymer organic semiconductor having a unit having a large ⁇ -conjugated area has a problem in handling in the coating process because its solubility is lowered when the molecular weight is increased and the stability in the solution is deteriorated accordingly.
  • the molecular arrangement has a great influence on the properties, so unless the chain-like substituents are placed at appropriate positions in the structure, the arrangement and arrangement of the molecules in the organic semiconductor film after drying is not appropriate. Disappear.
  • the molecular arrangement since the molecular arrangement also has a great influence on mobility, even if solubility is improved, it does not necessarily lead to further improvement in mobility. Therefore, it is difficult to achieve both solubility and mobility.
  • Patent Document 1 only provides a dimer structure.
  • Non-Patent Document 1 although polymerization was successful, the side chain was not appropriate and the ⁇ -conjugated area of the unit structure was small, so that sufficient semiconductor characteristics were not obtained.
  • the present invention has been made in view of such circumstances, and the LUMO / HOMO level is deep, and the unit structure has a wide ⁇ -conjugated plane, and can have a high molecular weight due to high solubility.
  • the present invention provides a boron-containing polymer compound for an organic semiconductor that can be suitably used for applications such as an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic paper, thermoelectric conversion element, and optical sensor.
  • the structure W is represented by the following formula (1) including a structure W having at least two boron-nitrogen coordination bonds and a structure ⁇ that is a divalent substituent having a conjugated structure.
  • a high molecular compound containing a structural unit m represents 0 or 1;
  • the structure W is represented by the following formula (2) or (3): Rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure, Rings Y 1 and Y 2 are 5-membered rings having the boron-nitrogen coordination bond, any one of ⁇ 1 and ⁇ 3 is a nitrogen atom, one of ⁇ 2 and ⁇ 4 is a nitrogen atom, R 1 to R 4 may be the same or different, may be bonded to boron via another skeleton, and may have at least a linear or branched alkyl group having 10 to 40 carbon atoms that may be substituted.
  • the present inventor has studied a boron-containing polymer compound having excellent mobility. As a result, at least two boron-nitrogen coordination bonds are introduced into a unit structure having a wide conjugate plane, and an alkyl group is contained on the boron atom. It has been found that by introducing a substituent, a polymer compound having a deep LUMO / HOMO level and a high molecular weight contributing to improvement in mobility and having a wide conjugated plane in the unit structure can be provided.
  • the polymer compound can be used as an organic semiconductor.
  • the weight average amount is 2 ⁇ 10 4 to 1 ⁇ 10 6 .
  • W is bonded to adjacent W or ⁇ via a 5-membered ring in W.
  • the organic semiconductor containing said boron containing high molecular compound is provided.
  • the boron-containing polymer compound according to an embodiment of the present invention can be used as an organic semiconductor, and is a polymer compound represented by the following formula (1).
  • the unit structure includes a structure ⁇ which is a divalent substituent having a conjugated structure in addition to W. That is, m is 0 or 1, preferably 1. This is because it is assumed that the structure containing ⁇ has both structures serving as a donor and an acceptor in the unit structure, the interaction between the molecular chains tends to be strong, and the mobility is improved. .
  • the unit structure represented by W in the above formula (1) is a structure represented by the following formula (2) or (3) having at least two boron-nitrogen coordination bonds.
  • the electronic bias between boron and nitrogen is thought to strengthen the interaction between the molecular chains.
  • the electronic bias becomes larger and the molecule It is considered that the mobility is improved by the stronger interaction between the chains.
  • W is composed of rings X 1 , X 2 , Y 1 , Y 2 , and Z, and rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure.
  • ⁇ 1 and ⁇ 2 may be the same as or different from each other, and are preferably the same. Further, ⁇ 3 and ⁇ 4 may be the same or different from each other, preferably the same. When they are the same, there is an advantage that the synthesis is easier than when they are different, and since the target property is high, the arrangement and arrangement of the molecular chains are likely to be appropriate, and the mobility tends to be high.
  • One of ⁇ 1 and ⁇ 3 is a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in ring Y 1 , and the other is not particularly limited, but is, for example, a carbon atom.
  • One of ⁇ 2 and ⁇ 4 is a nitrogen atom that forms a boron-nitrogen coordination bond with a boron atom in the ring Y 2 , and the other is not particularly limited, but is, for example, a carbon atom.
  • Rings X 1 and X 2 are monocyclic or condensed rings having a conjugated structure and may contain a nitrogen atom that forms a boron-nitrogen coordination bond.
  • Rings X 1 and X 2 may not contain a hetero atom, but are preferably a hetero ring containing a hetero atom.
  • the heterocyclic ring is, for example, pyrrole, furan, thiophene, selenophene, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine and the like, and these are condensed structures, more preferably containing a sulfur atom.
  • thiophene thienothiophene
  • benzothiophene benzodithiophene
  • thiazole thiazolothiazole and the like, more preferably thiophene or thiazole.
  • rings X 1 and X 2 contain a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in the rings Y 1 and Y 2
  • examples thereof include imidazole, pyrazole, thiazole, and pyridine.
  • Preferred are thiazole and pyridine, and more preferred are rings X 1 and X 2 containing a sulfur atom, for example, thiazole.
  • the monocyclic ring or condensed ring of the rings X 1 and X 2 may be substituted as long as the semiconductor properties are not impaired, and the substituent is not limited, but specifically, a linear, branched, or cyclic alkyl Group, alkoxy group, alkylthio group, sulfo group, hydroxy group, carboxy group, amino group, amide group, ester group, phenyl group, etc., and substituted with sulfo group, hydroxy group, carboxy group, amino group, halogen group It may be a linear or branched alkyl group, an alkoxyalkyl group, an alkylene oxide group, a phenyl group or the like, and may have a plurality of substituents.
  • W is bonded to adjacent W or ⁇ via a 5-membered ring or 6-membered ring in W, preferably bonded via a 5-membered ring. This is because in the case of a five-membered ring, there is little steric repulsion with the adjacent W or ⁇ , it is easy to form a continuous planar structure, and the mobility is considered to be improved.
  • Ring Z is a monocyclic or condensed ring having a conjugated structure and may contain a nitrogen atom forming a boron-nitrogen coordination bond. Ring Z may or may not contain heteroatoms, such as benzene, naphthalene, anthracene, pyrazine, thienothiophene, benzodithiophene, thiazolothiazole, benzobisthiazole, and the like.
  • ring Z contains a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in rings Y 1 and Y 2
  • ring Z is, for example, pyrazine, thiazolothiazole, naphthyridine, benzobisthiazole, pyrazino Bisthiazole and the like.
  • Preferred is thiazolothiazole or benzobisthiazole.
  • Rings Y 1 and Y 2 are 5-membered rings having a boron-nitrogen coordination bond.
  • the boron atoms forming the boron-nitrogen coordination bond in the rings Y 1 and Y 2 have alkyl group-containing substituents R 1 to R 4 which may be the same or different.
  • the two boron atoms may be located on different sides as in the above formula (2), or may be located on the same side as in the above formula (3). You may do it.
  • the appropriate position differs depending on the substituents introduced into each ring, so that the position is not limited to any one. In any case, it has two boron-nitrogen coordination bonds, and the same effect is considered to be achieved. . However, from the viewpoint of ease of synthesis, it is considered that it is often advantageous to be located on different sides as in the above formula (2).
  • R 1 to R 4 may be the same or different, and are monovalent substituents having at least one linear or branched alkyl group having 10 to 40 carbon atoms which may be substituted.
  • the alkyl group may be directly bonded to the boron atom or may be bonded via another skeleton.
  • the number of carbon atoms of the alkyl group is preferably 12 or more, more preferably 14 or more.
  • the number of carbon atoms of the alkyl group is preferably 30 or less, more preferably 25 or less.
  • the said carbon number is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 32, 33, 34, 35, 36, 37, 38, 39, 40, and may be within a range between any two of the numerical values exemplified here.
  • the solubility in a solvent mainly means the solubility in a halogen solvent, an aromatic solvent, etc., specifically, chloroform, chlorobenzene, dichlorobenzene, toluene, mesitylene, anisole, tetralin, cyclohexyl. It means solubility in benzene.
  • Examples of the substituent that may substitute the alkyl group in R 1 to R 4 include a sulfo group, a hydroxy group, an alkoxy group, an alkylthio group, a carboxy group, an ester group, an amino group, an amide group, a halogen group, A phenyl group and the like;
  • examples of the other skeleton include heteroatoms such as oxygen, nitrogen, and sulfur, a benzene ring, a naphthalene ring, an azulene ring, and an anthracene ring.
  • Aromatic ring such as phenanthrene ring, pyrene ring, chrysene ring, tetracene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyranthrene ring, pyridine , Imidazole, thiophene and the like, and a plurality of them may be combined. Further, an alkyl chain having 1 to 6 carbon atoms may be interposed between another skeleton and boron.
  • R 1 to R 4 are preferably such that a linear or branched alkyl group is directly bonded to boron, or bonded to boron through oxygen or sulfur and / or a phenyl group, benzyl group, phenethyl group, Preferably, a linear or branched alkyl group is directly bonded to boron, and more preferably, a linear alkyl group is directly bonded to boron.
  • Synthesis of boron-containing compounds can be synthesized by various methods.
  • W represented by the above formula (2) can be synthesized by the following reaction formula (5) or It can be synthesized by the route of reaction formula (6).
  • R 1 to R 4 in Formula (5) are the same as in Chemical Formula (2), and R 5 represents halogen.
  • R 1 to R 4 in formula (6) are the same as in chemical formula (2), and R 5 represents halogen.
  • the reaction vessel is not particularly limited, and glass, Teflon (registered trademark), or the like can be used.
  • the reaction solvent is not particularly limited, and may be any solvent in which the reaction proceeds, and examples thereof include tetrahydrofuran, tert-butyl methyl ether, acetonitrile, phenol, benzene, toluene and the like.
  • the inert gas includes nitrogen, argon, helium and the like.
  • the stirring method is not particularly limited, but a stirrer or a shaker may be used.
  • the purification step may be any step that can isolate the target product, and known methods can be used. Specific examples include separation extraction, isolation by column chromatography, and recrystallization. Isolation and purification may be performed in combination.
  • the base is not particularly limited, and may be any base that allows BN crosslinking reaction to proceed.
  • Examples of the base include alkyl lithium, and specific examples include methyl lithium, n-butyl lithium, sec-butyl lithium. Tert-butyllithium and the like.
  • the cooling temperature when adding the base is ⁇ 100 ° C. to ⁇ 50 ° C., preferably ⁇ 90 ° C. to ⁇ 70 ° C. Specifically, this temperature is, for example, ⁇ 100, ⁇ 90, ⁇ 80, ⁇ 70, ⁇ 60, or 50 ° C., and may be within a range between any two of the numerical values exemplified here.
  • the stirring for several hours after the addition of the base is not particularly limited, but is, for example, 1 to 6 hours, and preferably 1 to 4 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5 or 6 hours, and may be within a range between any two of the numerical values exemplified here.
  • the substituted borane is not particularly limited as long as it is a borane having substituents R 1 to R 4 that can be used in the present invention and in which a BN crosslinking reaction proceeds.
  • the stirring time after adding the borane is not particularly limited, but is, for example, 1 to 24 hours, preferably 8 to 24 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 21 or 24 hours. It may be within the range between any two.
  • the stirring temperature after adding the borane is ⁇ 78 ° C. to 25 ° C., preferably 0 ° C. to 25 ° C. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, or 25 ° C., and may be within a range between any two of the numerical values exemplified here.
  • boron tribromide is used as borane
  • BBr 2 is converted into a crosslinked product
  • a Grignard reaction is performed using a Grignard reagent such as alkylmagnesium bromide to introduce substituents R 1 to R 4 . May be.
  • ⁇ in the above formula (1) represents a divalent substituent having a conjugated structure, and is preferably represented by the following formula (7).
  • the group is unsubstituted or substituted with one or more groups R 6 and a and b may be the same or different and represent an integer of 0-2.
  • R 6 represents H, a halogen, a cyano group, or a linear or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group, or an alkylthio group.
  • the site bonded to W is —CH ⁇ CH—, —C ⁇ C—, or a 5-membered ring. This is because in these cases, there is little steric repulsion with the bonded W, it is easy to form a continuous planar structure, and the mobility is considered to be improved.
  • the structure shown in the following formula (8) is exemplified, but not limited thereto.
  • the boron-containing polymer compound of the present invention may contain a copolymer containing the structure represented by the chemical formula (1) in the polymer compound, but in order to further strengthen the interaction between the molecular chains.
  • the weight average molecular weight (Mw) of the boron-containing polymer compound of the present invention is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”), and is usually 2 ⁇ 10 4 to 2 ⁇ . 10 8 .
  • the weight average molecular weight of the polymer compound is preferably 2 ⁇ 10 4 to 1 ⁇ 10 6 , more preferably 3 ⁇ 10 4 to 5 ⁇ 10. 5 .
  • the method for polymerizing the boron-containing polymer compound including the above formula (1) is not particularly limited, but Suzuki coupling, Still coupling Ullmann reaction, Gracer reaction, Heck reaction, Negishi coupling, Sonogashira coupling, Kumada Coupling and the like can be used, and Suzuki coupling and Stille coupling are preferable in terms of ease of synthesis and few restrictions on the monomers that can be used.
  • W and / or ⁇ bonded with boronic acid or a boronic acid ester and halogenated W and / or ⁇ are used as raw materials in the presence of a palladium catalyst and a base. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated in an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
  • W and / or ⁇ bonded with organotin is reacted with halogenated W and / or ⁇ in the presence of a palladium catalyst. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
  • boron-containing polymer compound of the present invention is not limited, but it can be used as a p-type organic semiconductor, an n-type organic semiconductor, an ambipolar semiconductor, an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic It can be suitably used for applications such as paper, thermoelectric conversion elements, and optical sensors.
  • the weight average molecular weight of the polymer compound (polymer) was determined by using a high-speed GPC device (manufactured by Tosoh Corporation, model HLC-8320GPC ECcoSEC), an ultraviolet absorption detector (manufactured by Tosoh Corporation, model UV-8320).
  • the measurement solvent was chloroform
  • the GPC column was TSKguardcolumn HHR-H ⁇ 1 + TSKgel GMHHR-H ⁇ 1 (both manufactured by Tosoh Corporation).
  • ⁇ Evaluation of solubility> The boron-containing polymer compound was mixed with chloroform at 0.5% by weight and stirred at 20 ° C. for 15 minutes. A sample that was completely dissolved was marked with ⁇ , and a sample that had undissolved was marked with ⁇ .
  • HOMO ionization potential
  • a solution prepared by dissolving a boron-containing polymer compound (P1) in chloroform at a concentration of 5 mg / g was dropped onto a conductive film of glass with a fluorine-doped tin oxide film, and dried at room temperature in the atmosphere as a measurement sample. The ionization potential was measured using an ionization potential measuring apparatus (PYS-201, manufactured by Sumitomo Heavy Industries, Ltd.).
  • the mobility was measured by evaluating a field effect transistor (TFT).
  • TFT field effect transistor
  • ZEOCOAT ES2110-10 manufactured by Nippon Zeon Co., Ltd.
  • spin coating 500 rpm / 3 sec. And 2000 rpm / 15 sec.
  • a glass substrate on which a Cr gate electrode having a thickness of 500 mm was formed was formed, and 90 ° C. for 2 min. After heating at 150 ° C. for 1 hr.
  • a gate insulating film was formed by heating at Next, a boron-containing polymer compound (P1) solution (0.5 wt%, chlorobenzene solvent) is applied onto the substrate by a spin coating method (1000 rpm, 60 sec.), And is heated at 80 ° C. for 30 minutes on a hot plate in nitrogen. .
  • An organic semiconductor thin film was formed by annealing.
  • gold was vacuum-deposited to a film thickness of 50 nm using a metal mask to form a source electrode and a drain electrode having a channel length of 50 ⁇ m, and a bottom gate / top contact type organic thin film transistor was manufactured.
  • the organic transistor fabricated as described above was measured for current-voltage (IV) characteristics in the atmosphere, and the charge mobility was determined from the saturation region.
  • reaction solution was returned to room temperature and stirred at room temperature for 1 hour. After concentration of the reaction solution, 0.39 g (0.24 mmol) of the boron-containing compound (A1-2) was obtained as a pale orange solid in a yield of 79% by column chromatography using a developing solvent chloroform.
  • Synthesis Example 2 Synthesis of boron-containing compounds A2 and A2-2 / Synthesis of boron-containing compound A2
  • dimesitylfluoroborane was used as a raw material instead of trihexadecylborane.
  • 0.463 g (0.543 mmol) was used as a yellow solid in 28% yield.
  • Example 1 Synthesis and Evaluation of Boron-Containing Polymer Compound (P1) 0.10 g (0.0624 mmol) of boron-containing compound (A1-2), 5,5′-dibromo-2, 2′-bithiophene (Tokyo Chemical Industry) 20.2 mg (0.0624 mmol), tris (dibenzylideneacetone) dipalladium 2.9 mg (5 mol%), tri (o-tolyl) phosphine 1.9 mg (10 mol%), Chlorobenzene (5 mL) was added, and the mixture was stirred for 8 hours under heating under reflux.
  • P1 Synthesis and Evaluation of Boron-Containing Polymer Compound (P1) 0.10 g (0.0624 mmol) of boron-containing compound (A1-2), 5,5′-dibromo-2, 2′-bithiophene (Tokyo Chemical Industry) 20.2 mg (0.0624 mmol), tris (dibenzylideneacetone
  • Example 2 Synthesis and evaluation of boron-containing polymer compound (P2)
  • P1 synthesis method of boron-containing polymer compound (P1)
  • 5,5'-dibromo-2,2'-bithiophene Tokyo Chemical Industry
  • 5,5 ′′ -dibromo-2,2 ′: 5 ′, 2 ′′ -terthiophene Tokyo Chemical Industry
  • 63 mg of a boron-containing polymer compound (P2) was obtained as a dark purple solid.
  • the evaluation results are shown in Table 1.
  • Example 3 Synthesis and evaluation of boron-containing polymer compound (P3)
  • P3 In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) Using 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole, 52 mg of a boron-containing polymer compound (P3) was obtained as a blue solid.
  • the evaluation results are shown in Table 1.
  • Example 4 Synthesis and evaluation of boron-containing polymer compound (P4 )
  • P4 boron-containing polymer compound
  • P1 synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry)
  • 2,6-dibromodithieno [3,2-b: 2 ′, 3′-d] thiophene 58 mg of boron-containing compound (P4) was obtained as a dark purple solid.
  • the evaluation results are shown in Table 1.
  • Example 5 Synthesis and evaluation of boron-containing polymer compound (P5 )
  • P5 boron-containing polymer compound
  • P1 synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry)
  • a boron-containing polymer compound (P5) was obtained as a green solid.
  • Table 1 The evaluation results are shown in Table 1.
  • Compound B1 was prepared according to J.I. Mater. Chem. C, 2014, 2, 3457 and J.H. Mater. Chem. C, 2014, 2, 6376 were referred to and synthesized.
  • Comparative Example 2 Instead of the boron-containing polymer compound (P1) in Example 1, P3HT (manufactured by Soken Chemical Co., Ltd., Verazol HT, weight average molecular weight 47,000) was used, and the annealing conditions for transistor fabrication were 150 ° C. for 30 min. The evaluation was performed in the same manner except that it was changed to. The results are shown in Table 1.
  • P3HT manufactured by Soken Chemical Co., Ltd., Verazol HT, weight average molecular weight 47,000
  • Examples 1 to 5 all showed higher solubility in chloroform than the comparative examples.
  • semiconductor characteristics p-type semiconductor characteristics were exhibited, and a mobility of 10 ⁇ 4 cm 2 / Vs or higher and an on / off value of 10 4 or higher were exhibited.
  • Comparative Example 1 could not be polymerized, and Comparative Example 2 was undissolved in chloroform, and high solubility was not obtained.
  • semiconductor characteristics since the ionization potential is shallow, the atmospheric stability is low and the on / off value is low.

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Abstract

Provided is a boron-containing polymer for organic semiconductors which has deep LUMO/HOMO potentials and which contains a unit structure having a large π-conjugated plane and, despite this, can be made to have a high molecular weight due to the high solubility. According to some embodiments of the present invention, provided is a boron-containing polymer containing a structural unit represented by formula (1), which includes a structure W that has at least two boron-nitrogen coordination bonds and a structure π that is a divalent substituent having a conjugated structure. In formula (1), m is 0 or 1, and structure W is represented by formula (2) or (3). In formulae (2) and (3), rings X1, X2, and Z each represent a monocycle or fused ring having a conjugated structure, rings Y1 and Y2 each represent a five-membered ring having the boron-nitrogen coordination bond, either α1 or α3 is a nitrogen atom, either α2 or α4 is a nitrogen atom, and R1 to R4 may be the same or different and each represent a monovalent substituent which comprises at least one optionally substituted, linear or branched C10-40 alkyl group and which may have be bonded to the boron atom through another skeleton.

Description

ホウ素含有高分子化合物及びその用途Boron-containing polymer compound and use thereof
　本発明は、ホウ素含有高分子化合物及びその用途に関する。 The present invention relates to a boron-containing polymer compound and its use.
　有機半導体素子の実用化に際しては、高性能且つ、安価な塗布プロセスによる製造方法が適用可能な有機半導体が必要となる。中でも高分子有機半導体は、塗布に際して優れた膜質が得られ易く素子特性も安定し易いという利点がある。そして、高分子有機半導体をより高移動度にするには、π共役面積が大きい単位構造を導入し、且つ、より高分子量体であることが望ましいことが知られている。 When putting an organic semiconductor element into practical use, an organic semiconductor to which a high-performance and inexpensive manufacturing method using a coating process is applicable is necessary. Among them, the polymer organic semiconductor has an advantage that an excellent film quality can be easily obtained upon application and the device characteristics are easily stabilized. It is known that in order to make the high molecular organic semiconductor more mobile, it is desirable that a unit structure having a large π-conjugated area is introduced and that the high molecular weight semiconductor be a higher molecular weight body.
　一方、ホウ素－窒素配位結合構造の導入により、ＬＵＭＯ／ＨＯＭＯ準位を深化させることが非特許文献１に開示されており、有機半導体性能の向上も可能であることが特許文献１に開示されている。 On the other hand, it is disclosed in Non-Patent Document 1 that the LUMO / HOMO level is deepened by introducing a boron-nitrogen coordination bond structure, and it is disclosed in Patent Document 1 that the organic semiconductor performance can be improved. ing.
国際公開第２００６／０７０８１７号International Publication No. 2006/070817
　しかしながら、π共役面積が大きいユニットを有する高分子有機半導体は、高分子量化すると溶解性が低下し、それに伴い、溶液での安定性が悪くなるため、塗布プロセスにおける取扱いに問題があった。一般に、より溶解性を高めるためには、π共役ユニットに鎖状置換基を結合させ、その鎖状置換基を伸長させることや、分岐させることなどが考えられる。しかし、有機半導体においては分子の配列が特性に大きな影響を与えるため、構造上適切な位置に鎖状置換基を配置させなければ、乾燥後の有機半導体膜内における分子の配置・配列が適切ではなくなる。有機半導体において、分子の配列も移動度に大きな影響を与えるため、溶解性が向上したとしても、更なる移動度の向上に繋がるとは限らない。従って、溶解性と移動度の両立は困難であった。 However, a polymer organic semiconductor having a unit having a large π-conjugated area has a problem in handling in the coating process because its solubility is lowered when the molecular weight is increased and the stability in the solution is deteriorated accordingly. In general, in order to further increase the solubility, it is conceivable to bond a chain substituent to the π-conjugated unit and extend or branch the chain substituent. However, in organic semiconductors, the molecular arrangement has a great influence on the properties, so unless the chain-like substituents are placed at appropriate positions in the structure, the arrangement and arrangement of the molecules in the organic semiconductor film after drying is not appropriate. Disappear. In an organic semiconductor, since the molecular arrangement also has a great influence on mobility, even if solubility is improved, it does not necessarily lead to further improvement in mobility. Therefore, it is difficult to achieve both solubility and mobility.
　また、ＬＵＭＯ／ＨＯＭＯ準位を深化させ、有機半導体の性能を向上させる可能性は示されているが、特許文献１では得られるのはダイマー構造にとどまる。非特許文献１ではポリマー化には成功しているものの、側鎖が適切ではなく、単位構造のπ共役面積も小さいため、十分な半導体特性が得られていなかった。 Moreover, although the possibility of deepening the LUMO / HOMO level and improving the performance of the organic semiconductor has been shown, Patent Document 1 only provides a dimer structure. In Non-Patent Document 1, although polymerization was successful, the side chain was not appropriate and the π-conjugated area of the unit structure was small, so that sufficient semiconductor characteristics were not obtained.
　本発明はこのような事情に鑑みてなされたものであり、ＬＵＭＯ／ＨＯＭＯ準位が深く、且つ、単位構造中に広いπ共役平面を有しながら、高い可溶性によって高分子量化も可能であり、有機薄膜太陽電池、有機ＥＬ、有機トランジスタ、有機メモリー、電子ペーパー、熱電変換素子、光センサなどの用途に対して好適に用いることができる有機半導体用ホウ素含有高分子化合物を提供するものである。 The present invention has been made in view of such circumstances, and the LUMO / HOMO level is deep, and the unit structure has a wide π-conjugated plane, and can have a high molecular weight due to high solubility. The present invention provides a boron-containing polymer compound for an organic semiconductor that can be suitably used for applications such as an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic paper, thermoelectric conversion element, and optical sensor.
　本発明のいくつかの態様によれば、ホウ素－窒素配位結合を少なくとも２つ有する構造Ｗと、共役構造を持つ２価の置換基である構造πを含んだ下記式（１）で表される構造単位を含む高分子化合物であって
Figure JPOXMLDOC01-appb-C000004
 ｍは０または１を表し、
構造Ｗは、下記式（２）または（３）で表され、
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 環Ｘ１、Ｘ２、Ｚは共役構造を持つ単環または縮合環を示し、
環Ｙ１、Ｙ２は前記ホウ素－窒素配位結合を有する５員環であり、
α１及びα３の何れか一方が窒素原子であり、
α２及びα４の何れか一方が窒素原子であり、
Ｒ１～Ｒ４は同一でも異なっていてもよく、他の骨格を介してホウ素に結合していてもよく、置換されていてもよい炭素数１０～４０の直鎖または分岐のアルキル基を少なくとも１つ有する１価の置換基を表す、
ホウ素含有高分子化合物が提供される。 According to some embodiments of the present invention, the structure W is represented by the following formula (1) including a structure W having at least two boron-nitrogen coordination bonds and a structure π that is a divalent substituent having a conjugated structure. A high molecular compound containing a structural unit
Figure JPOXMLDOC01-appb-C000004
 m represents 0 or 1;
The structure W is represented by the following formula (2) or (3):
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 Rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure,
Rings Y 1 and Y 2 are 5-membered rings having the boron-nitrogen coordination bond,
any one of α 1 and α 3 is a nitrogen atom,
one of α 2 and α 4 is a nitrogen atom,
R 1 to R 4 may be the same or different, may be bonded to boron via another skeleton, and may have at least a linear or branched alkyl group having 10 to 40 carbon atoms that may be substituted. Represents a monovalent substituent having one,
Boron-containing polymeric compounds are provided.
　本発明者が、移動度に優れたホウ素含有高分子化合物について検討を行ったところ、少なくとも２つのホウ素－窒素配位結合を共役平面の広い単位構造中に導入し、ホウ素原子上にアルキル基含有置換基を導入することによって、ＬＵＭＯ／ＨＯＭＯ準位が深く、且つ、移動度の向上に寄与する高分子量であり、単位構造中に広い共役平面を有する高分子化合物を提供できることを見出した。また該高分子化合物は有機半導体として用いることが可能である。 The present inventor has studied a boron-containing polymer compound having excellent mobility. As a result, at least two boron-nitrogen coordination bonds are introduced into a unit structure having a wide conjugate plane, and an alkyl group is contained on the boron atom. It has been found that by introducing a substituent, a polymer compound having a deep LUMO / HOMO level and a high molecular weight contributing to improvement in mobility and having a wide conjugated plane in the unit structure can be provided. The polymer compound can be used as an organic semiconductor.
　以下、本発明の種々の実施形態を例示する。以下に示す実施形態は互いに組み合わせ可能である。
　好ましくは、重量平均分量が２×１０４～１×１０６である。
　好ましくは、Ｗは、隣接するＷまたはπと、Ｗ中の５員環を介して結合している。
　本発明の別の観点によれば、上記のホウ素含有高分子化合物を含有する有機半導体が提供される。 Hereinafter, various embodiments of the present invention will be exemplified. The following embodiments can be combined with each other.
Preferably, the weight average amount is 2 × 10 4 to 1 × 10 6 .
Preferably, W is bonded to adjacent W or π via a 5-membered ring in W.
According to another viewpoint of this invention, the organic semiconductor containing said boron containing high molecular compound is provided.
　以下、本発明の一実施形態について説明する。以下に示す実施形態中で示した各種特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, an embodiment of the present invention will be described. Various characteristic items shown in the following embodiments can be combined with each other. In addition, the invention is independently established for each feature.
　本発明の一実施形態によるホウ素含有高分子化合物は有機半導体として用いることが可能であり、下記式（１）で表される高分子化合物である。
Figure JPOXMLDOC01-appb-C000007
 The boron-containing polymer compound according to an embodiment of the present invention can be used as an organic semiconductor, and is a polymer compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000007
　すなわち、少なくともホウ素－窒素配位結合を少なくとも２つ有する構造Ｗを含む構造を単位構造とした高分子化合物である。好ましくは、単位構造はＷに加えて共役構造を持つ２価の置換基である構造πを含む。すなわち、ｍは０または１であり、好ましくは１である。なぜなら、πを含む構成にすることにより、単位構造中にドナー及びアクセプターの役割を果たす両構造を有し、分子鎖間の相互作用が強くなり易く、移動度が向上していると推測される。 That is, a polymer compound having a structure including a structure W having at least two boron-nitrogen coordination bonds as a unit structure. Preferably, the unit structure includes a structure π which is a divalent substituent having a conjugated structure in addition to W. That is, m is 0 or 1, preferably 1. This is because it is assumed that the structure containing π has both structures serving as a donor and an acceptor in the unit structure, the interaction between the molecular chains tends to be strong, and the mobility is improved. .
　上記式（１）中Ｗで表される単位構造は、ホウ素－窒素配位結合を少なくとも２つ有する下記式（２）または（３）で表される構造である。
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
 The unit structure represented by W in the above formula (1) is a structure represented by the following formula (2) or (3) having at least two boron-nitrogen coordination bonds.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
　ホウ素－窒素配位結合を単位構造中に少なくとも２つ有することが、移動度の観点から好ましい。ホウ素－窒素間の電子的な偏りが分子鎖間の相互作用を強めると考えられ、ホウ素－窒素配位結合を単位構造中に２つ以上含むことにより、より電子的な偏りが大きくなり、分子鎖間の相互作用が強くなることで移動度が向上すると考えられる。合成の容易性の観点からホウ素－窒素配位結合を単位構造中に２つ有することがより好ましい。 From the viewpoint of mobility, it is preferable to have at least two boron-nitrogen coordination bonds in the unit structure. The electronic bias between boron and nitrogen is thought to strengthen the interaction between the molecular chains. By including two or more boron-nitrogen coordination bonds in the unit structure, the electronic bias becomes larger and the molecule It is considered that the mobility is improved by the stronger interaction between the chains. From the viewpoint of ease of synthesis, it is more preferable to have two boron-nitrogen coordination bonds in the unit structure.
　ホウ素－窒素配位結合を有することによる別の効果として、ＬＵＭＯ／ＨＯＭＯ準位を深くし、大気安定性が向上することが期待される。本発明の一実施形態ではホウ素－窒素配位結合を単位構造中に２以上含むことにより、さらに効果を奏すると考えられる。 As another effect of having a boron-nitrogen coordination bond, it is expected that the LUMO / HOMO level is deepened and the atmospheric stability is improved. In one embodiment of the present invention, it is considered that a further effect can be obtained by including two or more boron-nitrogen coordination bonds in the unit structure.
　Ｗは、環Ｘ１と、Ｘ２と、Ｙ１と、Ｙ２と、Ｚにより構成され、環Ｘ１、Ｘ２、Ｚは共役構造を持つ単環または縮合環を示す。 W is composed of rings X 1 , X 2 , Y 1 , Y 2 , and Z, and rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure.
　α１とα２は、互いに同一でも異なっていてもよく、好ましくは同一である。また、α３とα４は、互いに同一でも異なっていてもよく、好ましくは同一である。同一である場合には、異なる場合に比べ合成が容易である利点を有し、また対象性が高いことから分子鎖の配置・配列が適切になり易く、移動度が高くなり易い。 α 1 and α 2 may be the same as or different from each other, and are preferably the same. Further, α 3 and α 4 may be the same or different from each other, preferably the same. When they are the same, there is an advantage that the synthesis is easier than when they are different, and since the target property is high, the arrangement and arrangement of the molecular chains are likely to be appropriate, and the mobility tends to be high.
　α１とα３の一方は、環Ｙ１中のホウ素原子とホウ素－窒素配位結合を形成する窒素原子であり、他方は特に限定されないが、例えば炭素原子である。また、α２とα４の一方は、環Ｙ２中のホウ素原子とホウ素－窒素配位結合を形成する窒素原子であり、他方は特に限定されないが、例えば炭素原子である。 One of α 1 and α 3 is a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in ring Y 1 , and the other is not particularly limited, but is, for example, a carbon atom. One of α 2 and α 4 is a nitrogen atom that forms a boron-nitrogen coordination bond with a boron atom in the ring Y 2 , and the other is not particularly limited, but is, for example, a carbon atom.
　環Ｘ１、Ｘ２は共役構造を持つ単環または縮合環であり、ホウ素－窒素配位結合を形成する窒素原子を含む場合がある。 Rings X 1 and X 2 are monocyclic or condensed rings having a conjugated structure and may contain a nitrogen atom that forms a boron-nitrogen coordination bond.
　環Ｘ１、Ｘ２はヘテロ原子を含まなくてもよいが、好ましくはヘテロ原子を含む複素環である。複素環は、例えば、ピロール、フラン、チオフェン、セレノフェン、イミダゾール、ピラゾール、オキサゾール、チアゾール、ピリジン、ピリミジン、ピリダジン、ピラジン等であり、またこれらが縮合した構造であり、より好ましくは硫黄原子を含有し、例えば、チオフェン、チエノチオフェン、ベンゾチオフェン、ベンゾジチオフェン、チアゾール、チアゾロチアゾール等であり、さらに好ましくは、チオフェンまたはチアゾールである。 Rings X 1 and X 2 may not contain a hetero atom, but are preferably a hetero ring containing a hetero atom. The heterocyclic ring is, for example, pyrrole, furan, thiophene, selenophene, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine and the like, and these are condensed structures, more preferably containing a sulfur atom. For example, thiophene, thienothiophene, benzothiophene, benzodithiophene, thiazole, thiazolothiazole and the like, more preferably thiophene or thiazole.
　環Ｘ１、Ｘ２が環Ｙ１、Ｙ２中のホウ素原子とホウ素－窒素配位結合を形成する窒素原子を含む場合には、例えば、イミダゾール、ピラゾール、チアゾール、ピリジン等である。好ましくは、チアゾール、ピリジンであり、さらに好ましくは環Ｘ１、Ｘ２は硫黄原子を含有し、例えば、チアゾールである。 When the rings X 1 and X 2 contain a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in the rings Y 1 and Y 2 , examples thereof include imidazole, pyrazole, thiazole, and pyridine. Preferred are thiazole and pyridine, and more preferred are rings X 1 and X 2 containing a sulfur atom, for example, thiazole.
　環Ｘ１及びＸ２の単環または縮合環は、半導体特性を損なわない範囲で置換されていてもよく、置換基には限定はないが、具体的には直鎖、分岐、または環状のアルキル基、アルコキシ基、アルキルチオ基、スルホ基、ヒドロキシ基、カルボキシ基、アミノ基、アミド基、エステル基、フェニル基等、及び、スルホ基、ヒドロキシ基、カルボキシ基、アミノ基、ハロゲン基で置換された直鎖または分岐状のアルキル基、アルコキシアルキル基、アルキレンオキサイド基、フェニル基等であってもよく、置換基は複数有してもよい。 The monocyclic ring or condensed ring of the rings X 1 and X 2 may be substituted as long as the semiconductor properties are not impaired, and the substituent is not limited, but specifically, a linear, branched, or cyclic alkyl Group, alkoxy group, alkylthio group, sulfo group, hydroxy group, carboxy group, amino group, amide group, ester group, phenyl group, etc., and substituted with sulfo group, hydroxy group, carboxy group, amino group, halogen group It may be a linear or branched alkyl group, an alkoxyalkyl group, an alkylene oxide group, a phenyl group or the like, and may have a plurality of substituents.
　Ｗは、隣接するＷまたはπと、Ｗ中の５員環または６員環を介して結合しており、好ましくは５員環を介して結合している。５員環の場合には隣接するＷまたはπとの立体反発が少なく、連続した平面構造を形成し易くなり、移動度が向上すると考えられるからである。 W is bonded to adjacent W or π via a 5-membered ring or 6-membered ring in W, preferably bonded via a 5-membered ring. This is because in the case of a five-membered ring, there is little steric repulsion with the adjacent W or π, it is easy to form a continuous planar structure, and the mobility is considered to be improved.
　環Ｚは共役構造を持つ単環または縮合環であり、ホウ素－窒素配位結合を形成する窒素原子を含む場合がある。環Ｚはヘテロ原子を含んでも含まなくてもよく、例えば、ベンゼン、ナフタレン、アントラセン、ピラジン、チエノチオフェン、ベンゾジチオフェン、チアゾロチアゾール、ベンゾビスチアゾール等である。 Ring Z is a monocyclic or condensed ring having a conjugated structure and may contain a nitrogen atom forming a boron-nitrogen coordination bond. Ring Z may or may not contain heteroatoms, such as benzene, naphthalene, anthracene, pyrazine, thienothiophene, benzodithiophene, thiazolothiazole, benzobisthiazole, and the like.
　環Ｚが環Ｙ１、Ｙ２中のホウ素原子とホウ素－窒素配位結合を形成する窒素原子を含む場合には、環Ｚは例えば、ピラジン、チアゾロチアゾール、ナフチリジン、ベンゾビスチアゾール、ピラジノビスチアゾール等である。好ましくは、チアゾロチアゾールまたはベンゾビスチアゾールである。 When ring Z contains a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in rings Y 1 and Y 2 , ring Z is, for example, pyrazine, thiazolothiazole, naphthyridine, benzobisthiazole, pyrazino Bisthiazole and the like. Preferred is thiazolothiazole or benzobisthiazole.
　環Ｙ１、Ｙ２はホウ素－窒素配位結合を有する５員環である。環Ｙ１及びＹ２中でホウ素－窒素配位結合を形成するホウ素原子は同一でも異なってもよいアルキル基含有置換基Ｒ１～Ｒ４を有する。 Rings Y 1 and Y 2 are 5-membered rings having a boron-nitrogen coordination bond. The boron atoms forming the boron-nitrogen coordination bond in the rings Y 1 and Y 2 have alkyl group-containing substituents R 1 to R 4 which may be the same or different.
　Ｗがホウ素－窒素配位結合を２つ有する場合、２つのホウ素原子は、上記（２）式のように異なる側に位置していてもよく、上記（３）式のように同じ側に位置していてもよい。各環に導入される置換基により適切な位置は異なるため何れかに限定されるものではなく、また何れの場合でもホウ素－窒素配位結合を２つ有するため同様の効果を奏するものと考えられる。ただ、合成の容易性の観点からは、上記（２）式の様に異なる側に位置していることが優位な場合が多いと考えられる。 When W has two boron-nitrogen coordination bonds, the two boron atoms may be located on different sides as in the above formula (2), or may be located on the same side as in the above formula (3). You may do it. The appropriate position differs depending on the substituents introduced into each ring, so that the position is not limited to any one. In any case, it has two boron-nitrogen coordination bonds, and the same effect is considered to be achieved. . However, from the viewpoint of ease of synthesis, it is considered that it is often advantageous to be located on different sides as in the above formula (2).
　Ｒ１～Ｒ４は同一でも異なっていてもよく、置換されていてもよい直鎖または分岐の炭素数１０～４０のアルキル基を少なくとも１つ有する１価の置換基である。Ｒ１～Ｒ４は、アルキル基がホウ素原子に直接結合していても、他の骨格を介して結合していてもよい。上記アルキル基の炭素数は、好ましくは１２以上であり、より好ましくは１４以上である。上記アルキル基の炭素数は、好ましくは３０以下であり、より好ましくは２５以下である。なお、上記炭素数は、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５、２６、２７、２８、２９、３０、３１、３２、３３、３４、３５、３６、３７、３８、３９、４０であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。このようなアルキル基含有置換基を導入した場合、溶媒への溶解性が高く塗布プロセスにより有機半導体を作製することができる。ここで、溶媒への溶解性とは、主にハロゲン系溶媒、芳香族系溶媒等への溶解性を意味し、具体的にはクロロホルム、クロロベンゼン、ジクロロベンゼン、トルエン、メシチレン、アニソール、テトラリン、シクロヘキシルベンゼンに対する溶解性を意味する。 R 1 to R 4 may be the same or different, and are monovalent substituents having at least one linear or branched alkyl group having 10 to 40 carbon atoms which may be substituted. In R 1 to R 4 , the alkyl group may be directly bonded to the boron atom or may be bonded via another skeleton. The number of carbon atoms of the alkyl group is preferably 12 or more, more preferably 14 or more. The number of carbon atoms of the alkyl group is preferably 30 or less, more preferably 25 or less. In addition, the said carbon number is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 32, 33, 34, 35, 36, 37, 38, 39, 40, and may be within a range between any two of the numerical values exemplified here. When such an alkyl group-containing substituent is introduced, the organic semiconductor can be produced by a coating process with high solubility in a solvent. Here, the solubility in a solvent mainly means the solubility in a halogen solvent, an aromatic solvent, etc., specifically, chloroform, chlorobenzene, dichlorobenzene, toluene, mesitylene, anisole, tetralin, cyclohexyl. It means solubility in benzene.
　Ｒ１～Ｒ４の中のアルキル基を置換してもよい置換基としては、例えば、スルホ基、ヒドロキシ基、アルコキシ基、アルキルチオ基、カルボキシ基、エステル基、アミノ基、アミド基、ハロゲン基、フェニル基等である。 Examples of the substituent that may substitute the alkyl group in R 1 to R 4 include a sulfo group, a hydroxy group, an alkoxy group, an alkylthio group, a carboxy group, an ester group, an amino group, an amide group, a halogen group, A phenyl group and the like;
　Ｒ１～Ｒ４が他の骨格を介して結合している場合には、上記他の骨格としては、例えば、酸素、窒素、硫黄等のヘテロ原子、ベンゼン環、ナフタレン環、アズレン環、アントラセン環、フェナントレン環、ピレン環、クリセン環、テトラセン環、トリフェニレン環、アセナフテン環、コロネン環、フルオレン環、フルオラントレン環、ペンタセン環、ペリレン環、ペンタフェン環、ピセン環、ピラントレン環等の芳香環、ピリジン、イミダゾール、チオフェン等の複素環であり、複数を組み合わせても良い。更に、他の骨格とホウ素との間に更に炭素数が１～６のアルキル鎖を介しても良い。 When R 1 to R 4 are bonded via another skeleton, examples of the other skeleton include heteroatoms such as oxygen, nitrogen, and sulfur, a benzene ring, a naphthalene ring, an azulene ring, and an anthracene ring. , Aromatic ring such as phenanthrene ring, pyrene ring, chrysene ring, tetracene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyranthrene ring, pyridine , Imidazole, thiophene and the like, and a plurality of them may be combined. Further, an alkyl chain having 1 to 6 carbon atoms may be interposed between another skeleton and boron.
　Ｒ１～Ｒ４は、好ましくは、直鎖または分岐のアルキル基が直接ホウ素に結合、または、酸素または硫黄及び／またはフェニル基、ベンジル基、フェネチル基を介してホウ素に結合しており、より好ましくは、直鎖または分岐のアルキル基がホウ素に直接結合しており、さらに好ましくは、直鎖のアルキル基がホウ素に直接結合している。 R 1 to R 4 are preferably such that a linear or branched alkyl group is directly bonded to boron, or bonded to boron through oxygen or sulfur and / or a phenyl group, benzyl group, phenethyl group, Preferably, a linear or branched alkyl group is directly bonded to boron, and more preferably, a linear alkyl group is directly bonded to boron.
　Ｗの具体的な構造として、具体的には、下記式（４）に示す構造が例示されるがこれに限定されない。
Figure JPOXMLDOC01-appb-C000010
 Specific examples of the structure of W include, but are not limited to, the structure represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000010
＜１．ホウ素含有化合物の合成＞
　上記式（２）または式（３）で表されるＷの合成は、種々の方法により合成可能であるが、上記式（２）で表されるＷは、例えば下記反応式（５）または下記反応式（６）の経路で合成することができる。
Figure JPOXMLDOC01-appb-C000011
 （式（５）中のＲ１～Ｒ４は、化学式（２）と同じであり、Ｒ５はハロゲンを表す。）
Figure JPOXMLDOC01-appb-C000012
 （式（６）中のＲ１～Ｒ４は、化学式（２）と同じであり、Ｒ５はハロゲンを表す。） <1. Synthesis of boron-containing compounds>
Synthesis of W represented by the above formula (2) or formula (3) can be synthesized by various methods. For example, W represented by the above formula (2) can be synthesized by the following reaction formula (5) or It can be synthesized by the route of reaction formula (6).
Figure JPOXMLDOC01-appb-C000011
 (R 1 to R 4 in Formula (5) are the same as in Chemical Formula (2), and R 5 represents halogen.)
Figure JPOXMLDOC01-appb-C000012
 (R 1 to R 4 in formula (6) are the same as in chemical formula (2), and R 5 represents halogen.)
＜１－１．ホウ素置換基の導入＞
　不活性ガスで置換した反応容器に化合物ＷＡ－１またはＷＢ－１、反応溶媒を計量し、冷却した後、塩基を加え、数時間撹拌した後、置換ボランを加え攪拌を行う。反応終了後、精製工程を行いホウ素置換基が導入されたＷＡ－２またはＷＢ－２が得られる。 <1-1. Introduction of boron substituent>
The compound WA-1 or WB-1 and the reaction solvent are weighed in a reaction vessel substituted with an inert gas, cooled, a base is added, and the mixture is stirred for several hours, and then substituted borane is added and stirred. After completion of the reaction, a purification step is performed to obtain WA-2 or WB-2 having a boron substituent introduced.
　前記反応容器は、特に限定されないが、ガラス製やテフロン（登録商標）製などを用いることができる。 The reaction vessel is not particularly limited, and glass, Teflon (registered trademark), or the like can be used.
　前記反応溶媒としては、特に限定されないが、反応が進行する溶媒であればよく、テトラヒドロフラン、ｔｅｒｔ－ブチルメチルエーテル、アセトニトリル、フェノール、ベンゼン、トルエン等があげられる。 The reaction solvent is not particularly limited, and may be any solvent in which the reaction proceeds, and examples thereof include tetrahydrofuran, tert-butyl methyl ether, acetonitrile, phenol, benzene, toluene and the like.
　前記不活性ガスは窒素、アルゴン、ヘリウムなどがあげられる。 The inert gas includes nitrogen, argon, helium and the like.
　前記攪拌方法は、特に限定はしないが、スターラーを用いてもよく、振とう機を用いてもよい。 The stirring method is not particularly limited, but a stirrer or a shaker may be used.
　前記精製工程は、目的物が単離できる工程であればよく、公知の方法を用いることができ、具体的に分液抽出、カラムクロマトグラフィーによる単離、再結晶などの方法があげられ、それらを組み合わせて単離精製を行っても良い。 The purification step may be any step that can isolate the target product, and known methods can be used. Specific examples include separation extraction, isolation by column chromatography, and recrystallization. Isolation and purification may be performed in combination.
　前記塩基としては、特に限定されないが、Ｂ－Ｎ架橋反応が進行する塩基であればよく、アルキルリチウム等の塩基があげられ、具体的には、メチルリチウム、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウム等があげられる。 The base is not particularly limited, and may be any base that allows BN crosslinking reaction to proceed. Examples of the base include alkyl lithium, and specific examples include methyl lithium, n-butyl lithium, sec-butyl lithium. Tert-butyllithium and the like.
　前記塩基を加える際の冷却温度は、－１００℃～－５０℃であり、好ましくは－９０℃～－７０℃である。この温度は、具体的には例えば、－１００、－９０、－８０、－７０、－６０または５０℃であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The cooling temperature when adding the base is −100 ° C. to −50 ° C., preferably −90 ° C. to −70 ° C. Specifically, this temperature is, for example, −100, −90, −80, −70, −60, or 50 ° C., and may be within a range between any two of the numerical values exemplified here.
　前記塩基を加えたあとの数時間の撹拌は、特に限定はしないが、例えば１～６時間であり、好ましくは１～４時間である。この時間は、具体的には例えば、１、２、３、４、５または６時間であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The stirring for several hours after the addition of the base is not particularly limited, but is, for example, 1 to 6 hours, and preferably 1 to 4 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5 or 6 hours, and may be within a range between any two of the numerical values exemplified here.
　前記置換ボランとしては、本発明に用いることが可能な置換基Ｒ１～Ｒ４を有し、Ｂ－Ｎ架橋反応が進行するボランであれば特に制限はされない。 The substituted borane is not particularly limited as long as it is a borane having substituents R 1 to R 4 that can be used in the present invention and in which a BN crosslinking reaction proceeds.
　前記ボランを加えたあとの撹拌時間は、特に限定はしないが、例えば１～２４時間であり、好ましくは８～２４時間である。この時間は、具体的には例えば、１、２、３、４、５、６、７、８、９、１０、１１、１２、１５、１８、２１または２４時間であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The stirring time after adding the borane is not particularly limited, but is, for example, 1 to 24 hours, preferably 8 to 24 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 21 or 24 hours. It may be within the range between any two.
　前記ボランを加えたあとの撹拌温度は、－７８℃～２５℃であり、好ましくは０℃～２５℃である。この温度は、具体的には例えば、０、５、１０、１５、２０または、２５℃であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The stirring temperature after adding the borane is −78 ° C. to 25 ° C., preferably 0 ° C. to 25 ° C. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, or 25 ° C., and may be within a range between any two of the numerical values exemplified here.
　また、Ｂ－Ｎ架橋反応において、ボランにボロントリブロマイドを用いて、ＢＢｒ２を架橋体とし、その後、アルキルマグネシウムブロマイドのようなグリニャール試薬を用いてグリニャール反応行い置換基Ｒ１～Ｒ４を導入してもよい。 Also, in the BN crosslinking reaction, boron tribromide is used as borane, BBr 2 is converted into a crosslinked product, and then a Grignard reaction is performed using a Grignard reagent such as alkylmagnesium bromide to introduce substituents R 1 to R 4 . May be.
　上記式（１）中のπは共役構造を持つ２価の置換基を表し、好ましくは下記式（７）で表される。
Figure JPOXMLDOC01-appb-C000013
 　ここで、Ｖ１及びＶ２は同一でも異なってもよく、－ＣＲ６＝ＣＲ６－、－Ｃ≡Ｃ－、２～４０個の炭素原子を有する２価の芳香環または複素環であり、該基は無置換であるか、１個以上の基Ｒ６で置換されており、ａ及びｂは、同一でも異なっていてもよく、０～２の整数を表す。
　Ｒ６はＨ、ハロゲン、シアノ基、あるいは炭素数１～４０である直鎖または分岐鎖のアルキル基、アルコキシ基、アルキルチオ基を表す。
　より好ましくは、Ｗと結合している部位が、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、あるいは、５員環である。これらの場合には結合しているＷとの立体反発が少なく、連続した平面構造を形成し易くなり、移動度が向上すると考えられるからである。具体的には、下記式（８）に示す構造が例示されるがこれに限定されない。
Figure JPOXMLDOC01-appb-C000014
 Π in the above formula (1) represents a divalent substituent having a conjugated structure, and is preferably represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000013
 Here, V 1 and V 2 may be the same or different and are —CR 6 = CR 6 —, —C≡C—, a divalent aromatic ring or heterocyclic ring having 2 to 40 carbon atoms, The group is unsubstituted or substituted with one or more groups R 6 and a and b may be the same or different and represent an integer of 0-2.
R 6 represents H, a halogen, a cyano group, or a linear or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group, or an alkylthio group.
More preferably, the site bonded to W is —CH═CH—, —C≡C—, or a 5-membered ring. This is because in these cases, there is little steric repulsion with the bonded W, it is easy to form a continuous planar structure, and the mobility is considered to be improved. Specifically, the structure shown in the following formula (8) is exemplified, but not limited thereto.
Figure JPOXMLDOC01-appb-C000014
　本発明のホウ素含有高分子化合物は、高分子化合物中に前記化学式（１）に示された構造を含んだ共重合体を含んでいれば良いが、分子鎖間の相互作用をより強くするため、前記化学式（１）中のｍが１である、Ｗとπが交互に配置された交互共重合体を含んでいることが好ましい。 The boron-containing polymer compound of the present invention may contain a copolymer containing the structure represented by the chemical formula (1) in the polymer compound, but in order to further strengthen the interaction between the molecular chains. In addition, it is preferable to include an alternating copolymer in which m in the chemical formula (1) is 1, and W and π are alternately arranged.
　本発明のホウ素含有高分子化合物の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」という。）で測定したポリスチレン換算の値であり、通常、２×１０４～２×１０８である。移動度と、溶解性及び成膜性のバランスの観点から、高分子化合物の重量平均分子量は２×１０４～１×１０６であることが好ましく、より好ましくは３×１０４～５×１０５である。 The weight average molecular weight (Mw) of the boron-containing polymer compound of the present invention is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”), and is usually 2 × 10 4 to 2 ×. 10 8 . From the viewpoint of the balance between mobility, solubility, and film formability, the weight average molecular weight of the polymer compound is preferably 2 × 10 4 to 1 × 10 6 , more preferably 3 × 10 4 to 5 × 10. 5 .
　上記式（１）を含むホウ素含有高分子化合物の重合方法としては、特に限定は無いが、鈴木カップリング、スティルカップリングウルマン反応、グレーサー反応、ヘック反応、根岸カップリング、園頭カップリング、熊田カップリングなどを用いることができ、合成の容易さや、使用できるモノマーの制限が少ないという点で鈴木カップリングやスティルカップリングが好ましい。 The method for polymerizing the boron-containing polymer compound including the above formula (1) is not particularly limited, but Suzuki coupling, Still coupling Ullmann reaction, Gracer reaction, Heck reaction, Negishi coupling, Sonogashira coupling, Kumada Coupling and the like can be used, and Suzuki coupling and Stille coupling are preferable in terms of ease of synthesis and few restrictions on the monomers that can be used.
鈴木カップリングによる重合を行う方法としては、通常、ホウ素酸またはホウ素酸エステルが結合したＷ及び／またはπと、ハロゲン化されたＷ及び／またはπを原料として、パラジウム触媒および塩基の存在下で反応させて重合することが挙げられ、アルゴンガス、窒素ガス等の不活性雰囲気下において、触媒が失活しない反応系で行うことが好ましい。例えば、アルゴンガスや窒素ガス等で十分置換された系で行うことが好ましい。 As a method for performing polymerization by Suzuki coupling, usually, W and / or π bonded with boronic acid or a boronic acid ester and halogenated W and / or π are used as raw materials in the presence of a palladium catalyst and a base. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated in an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
スティルカップリングによる重合を行う方法としては、通常、有機スズが結合したＷ及び／またはπと、ハロゲン化されたＷ及び／またはπを原料として、パラジウム触媒の存在下で反応させて重合することが挙げられ、アルゴンガス、窒素ガス等の不活性雰囲気下において、触媒が失活しない反応系で行うことが好ましい。例えば、アルゴンガスや窒素ガス等で十分置換された系で行うことが好ましい。 As a method of performing polymerization by Still coupling, usually, W and / or π bonded with organotin is reacted with halogenated W and / or π in the presence of a palladium catalyst. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
　本発明のホウ素含有高分子化合物の用途には限定はないが、ｐ型有機半導体、ｎ型有機半導体、アンバイポーラ型半導体として利用でき、有機薄膜太陽電池、有機ＥＬ、有機トランジスタ、有機メモリー、電子ペーパー、熱電変換素子、光センサなどの用途に好適に用いることができる。 The use of the boron-containing polymer compound of the present invention is not limited, but it can be used as a p-type organic semiconductor, an n-type organic semiconductor, an ambipolar semiconductor, an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic It can be suitably used for applications such as paper, thermoelectric conversion elements, and optical sensors.
＜分子量の測定＞
以下の実施例において、高分子化合物（重合体）の重量平均分子量は、高速ＧＰＣ装置（東ソー株式会社製、型式ＨＬＣ－８３２０ＧＰＣ ＥＣｃｏＳＥＣ）、紫外吸光検出器（東ソー株式会社製、型式ＵＶ－８３２０）を用いて測定し、ポリスチレン換算によって算出した。測定溶媒はクロロホルムを用い、ＧＰＣカラムは、ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ－Ｈ×１＋ＴＳＫｇｅｌ ＧＭＨＨＲ－Ｈ×１（いずれも東ソー株式会社製）を用いた。 <Measurement of molecular weight>
In the following examples, the weight average molecular weight of the polymer compound (polymer) was determined by using a high-speed GPC device (manufactured by Tosoh Corporation, model HLC-8320GPC ECcoSEC), an ultraviolet absorption detector (manufactured by Tosoh Corporation, model UV-8320). Was calculated using polystyrene conversion. The measurement solvent was chloroform, and the GPC column was TSKguardcolumn HHR-H × 1 + TSKgel GMHHR-H × 1 (both manufactured by Tosoh Corporation).
＜可溶性の評価＞
　ホウ素含有高分子化合物を、０．５重量％になるようにしてクロロホルムに混合し、２０℃で１５分間撹拌した。完全に溶解したものを○、溶け残りがあるものを×とした。
＜イオン化ポテンシャル（ＨＯＭＯ）の測定＞
　ホウ素含有高分子化合物（Ｐ１）を５ｍｇ／ｇの濃度でクロロホルムに溶解させた溶液をフッ素ドープ酸化スズ膜付きガラスの導電膜上に滴下させ、室温、大気下で乾燥させたものを測定サンプルとして、イオン化ポテンシャル測定装置（ＰＹＳ－２０１、住友重機械工業製）を用いて測定した。 <Evaluation of solubility>
The boron-containing polymer compound was mixed with chloroform at 0.5% by weight and stirred at 20 ° C. for 15 minutes. A sample that was completely dissolved was marked with ◯, and a sample that had undissolved was marked with ×.
<Measurement of ionization potential (HOMO)>
A solution prepared by dissolving a boron-containing polymer compound (P1) in chloroform at a concentration of 5 mg / g was dropped onto a conductive film of glass with a fluorine-doped tin oxide film, and dried at room temperature in the atmosphere as a measurement sample. The ionization potential was measured using an ionization potential measuring apparatus (PYS-201, manufactured by Sumitomo Heavy Industries, Ltd.).
＜エネルギーギャップ（Ｅｇ）及びＬＵＭＯの測定＞
ホウ素含有高分子化合物をクロロホルムに溶解させた溶液を、紫外可視近赤分光光度計（ＪＡＳＣＯ、Ｖ－６７０）によって紫外可視光吸収スペクトルを測定し、スペクトルの長波長側の吸収端での波長をエネルギーに換算した値をＥｇとした。また、イオン化ポテンシャル（ＨＯＭＯ）とＥｇの値を差し引き、ＬＵＭＯを換算した。 <Measurement of energy gap (Eg) and LUMO>
A solution in which a boron-containing polymer compound is dissolved in chloroform is measured with an ultraviolet-visible near-red spectrophotometer (JASCO, V-670), and an ultraviolet-visible light absorption spectrum is measured. The value converted into energy was defined as Eg. Also, the ionization potential (HOMO) and Eg values were subtracted to convert LUMO.
＜移動度の測定＞
　移動度の測定は電界効果トランジスタ（ＴＦＴ）の評価によって行った。
　厚さ５００ÅのＣｒゲート電極を作成したガラス基板上に、ＺＥＯＣＯＡＴ ＥＳ２１１０－１０(日本ゼオン株式会社製)をスピンコート法(５００ｒｐｍ／３ｓｅｃ．及び２０００ｒｐｍ／１５ｓｅｃ.)によって塗布し、９０℃２ｍｉｎ．で加熱した後、更に１５０℃１ｈｒ．で加熱することによってゲート絶縁膜を形成した。次に、ホウ素含有高分子化合物（Ｐ１）溶液（０．５ｗｔ％、クロロベンゼン溶媒）を、基板上にスピンコート法（１０００ｒｐｍ、６０ｓｅｃ．）によって塗布し、窒素下中、ホットプレート上で８０℃３０ｍｉｎ．でアニール処理を行い、有機半導体薄膜を形成した。次に、メタルマスクを用いて金を５０ｎｍの膜厚に真空蒸着することで、５０μｍのチャネル長を持つソース電極、ドレイン電極を形成し、ボトムゲート・トップコンタクト型の有機薄膜トランジスタを作製した。
　以上のように作製した有機トランジスタを大気下にて電流－電圧（Ｉ－Ｖ）特性を測定し、飽和領域から電荷移動度を求めた。 <Measurement of mobility>
The mobility was measured by evaluating a field effect transistor (TFT).
ZEOCOAT ES2110-10 (manufactured by Nippon Zeon Co., Ltd.) was applied by spin coating (500 rpm / 3 sec. And 2000 rpm / 15 sec.) On a glass substrate on which a Cr gate electrode having a thickness of 500 mm was formed, and 90 ° C. for 2 min. After heating at 150 ° C. for 1 hr. A gate insulating film was formed by heating at Next, a boron-containing polymer compound (P1) solution (0.5 wt%, chlorobenzene solvent) is applied onto the substrate by a spin coating method (1000 rpm, 60 sec.), And is heated at 80 ° C. for 30 minutes on a hot plate in nitrogen. . An organic semiconductor thin film was formed by annealing. Next, gold was vacuum-deposited to a film thickness of 50 nm using a metal mask to form a source electrode and a drain electrode having a channel length of 50 μm, and a bottom gate / top contact type organic thin film transistor was manufactured.
The organic transistor fabricated as described above was measured for current-voltage (IV) characteristics in the atmosphere, and the charge mobility was determined from the saturation region.
＜Ｗの合成＞
合成例１：ホウ素含有化合物Ａ１、Ａ１－２の合成
・２，５－ビス（３－ブロモ－２－チエニル）ベンゾビスチアゾール（Ａ１－１）の合成
　窒素置換した５００ｍＬシュレンク管に２，５－ジアミノ－１，４－ベンゼンジチオール二塩酸塩４．４０ｇ（１７．９ｍｍｏｌ）とポリリン酸５０ｇを投入し、１００℃で３時間加熱攪拌した。この溶液に、３－ブロモチオフェン－２－カルボン酸７．８０ｇ（３７．７ｍｍｏｌ）のスルホラン（４７ｇ）溶液を加え、さらに１００℃で５時間過熱攪拌した。反応溶液を室温に戻し、水を加えた後、ろ過で固体を回収した。得られた個体をジメチルホルムアミドにより洗浄することで、２，５－ビス（３－ブロモ－２－チエニル）ベンゾビスチアゾール（Ａ１－１）８．０３ｇ（１５．６ｍｍｏｌ）を淡黄色の固体として収率８７％で得た。 <Synthesis of W>
Synthesis Example 1: Synthesis of boron-containing compounds A1 and A1-2-Synthesis of 2,5-bis (3-bromo-2-thienyl) benzobisthiazole (A1-1) 2,5-bis (3-1-1) was added to a nitrogen-substituted 500 mL Schlenk tube. Diamino-1,4-benzenedithiol dihydrochloride (4.40 g, 17.9 mmol) and polyphosphoric acid (50 g) were added, and the mixture was heated and stirred at 100 ° C. for 3 hours. To this solution was added a solution of 7.80 g (37.7 mmol) of 3-bromothiophene-2-carboxylic acid in sulfolane (47 g), and the mixture was further heated and stirred at 100 ° C. for 5 hours. The reaction solution was returned to room temperature, water was added, and the solid was collected by filtration. The obtained solid was washed with dimethylformamide to obtain 8.03 g (15.6 mmol) of 2,5-bis (3-bromo-2-thienyl) benzobisthiazole (A1-1) as a pale yellow solid. Obtained at a rate of 87%.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
・ホウ素含有化合物Ａ１の合成
　窒素置換した５００ｍＬシュレンク管に２，５－ビス（３－ブロモ－２－チエニル）ベンゾビスチアゾール（化合物Ａ１－１）１．００ｇ（１．９４ｍｍｏｌ）、脱水テトラヒドロフラン７５ｍＬを投入し、ｔｅｒｔ－ブチルリチウム１．６Ｍ溶液５．１ｍＬ（８．１５ｍｍｏｌ）を－７８℃で滴下し、そのまま１時間攪拌した。この溶液に、後述するトリへキサデシルボラン０．９１Ｍ溶液４２．７ｍＬ（３．８９ｍｍｏｌ）を－７８℃で滴下した。
　ここで、トリヘキサデシルボラン溶液は、窒素置換したシュレンク管に１－ヘキサデセン３．３ｍＬ（１１．６ｍｍｏｌ）、脱水テトラヒドロフラン３５ｍｌを投入し、ボラン－テトラヒドロフラン　コンプレックス０．９Ｍ溶液４．３ｍＬ（３．８８ｍｍｏｌ）を０℃で滴下し、そのまま１時間攪拌することで調整した。
　反応溶液をゆっくりと室温に戻し、室温で３時間撹拌した。反応液を濃縮後、展開溶媒にヘキサンを用いたカラムクロマトグラフィーにより、ホウ素含有化合物（Ａ１）１．０９ｇ（０．８５ｍｍｏｌ）を淡黄色の固体として収率４４％で得た。 Synthesis of boron-containing compound A1 To a nitrogen-substituted 500 mL Schlenk tube, 1.00 g (1.94 mmol) of 2,5-bis (3-bromo-2-thienyl) benzobisthiazole (compound A1-1) and 75 mL of dehydrated tetrahydrofuran were added. Then, 5.1 mL (8.15 mmol) of a tert-butyllithium 1.6M solution was added dropwise at −78 ° C., and the mixture was stirred as it was for 1 hour. To this solution, 42.7 mL (3.89 mmol) of a trihexadecylborane 0.91M solution described later was added dropwise at −78 ° C.
Here, the trihexadecylborane solution was charged with 3.3 mL (11.6 mmol) of 1-hexadecene and 35 mL of dehydrated tetrahydrofuran in a Schlenk tube purged with nitrogen, and 4.3 mL (3.88 mmol) of a borane-tetrahydrofuran complex 0.9M solution. ) Was added dropwise at 0 ° C. and the mixture was stirred for 1 hour.
The reaction solution was slowly returned to room temperature and stirred at room temperature for 3 hours. After concentration of the reaction solution, 1.09 g (0.85 mmol) of the boron-containing compound (A1) was obtained as a pale yellow solid in a yield of 44% by column chromatography using hexane as a developing solvent.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
・ホウ素含有化合物Ａ１－２の合成
　窒素置換した１００ｍＬシュレンク管にホウ素含有化合物（化合物Ａ１）０．４０ｇ（０．３１ｍｍｏｌ）、脱水テトラヒドロフラン２０ｍＬを投入し、テトラメチルピペリジルマグネシウムクロリド・リチウムクロリド１．０Ｍ溶液１．９ｍＬ（１．９０ｍｍｏｌ）を０℃で滴下し、そのまま１時間攪拌した。この溶液に、０℃でトリメチルスズクロリド０．３８ｇ（１．９０ｍｍｏｌ）を加え、同じ温度で１時間攪拌した。その後、反応溶液を室温に戻し、室温で１時間撹拌した。反応液を濃縮後、展開溶媒クロロホルムを用いたカラムクロマトグラフィーにより、ホウ素含有化合物（Ａ１－２）０．３９ｇ（０．２４ｍｍｏｌ）を淡橙色の固体として収率７９％で得た。 Synthesis of boron-containing compound A1-2 Boron-containing compound (compound A1) 0.40 g (0.31 mmol) and dehydrated tetrahydrofuran 20 mL were charged into a nitrogen-substituted 100 mL Schlenk tube, and tetramethylpiperidylmagnesium chloride / lithium chloride 1.0 M 1.9 mL (1.90 mmol) of the solution was added dropwise at 0 ° C. and stirred as it was for 1 hour. To this solution, 0.38 g (1.90 mmol) of trimethyltin chloride was added at 0 ° C., and the mixture was stirred at the same temperature for 1 hour. Then, the reaction solution was returned to room temperature and stirred at room temperature for 1 hour. After concentration of the reaction solution, 0.39 g (0.24 mmol) of the boron-containing compound (A1-2) was obtained as a pale orange solid in a yield of 79% by column chromatography using a developing solvent chloroform.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
合成例２：ホウ素含有化合物Ａ２、Ａ２－２の合成
・ホウ素含有化合物Ａ２の合成
　ホウ素含有化合物Ａ１の合成法において、トリヘキサデシルボランの代わりにジメシチルフルオロボランを原料として用いることで、Ａ２を０．４６３ｇ（０．５４３ｍｍｏｌ）黄色の固体として収率２８％で得た。
Figure JPOXMLDOC01-appb-C000018
 Synthesis Example 2: Synthesis of boron-containing compounds A2 and A2-2 / Synthesis of boron-containing compound A2 In the synthesis method of boron-containing compound A1, dimesitylfluoroborane was used as a raw material instead of trihexadecylborane. Of 0.463 g (0.543 mmol) as a yellow solid in 28% yield.
Figure JPOXMLDOC01-appb-C000018
・ホウ素含有化合物（Ａ２－２）の合成
　ホウ素化合物Ａ２－２は、Ａ２が不溶であったため、合成することが出来なかった。
Figure JPOXMLDOC01-appb-C000019
 Synthesis of boron-containing compound (A2-2) Boron compound A2-2 could not be synthesized because A2 was insoluble.
Figure JPOXMLDOC01-appb-C000019
＜ホウ素含有高分子化合物の合成と評価＞
実施例１：ホウ素含有高分子化合物（Ｐ１）の合成と評価
　窒素置換した２０ｍＬシュレンク管にホウ素含有化合物（Ａ１－２）を０．１０ｇ（０．０６２４ｍｍｏｌ）、５，５'－ジブロモ－２，２'－ビチオフェン（東京化成工業）を２０．２ｍｇ（０．０６２４ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム２．９ｍｇ（５ｍｏｌ％）、トリ（ｏ－トリル）ホスフィン１．９ｍｇ（１０ｍｏｌ％）、クロロベンゼン５ｍＬを投入し、８時間加熱還流条件で攪拌した。その後、２－トリブチルスタンニルチオフェン１００ｍｇ（０．３０９ｍｍｏｌ）を加え、３０分間反応させた。室温に戻し、メタノールを加え、固体をろ過で回収し、メタノール及びヘキサンを使用したソックスレー精製で、低分子体を除去した。最後にクロロホルムを使用したソックスレー精製により、抽出したクロロホルムを濃縮し、メタノールを加え、固体を析出させ、ろ過により回収することで、ホウ素含有高分子化合物（Ｐ１）６１ｍｇを濃紫色の固体として得た。得られた高分子化合物の重量平均分子量をＧＰＣ法により測定したところ、６３０００であった。測定されたＨＯＭＯの値は－５．７ｅＶ、Ｅｇの値は２．０ｅＶであり、それらから換算したＬＵＭＯは－３．７ｅＶであった。また、可溶性試験を行ったところ、クロロホルム十分に溶解した。トランジスタによる評価を行ったところ、１．８×１０－３ｃｍ２／Ｖｓであり、on/off値は１０６であった。評価結果を表１に示す。
Figure JPOXMLDOC01-appb-C000020
 （Ｐ１） <Synthesis and evaluation of boron-containing polymer compounds>
Example 1: Synthesis and Evaluation of Boron-Containing Polymer Compound (P1) 0.10 g (0.0624 mmol) of boron-containing compound (A1-2), 5,5′-dibromo-2, 2′-bithiophene (Tokyo Chemical Industry) 20.2 mg (0.0624 mmol), tris (dibenzylideneacetone) dipalladium 2.9 mg (5 mol%), tri (o-tolyl) phosphine 1.9 mg (10 mol%), Chlorobenzene (5 mL) was added, and the mixture was stirred for 8 hours under heating under reflux. Thereafter, 100 mg (0.309 mmol) of 2-tributylstannylthiophene was added and reacted for 30 minutes. It returned to room temperature, methanol was added, solid was collect | recovered by filtration, and the low molecular body was removed by Soxhlet refinement | purification using methanol and hexane. Finally, the extracted chloroform was concentrated by Soxhlet purification using chloroform, methanol was added, the solid was precipitated, and recovered by filtration to obtain 61 mg of a boron-containing polymer compound (P1) as a dark purple solid. . It was 63000 when the weight average molecular weight of the obtained high molecular compound was measured by GPC method. The measured HOMO value was -5.7 eV, Eg value was 2.0 eV, and the LUMO value converted from them was -3.7 eV. Moreover, when the solubility test was done, chloroform fully melt | dissolved. As a result of evaluation with a transistor, it was 1.8 × 10 −3 cm 2 / Vs, and the on / off value was 10 6 . The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-C000020
 (P1)
実施例２：ホウ素含有高分子化合物（Ｐ２）の合成と評価
　ホウ素含有高分子化合物（Ｐ１）の合成方法において、５，５'－ジブロモ－２，２'－ビチオフェン（東京化成工業）の代わりに５，５''－ジブロモ－２，２'：５'，２''－ターチオフェン（東京化成工業）を用いて、ホウ素含有高分子化合物（Ｐ２）６３ｍｇを濃紫色の固体として得た。評価結果を表１に示す。
Figure JPOXMLDOC01-appb-C000021
 Example 2: Synthesis and evaluation of boron-containing polymer compound (P2) In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) Using 5,5 ″ -dibromo-2,2 ′: 5 ′, 2 ″ -terthiophene (Tokyo Chemical Industry), 63 mg of a boron-containing polymer compound (P2) was obtained as a dark purple solid. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-C000021
実施例３：ホウ素含有高分子化合物（Ｐ３）の合成と評価
　ホウ素含有高分子化合物（Ｐ１）の合成方法において、５，５'－ジブロモ－２，２'－ビチオフェン（東京化成工業）の代わりに４，７－ビス（５－ブロモ－２－チエニル)－２，１，３－ベンゾチアジアゾールを用いて、ホウ素含有高分子化合物（Ｐ３）５２ｍｇを青色の固体として得た。評価結果を表１に示す。
Figure JPOXMLDOC01-appb-C000022
 Example 3: Synthesis and evaluation of boron-containing polymer compound (P3) In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) Using 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole, 52 mg of a boron-containing polymer compound (P3) was obtained as a blue solid. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-C000022
実施例４：ホウ素含有高分子化合物（Ｐ４）の合成と評価
　ホウ素含有高分子化合物（Ｐ１）の合成方法において、５，５'－ジブロモ－２，２'－ビチオフェン（東京化成工業）の代わりに２，６－ジブロモジチエノ［３，２－ｂ：２'，３'－ｄ]チオフェンを用いて、ホウ素含有化合物（Ｐ４）５８ｍｇを濃紫色の固体として得た。評価結果を表１に示す。
Figure JPOXMLDOC01-appb-C000023
 Example 4: Synthesis and evaluation of boron-containing polymer compound (P4 ) In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) By using 2,6-dibromodithieno [3,2-b: 2 ′, 3′-d] thiophene, 58 mg of boron-containing compound (P4) was obtained as a dark purple solid. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-C000023
実施例５：ホウ素含有高分子化合物（Ｐ５）の合成と評価
　ホウ素含有高分子化合物（Ｐ１）の合成方法において、５，５'－ジブロモ－２，２'－ビチオフェン（東京化成工業）の代わりに下記化合物Ｂを用いて、ホウ素含有高分子化合物（Ｐ５）８１ｍｇを緑色の固体として得た。評価結果を表１に示す。
なお、化合物Ｂ１は、Ｊ．Ｍａｔｅｒ．Ｃｈｅｍ．Ｃ，２０１４，２，３４５７及びＪ．Ｍａｔｅｒ．Ｃｈｅｍ．Ｃ，２０１４，２，６３７６を参考にして合成した。
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
 Example 5: Synthesis and evaluation of boron-containing polymer compound (P5 ) In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) Using the following compound B, 81 mg of a boron-containing polymer compound (P5) was obtained as a green solid. The evaluation results are shown in Table 1.
Compound B1 was prepared according to J.I. Mater. Chem. C, 2014, 2, 3457 and J.H. Mater. Chem. C, 2014, 2, 6376 were referred to and synthesized.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
比較例１
　前述のように、Ａ２を有する重合体は、Ａ２がクロロベンゼンに対する溶解性が無いことから、重合するための前駆体であるＡ２－２が合成できず、評価することができなかった。結果を表１に示す。 Comparative Example 1
As described above, since A2 has no solubility in chlorobenzene, A2-2, which is a precursor for polymerization, cannot be synthesized and evaluated. The results are shown in Table 1.
比較例２
　実施例１におけるホウ素含有高分子化合物（Ｐ１）の代わりにＰ３ＨＴ（綜研化学製、ベラゾールＨＴ、重量平均分子量４７，０００）を用い、トランジスタ作製におけるアニール条件を１５０℃３０ｍｉｎ．に変更した以外は同じ方法で評価を行った。結果を表１に示す。 Comparative Example 2
Instead of the boron-containing polymer compound (P1) in Example 1, P3HT (manufactured by Soken Chemical Co., Ltd., Verazol HT, weight average molecular weight 47,000) was used, and the annealing conditions for transistor fabrication were 150 ° C. for 30 min. The evaluation was performed in the same manner except that it was changed to. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
　実施例１～５は、比較例に対し、全てクロロホルムへの高い溶解性を示した。また、半導体特性については、ｐ型半導体特性を示し、１０－４ｃｍ２／Ｖｓ以上の移動度と、１０４以上のｏｎ／ｏｆｆ値を示した。一方、比較例１は重合することができず、比較例２は、クロロホルムに対して溶け残りがあり、高い溶解性が得られなかった。また、半導体特性に関しては、イオン化ポテンシャルが浅いことから、大気安定性も低くｏｎ／ｏｆｆ値が低い値となった。 Examples 1 to 5 all showed higher solubility in chloroform than the comparative examples. As for semiconductor characteristics, p-type semiconductor characteristics were exhibited, and a mobility of 10 −4 cm 2 / Vs or higher and an on / off value of 10 4 or higher were exhibited. On the other hand, Comparative Example 1 could not be polymerized, and Comparative Example 2 was undissolved in chloroform, and high solubility was not obtained. Regarding semiconductor characteristics, since the ionization potential is shallow, the atmospheric stability is low and the on / off value is low.

Claims (4)

  1. ホウ素－窒素配位結合を少なくとも２つ有する構造Ｗと、共役構造を持つ２価の置換基である構造πを含んだ下記式（１）で表される構造単位を含む高分子化合物であって
    Figure JPOXMLDOC01-appb-C000001
     ｍは０または１を表し、
    構造Ｗは、下記式（２）または（３）で表され、
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     環Ｘ１、Ｘ２、Ｚは共役構造を持つ単環または縮合環を示し、
    環Ｙ１、Ｙ２は前記ホウ素－窒素配位結合を有する５員環であり、
    α１及びα３の何れか一方が窒素原子であり、
    α２及びα４の何れか一方が窒素原子であり、
    Ｒ１～Ｒ４は同一でも異なっていてもよく、他の骨格を介してホウ素に結合していてもよく、置換されていてもよい炭素数１０～４０の直鎖または分岐のアルキル基を少なくとも１つ有する１価の置換基を表す、
    ホウ素含有高分子化合物。     A polymer compound including a structural unit represented by the following formula (1) including a structure W having at least two boron-nitrogen coordination bonds and a structure π that is a divalent substituent having a conjugated structure.
    Figure JPOXMLDOC01-appb-C000001
     m represents 0 or 1;
    The structure W is represented by the following formula (2) or (3):
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     Rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure,
    Rings Y 1 and Y 2 are 5-membered rings having the boron-nitrogen coordination bond,
    any one of α 1 and α 3 is a nitrogen atom,
    one of α 2 and α 4 is a nitrogen atom,
    R 1 to R 4 may be the same or different, may be bonded to boron via another skeleton, and may have at least a linear or branched alkyl group having 10 to 40 carbon atoms that may be substituted. Represents a monovalent substituent having one,
    Boron-containing polymer compound.
  2. 重量平均分子量が２×１０４～１×１０６である請求項１に記載のホウ素含有高分子化合物。 The boron-containing polymer compound according to claim 1, having a weight average molecular weight of 2 × 10 4 to 1 × 10 6 .
  3. Ｗは、隣接するＷまたはπと、Ｗ中の５員環を介して結合している、請求項１または２の何れか１つに記載のホウ素含有高分子化合物。 The boron-containing polymer compound according to claim 1, wherein W is bonded to adjacent W or π via a 5-membered ring in W.
  4. 請求項１～３の何れか１つに記載のホウ素含有高分子化合物を含有する有機半導体。 An organic semiconductor containing the boron-containing polymer compound according to any one of claims 1 to 3.
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