WO2021060042A1 - Compound, composition, film, structural body, and electronic device - Google Patents

Compound, composition, film, structural body, and electronic device Download PDF

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WO2021060042A1
WO2021060042A1 PCT/JP2020/034652 JP2020034652W WO2021060042A1 WO 2021060042 A1 WO2021060042 A1 WO 2021060042A1 JP 2020034652 W JP2020034652 W JP 2020034652W WO 2021060042 A1 WO2021060042 A1 WO 2021060042A1
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group
general formula
atom
compound
compound according
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PCT/JP2020/034652
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French (fr)
Japanese (ja)
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和平 金子
寛記 杉浦
伊勢　俊大
幸洋 奥野
剛史 中森
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富士フイルム株式会社
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Priority to JP2021548811A priority Critical patent/JP7316365B2/en
Publication of WO2021060042A1 publication Critical patent/WO2021060042A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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

Definitions

  • the present invention relates to compounds, membranes, structures and electronic devices.
  • FETs field effect transistors
  • RFIDs radio frequency identifiers: RF tags
  • organic EL Electro Luminescence
  • Patent Document 1 discloses an organic semiconductor compound having a triptycene skeleton.
  • the present invention relates to a compound having excellent reproducibility of carrier mobility when formed into a film, a structure provided with the film, and an electronic device containing the structure, regardless of the film forming method.
  • the purpose is to provide.
  • the present inventors have found that the above-mentioned problems can be solved by using a compound having a triptycene skeleton having a specific structure. That is, the present inventors have found that the above problems can be solved by the following configuration.
  • X represents an oxygen atom or a sulfur atom.
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
  • Z represents an oxygen atom, a sulfur atom, a selenium atom, or -NR 2- .
  • R 2 represents a hydrogen atom or an alkyl group.
  • * represents a binding site with A, B or Q in the above general formula
  • ** represents a binding site with a benzene ring in the above general formula.
  • (11) The compound according to any one of (1) to (10) above, wherein Y is a hydrogen atom.
  • a structure comprising a substrate and the film according to (17) above, which is arranged on the surface of the substrate.
  • An electronic device comprising the structure according to (18) above.
  • a compound having excellent reproducibility of carrier mobility when formed into a film, a structure provided with the film, and an electronic device containing the structure, regardless of the film forming method. can be provided.
  • the numerical range represented by using “-” means a range including the numerical values before and after “-” as the lower limit value and the upper limit value.
  • the "aliphatic hydrocarbon group”, “alkyl group”, “alkenyl group”, and “alkenyl group” are linear, branched, and cyclic unless otherwise specified. It shall include those having any of the above structures.
  • each component may be used alone or in combination of two or more.
  • the content of the component means the total content unless otherwise specified.
  • the same symbols (alphabets) are present in the general formula, they may be the same or different unless otherwise specified.
  • the compound of the present invention is a compound represented by the general formula (1) or (2) described later. Since the compound of the present invention has such a structure, it is considered that the above-mentioned effects can be obtained. The reason is not clear, but it is presumed to be as follows. As shown in the general formulas (1) and (2) described later, the compound of the present invention has B (an aliphatic hydrocarbon group having 5 to 22 carbon atoms which may have a substituent) and a triptycene skeleton. ..
  • L represents a single bond or a divalent linking group.
  • A represents a divalent conjugate system linking group having 2 to 10 conjugate rings.
  • B or Q in the general formula via a single bond or a divalent conjugated system linking group the total is 1.
  • B represents an aliphatic hydrocarbon group having 5 to 22 carbon atoms which may have a substituent.
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
  • Q represents a hydrogen atom or a halogen atom.
  • n represents 0 or 1.
  • X 1 , X 2 , X 3 and X 4 independently represent groups represented by the following general formulas (AB) or (BA), respectively.
  • Y represents a hydrogen atom or a substituent.
  • the general formula (1) two n in, and, X 1 in the formula (1), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1.
  • the general formula (2) two n in, and, X 1 in the general formula (2), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group is not particularly limited, but for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group, or an alkenylene group).
  • Alquinylene group divalent aromatic hydrocarbon group (eg, phenylene group), -O-, -S-, -SO 2- , -NR L- , -CO-, -NH-, -COO-, -CONR L- , -O-CO-O-, -SO 3- , -NHCOO-, -SO 2 NR L- , -NH-CO-NH- or a group combining two or more of these (for example, alkyleneoxy Groups, alkyleneoxycarbonyl groups, alkylenecarbonyloxy groups, etc.) and the like.
  • RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
  • the number of atoms connecting the partial structures linearly is an even number (however, the substituent is not included in the above number of atoms) for the reason that the performance reproducibility is better and the carrier mobility is higher. Is preferable.
  • the performance reproducibility is better and the carrier mobility is higher is also referred to as "the effect of the present invention is more excellent”.
  • *-(CH 2 ) 2n-1 Z-** is particularly preferable.
  • Z is an oxygen atom, a sulfur atom, a selenium atom, or, -NR 2 - represents an oxygen atom, preferably a sulfur atom, more preferably oxygen atom.
  • n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1.
  • R 2 represents a hydrogen atom or an alkyl group.
  • * represents a binding site with A, B or Q in the general formula
  • ** represents a binding site with a benzene ring (benzene ring constituting triptycene) in the general formula.
  • A represents a divalent conjugate system linking group having 2 to 10 conjugate rings.
  • A is a divalent conjugated system linking group.
  • the divalent conjugated system linking group is a divalent linking group in which the conjugated system is connected from one binding site to the other binding site.
  • the conjugated ring is an aromatic ring or an antiaromatic ring.
  • the aromatic ring is a ring in which the number of electrons contained in the ⁇ -electron system is 4n + 2 (n is an integer of 0 or more), and the antiaromatic ring is a ring in which the number of electrons contained in the ⁇ -electron system is 4n (n).
  • n is a ring of 1 or more).
  • the conjugated ring is preferably an aromatic ring because the effects of the present invention are more excellent.
  • aromatic ring examples include a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a furan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a selenophene ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyrazole ring, and an isoxazole ring.
  • Isothiazole ring triazole ring, flazan ring, oxadithiazole ring, thiathiazole ring, dioxazole ring, dithiazole ring, azulene ring and the like.
  • a benzene ring and a thiophene ring are preferable because the effects of the present invention are more excellent.
  • antiaromatic ring examples include cyclobutadiene, cyclooctatetraene, pentalene and the like.
  • A has 2-10 conjugate rings.
  • the number of conjugate rings as a single ring is counted.
  • A has a structure in which four conjugated rings are fused (below) (here, * is a binding site), so the number of conjugated rings is four.
  • A preferably has 3 to 8 conjugate rings, more preferably 4 to 6, for the reason that the effect of the present invention is more excellent.
  • the above-mentioned A may have a ring other than the conjugated ring as long as it satisfies the requirements (divalent conjugated system linking group, number of conjugated rings, total number of rings to be fused and number of rings to be bonded).
  • the 2,7-fluorenylene group has a structure in which two benzene rings and one pentadiene ring are fused, and has a pentadiene ring which is a ring other than the conjugated ring. It corresponds to the above A in order to satisfy the group, the number of conjugated rings, the total number of rings to be fused and the number of rings to be bonded).
  • A is a divalent conjugated system linking group (a divalent conjugated group in which the conjugated system is connected from one binding site to the other binding site), and as described later, one binding site to the other. Since the shape extends to the bonding site without branching, the conjugated rings (monocyclic conjugated rings) are fused or bonded by a single bond or a divalent conjugated system linking group.
  • the divalent conjugated system linking group that connects the conjugated rings to each other is not particularly limited as long as it is a divalent linking group that connects the conjugated system from one bonding site to the other bonding site, but the effect of the present invention is more excellent. For this reason, a vinylene group, an ethynylene group, an azo group, and an imino group are preferable.
  • the hydrogen atom of the vinylene group may be substituted.
  • the ring R having a binding site is A that is bound to the ring R via a single bond or a divalent conjugated system linking group and the number of rings fused to the ring R.
  • the total (total X) with the number of rings in the ring is 1, and for the other rings R, the number of rings fused to the ring R and the number of rings fused to the ring R via a single bond or a divalent conjugated system linking group are used.
  • the total (total Y) with the number of rings in A to be bonded is 2.
  • A has a shape that extends from one binding site to the other binding site without branching.
  • the requirement regarding the above total is also referred to as "requirement A".
  • the two benzene rings having a binding site are both fused with one pentadiene ring, and there is no other ring to be condensed or bonded, so that the total X is As for the remaining ring (pentadiene ring), the total Y is 2 because it is fused with the benzene ring at both ends and there is no other ring to be fused or bonded, which satisfies the requirement A.
  • the above-mentioned A is a condensed polycyclic conjugated heterocycle (particularly a condensed aromatic heterocycle) containing an interchalcogen atom (oxygen, sulfur, selenium, tellurium, polonium, livermorium) because the effect of the present invention is more excellent.
  • an interchalcogen atom oxygen, sulfur, selenium, tellurium, polonium, livermorium
  • the condensed polycyclic conjugated heterocycle include a benzothiophene ring and a benzothienobenzothiophene ring.
  • the above-mentioned A is preferably a charge transport group for the reason that the effect of the present invention is more excellent.
  • the above-mentioned A is preferably a group represented by the following general formula (A1), a group represented by the following general formula (A2), or a combination thereof, for the reason that the effect of the present invention is more excellent.
  • Ar 1 , Ar 2 and Ar 3 independently represent a conjugated ring (single ring).
  • p represents an integer from 0 to 8. * Represents the binding site.
  • Specific examples of the conjugated ring (monocycle) are as described above.
  • Ar represents a conjugated ring (monocyclic or condensed ring).
  • M represents a single bond or a divalent conjugated system linking group (for example, a vinylene group, an ethynylene group, an azo group, an imino group, in which the hydrogen atom of the vinylene group may be substituted).
  • q represents an integer from 0 to 8. * Represents the binding site.
  • conjugated ring (monocycle)
  • the conjugated ring is a fused ring
  • the condensed ring satisfies the above-mentioned requirement A.
  • the number of conjugate rings as a single ring included in the general formula (A2) (for fused rings, the number of conjugated rings constituting the fused rings is counted) is 10 at the maximum.
  • B is an aliphatic group having 5 to 22 carbon atoms which may have a substituent (for example, a group selected from the substituent group Z described later).
  • a substituent for example, a group selected from the substituent group Z described later.
  • the carbon atom constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfur atom, a silicon atom,>
  • C X (X represents an oxygen atom or a sulfur atom), or -NR 1-. It may have been.
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
  • the carbon atom in the substituent is not counted in the carbon number.
  • the aliphatic hydrocarbon group before substitution may have 5 to 22 carbon atoms.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group and the like. Among them, a linear alkyl group is preferable because the effect of the present invention is more excellent.
  • the aliphatic hydrocarbon group represented by B is preferably 8 to 20 carbon atoms, more preferably 10 to 20 carbon atoms, and particularly preferably 12 to 18 carbon atoms. Further, for the reason that the effect of the present invention is more excellent, the aliphatic hydrocarbon group represented by B is an unsubstituted alkyl group, a halogenated alkyl group, an unsubstituted alkenyl group, a halogenated alkenyl group, or an unsubstituted alkenyl group.
  • alkynyl group an alkenyl halide group, an alkyl group substituted with an oxygen atom, an alkenyl group substituted with an oxygen atom, or an alkynyl group substituted with an oxygen atom. More preferably, it is an unsubstituted alkyl group, a halogenated alkyl group, an unsubstituted alkenyl group, an unsubstituted alkynyl group, or an alkyl group substituted with an oxygen atom. It is particularly preferable that the alkyl group is unsubstituted or an alkyl group substituted with an oxygen atom.
  • Q represents a hydrogen atom or a halogen atom.
  • the above Q is preferably a hydrogen atom or a fluorine atom for the reason that the effect of the present invention is more excellent.
  • n represents 0 or 1. At least one of n in the general formulas (1) and (2) is preferably 1 for the reason that the effect of the present invention is more excellent.
  • the two n in the general formula (1) are preferably 1 for the reason that the effect of the present invention is more excellent.
  • the two n in the general formula (2) are preferably 1 for the reason that the effect of the present invention is more excellent.
  • X 1 , X 2 , X 3 and X 4 independently represent groups represented by the following general formulas (AB) or (BA), respectively.
  • L, A, B and Q in the general formulas (AB) and (BA) include L, A, B and in the general formulas (1) and (2). It is the same as Q.
  • m and n independently represent 0 or 1, respectively.
  • * represents a binding site.
  • m is preferably 1 for the reason that the effect of the present invention is more excellent.
  • n is preferably 1 for the reason that the effect of the present invention is more excellent.
  • the compound of the present invention is a compound represented by the general formula (1)
  • the above X 1 is a group represented by the general formula (AB) for the reason that the effect of the present invention is more excellent. Is preferable.
  • the compound of the present invention is a compound represented by the general formula (2)
  • the above X 1 is a group represented by the general formula (BA) for the reason that the effect of the present invention is more excellent. Is preferable.
  • n is the reason that the effect or the like of the present invention is more excellent, it is 1 preferable.
  • Y represents a hydrogen atom or a substituent (for example, a group selected from the substituent group Z described later).
  • the above-mentioned substituent may be a group represented by the above-mentioned general formula (AB) or (BA).
  • the Y is preferably a hydrogen atom because the effect of the present invention is more excellent.
  • the general formula (1) two n in, and, X 1 in the formula (1), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one One is 1.
  • the compound of the present invention has at least one group represented by B above.
  • each n contained in X 1 , X 2 , X 3 and X 4 in the general formula (1) is a general formula X 1 , X 2 , X 3 and X 4 in the general formula (1).
  • each n contained in X 1 , X 2 , X 3 and X 4 in the general formula (2) is a general X 1 , X 2 , X 3 and X 4 in the general formula (2). It represents each n (a total of four n) in the group represented by the formula (AB) or (BA).
  • 3 to 6 n are preferably 1 for the reason that the effect of the present invention is more excellent.
  • the compound of the present invention is preferably a compound represented by the above-mentioned general formula (1) for the reason that the effects of the present invention are more excellent.
  • the compound represented by the general formula (1) described above is preferably a compound represented by the following general formula (3) because the effects of the present invention and the like are more excellent.
  • L, A, B, Q and Y in the general formula (3) are the same as those of L, A, B, Q and Y in the general formula (1) described above. ..
  • m and n independently represent 0 or 1, respectively. However, at least one of the three n in the general formula (3) is 1.
  • the m in the general formula (3) is preferably 1 for the reason that the effect of the present invention is more excellent. It is preferable that m and n in the general formula (3) are both 1 for the reason that the effect of the present invention is more excellent.
  • the compound of the present invention is preferably a compound represented by the following general formula (4) for the reason that the effects of the present invention are more excellent.
  • L, A, B, Q and Y in the general formula (4) are the same as L, A, B, Q and Y in the general formulas (1) and (2) described above. Each is the same.
  • m and n independently represent 0 or 1, respectively. However, at least one of the three n in the general formula (4) is 1.
  • the m in the general formula (4) is preferably 1 for the reason that the effect of the present invention is more excellent. It is preferable that m and n in the general formula (4) are both 1 for the reason that the effect of the present invention is more excellent.
  • the compound of the present invention is preferably a compound represented by the following general formula (5) for the reason that the effects of the present invention are more excellent.
  • L, A, B, Q, X 2 , X 3 , X 4 and Y in the general formula (5) are described in L, A, B in the general formula (1) described above. , Q, X 2 , X 3 , X 4 and Y, respectively.
  • n represents 0 or 1. However, three of n in the general formula (5) and, each n is included in the general formula (5) X 2, X 3 and X 4 in, out of the total of six n, at least one is 1 ..
  • At least one of n in the general formula (5) is preferably 1 for the reason that the effect of the present invention is more excellent.
  • the three n in the general formula (5) are preferably 1 for the reason that the effect of the present invention is more excellent.
  • the method for synthesizing the compound of the present invention is not particularly limited, and the compound can be synthesized with reference to a usual method. For example, it can be synthesized as in the examples described later.
  • Substituent group Z includes halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, silyl group, alkoxy group, amino group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, Acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, Arylsulfonyl group, silyloxy group, heterocyclic oxy group, carbamoyl group, carbamoyl group, carbamoyl group, carbamoyl group, carbamoyl
  • halogen atom contained in the substituent group Z examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
  • the alkyl group contained in the substituent group Z is not particularly limited, but an alkyl group having 1 (3) to 30 carbon atoms is preferable, an alkyl group having 1 (3) to 20 carbon atoms is more preferable, and an alkyl group having 4 to 20 carbon atoms is more preferable. Alkyl groups of are more preferred.
  • the numbers in parentheses represent the number of carbon atoms in the case of a cycloalkyl group.
  • alkyl group which may have a substituent contained in the substituent group Z include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, an amyl group, a pentyl group, and a 1-methylpentyl group.
  • the alkenyl group contained in the substituent group Z is not particularly limited, but an alkenyl group having 2 to 20 carbon atoms is preferable, an alkenyl group having 2 to 12 carbon atoms is more preferable, and an alkenyl group having 2 to 8 carbon atoms is further preferable. ..
  • Examples of the alkenyl group which may have a substituent contained in the substituent group Z include a vinyl group, an allyl group, a 2-butenyl group, a 1-pentenyl group, and a 4-pentenyl group.
  • the alkynyl group contained in the substituent group Z is not particularly limited, but an alkynyl group having 2 to 20 carbon atoms is preferable, an alkynyl group having 2 to 12 carbon atoms is more preferable, and an alkynyl group having 2 to 8 carbon atoms is further preferable. ..
  • Examples of the alkynyl group which may have a substituent contained in the substituent group Z include an ethynyl group, a propargyl group, a 1-pentynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group and a tri-i-propylsilylethynyl group. , And 2-p-propylphenylethynyl groups.
  • the aryl group contained in the substituent group Z is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
  • Examples of the aryl group which may have a substituent contained in the substituent group Z include a phenyl group, a naphthyl group, a 2,4,6-trimethylphenyl group, a p- (t-butyl) phenyl group, and 4-.
  • Methyl-2,6-dipropylphenyl group 4-fluorophenyl group, 4-trifluoromethylphenyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, and 3, Examples include 4-dihepptoxyphenyl group.
  • the heterocyclic group contained in the substituent group Z includes, for example, three or more atoms constituting the ring, and at least one heteroatom and 1 to 30 carbon atoms as the atoms constituting the ring.
  • Examples include heterocyclic groups containing atoms.
  • the heterocyclic group includes an aromatic heterocyclic group (heteroaryl group) and an aliphatic heterocyclic group.
  • Examples of the hetero atom constituting the ring include a nitrogen atom, an oxygen atom, and a sulfur atom, and the number thereof is not particularly limited, but is, for example, one or two.
  • the number of carbon atoms constituting the ring is preferably 3 to 20, more preferably 5 to 12.
  • heterocyclic group a 5-membered ring, a 6-membered ring, or a group of these fused rings is preferable.
  • the heterocyclic group contained in the substituent group Z include a thienyl group, a thiazolyl group, an imidazolyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, a furanyl group, a selenophyl group, a piperidyl group, a morpholino group and a benzoxazolyl.
  • examples thereof include a group, a benzimidazolyl group, a benzthiazolyl group, a 2-hexylfuranyl group, and a pyranyl group.
  • the silyl group which may have a substituent contained in the substituent group Z is not particularly limited, but has a group selected from an alkyl group and an aryl group as the substituent and has 3 to 40 carbon atoms (more preferably). Is 3 to 30, more preferably 3 to 24), and a silyl group is preferable.
  • Examples of the silyl group which may have a substituent contained in the substituent group Z include a trimethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group.
  • the alkoxy group contained in the substituent group Z is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 12 carbon atoms is more preferable, and an alkoxy group having 1 to 8 carbon atoms is further preferable. preferable.
  • Examples of the alkoxy group contained in the substituent group Z include a methoxy group, an ethoxy group, and a butoxy group.
  • the amino group which may have a substituent contained in the substituent group Z is not particularly limited, but has an amino group or a group selected from an alkyl group and an aryl group as a substituent and has a carbon number of carbons. Amino groups of 1 to 20 (more preferably 1 to 10, still more preferably 1 to 6) are preferred. Examples of the amino group which may have a substituent contained in the substituent group Z include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, and an anilino group.
  • the aryloxy group contained in the substituent group Z is not particularly limited, but an aryloxy group having 6 to 20 carbon atoms is preferable, an aryloxy group having 6 to 16 carbon atoms is more preferable, and an aryloxy group having 6 to 12 carbon atoms is more preferable. Groups are even more preferred.
  • Examples of the aryloxy group contained in the substituent group Z include a phenyloxy group and 2-naphthyloxy.
  • the acyl group contained in the substituent group Z is not particularly limited, but an acyl group having 1 to 20 carbon atoms is preferable, an acyl group having 1 to 16 carbon atoms is more preferable, and an acyl group having 1 to 12 carbon atoms is further preferable. ..
  • Examples of the acyl group which may have a substituent contained in the substituent group Z include an acetyl group, a hexanoyl group, a benzoyl group, a formyl group, and a pivaloyl group.
  • the alkoxycarbonyl group contained in the substituent group Z is not particularly limited, but an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable, an alkoxycarbonyl group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonyl group having 2 to 12 carbon atoms is more preferable.
  • the group is more preferable, and the methoxycarbonyl group or the ethoxycarbonyl group is particularly preferable.
  • the aryloxycarbonyl group contained in the substituent group Z is not particularly limited, but an aryloxycarbonyl group having 7 to 20 carbon atoms is preferable, an aryloxycarbonyl group having 7 to 16 carbon atoms is more preferable, and an aryloxycarbonyl group having 7 to 10 carbon atoms is more preferable.
  • the aryloxycarbonyl group of the above is more preferable, and the phenyloxycarbonyl group is particularly preferable.
  • the acyloxy group contained in the substituent group Z is not particularly limited, but an acyloxy group having 2 to 20 carbon atoms is preferable, an acyloxy group having 2 to 16 carbon atoms is more preferable, and an acyloxy group having 2 to 10 carbon atoms is further preferable. ..
  • Examples of the acyloxy group which may have a substituent contained in the substituent group Z include an acetoxy group, a benzoyloxy group, and a (meth) acryloyloxy group.
  • the acylamino group contained in the substituent group Z is not particularly limited, but an acylamino group having 2 to 20 carbon atoms is preferable, an acylamino group having 2 to 16 carbon atoms is more preferable, and an acylamino group having 2 to 10 carbon atoms is further preferable. ..
  • Examples of the acylamino group contained in the substituent group Z include an acetylamino group and a benzoylamino group.
  • the aminocarbonylamino group contained in the substituent group Z is not particularly limited, but an aminocarbonylamino group having 2 to 20 carbon atoms is preferable, an aminocarbonylamino group having 2 to 16 carbon atoms is more preferable, and an aminocarbonylamino group having 2 to 12 carbon atoms is more preferable. Aminocarbonylamino groups are more preferred, and ureido groups are particularly preferred.
  • the alkoxycarbonylamino group contained in the substituent group Z is not particularly limited, but an alkoxycarbonylamino group having 2 to 20 carbon atoms is preferable, an alkoxycarbonylamino group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonylamino group having 2 to 12 carbon atoms is more preferable.
  • the alkoxycarbonylamino group of the above is more preferable, and the methoxycarbonylamino group is particularly preferable.
  • the aryloxycarbonylamino group contained in the substituent group Z is not particularly limited, but an aryloxycarbonylamino group having 7 to 20 carbon atoms is preferable, an aryloxycarbonylamino group having 7 to 16 carbon atoms is more preferable, and an aryloxycarbonylamino group having 7 to 16 carbon atoms is more preferable. 7-12 aryloxycarbonylamino groups are more preferred, and phenyloxycarbonylamino groups are particularly preferred.
  • the alkylthio group contained in the substituent group Z is not particularly limited, but an alkylthio group having 1 to 20 carbon atoms is preferable, an alkylthio group having 1 to 16 carbon atoms is more preferable, and an alkylthio group having 1 to 12 carbon atoms is further preferable. ..
  • Examples of the alkylthio group contained in the substituent group Z include a methylthio group, an ethylthio group, and an octylthio group.
  • the arylthio group contained in the substituent group Z is not particularly limited, but an arylthio group having 6 to 20 carbon atoms is preferable, an arylthio group having 6 to 16 carbon atoms is more preferable, and an arylthio group having 6 to 12 carbon atoms is further preferable. , Phenylthio groups are particularly preferred.
  • the group selected from the substituent group Z described above may further have a substituent.
  • a substituent examples include a group selected from the substituent group Z.
  • the number of substituents having a substituent (also referred to as a combined group) is not particularly limited, but for example, 1 to 6 is preferable, and 1 to 3 is more preferable.
  • the group to be combined is not particularly limited, and examples thereof include the above-mentioned groups in which each of the above-mentioned groups preferable as the group selected from the substituent group Z is substituted with another group selected from the substituent group Z. Be done.
  • halogen atom alkyl group, aryl group, heterocyclic group (heteroaryl group), alkoxy group (including hydroxyalkoxy group, halogenated alkoxy group, heteroarylalkoxy group), amino group, acyloxy group, hydroxy
  • An alkyl group having a group selected from the group consisting of a group, a sulfato group, and a phosphono group as a substituent, an aryl halide group or a (fluorinated) alkylaryl group, an alkynyl group having a silyl group as a substituent, etc. Can be mentioned.
  • an alkyl group having a halogen atom as a substituent (alkyl halide group) or an alkyl group having an aryl group as a substituent is preferable, and an alkyl group having a fluorine atom as a substituent (huh).
  • Alkyl compound group) or an alkyl group having an aryl group as a substituent is more preferable, and an alkyl group having an aryl group as a substituent is further preferable.
  • the compound of the present invention is, for example, an organic thin film that controls the amount of current or voltage, an organic photoelectric conversion element that converts light energy into electric power (for example, a solid-state imaging device for optical sensors, and a solar cell for energy conversion).
  • an organic photoelectric conversion element that converts light energy into electric power
  • OLED organic light emitting diode
  • phototransistor organic light emitting diode
  • OLET organic light emitting transistor
  • organic thermoelectric conversion element that converts heat energy into electric power
  • gas sensor for example, organic rectifying element, organic inverter, and information recording element.
  • the film of the present invention is a film (organic semiconductor film) containing the above-mentioned compound of the present invention.
  • the membrane of the present invention contains the above-mentioned compound of the present invention.
  • the film of the present invention may be a monolayer film or a laminated film.
  • the content of the compound of the present invention in the film of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, for the reason that the effect of the present invention is more excellent. , 50% by mass or more, and particularly preferably 90% by mass or more.
  • the upper limit is not particularly limited and is 100% by mass.
  • the upper limit of the content of the compound of the present invention in the film of the present invention is 90% by mass or less because the effect of the present invention is more excellent. It is preferably present, and more preferably 80% by mass or less.
  • the film of the present invention may contain a component (arbitrary component) other than the above-mentioned compound of the present invention.
  • the film of the present invention may contain a binder polymer.
  • the film quality may be improved by containing the binder polymer.
  • the content of the compound of the present invention and the binder polymer is not particularly limited, but the compound of the present invention and the binder polymer are phase-separated from each other along the film thickness direction in terms of carrier mobility. It is preferable to have.
  • the type of the binder polymer is not particularly limited, and a known binder polymer can be used.
  • the binder polymer include polystyrene, poly ( ⁇ -methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, and. Insulating polymers containing polypropylene and copolymers thereof are mentioned.
  • ethylene-propylene rubber acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroepolymer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene- Butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, methylphenyl vinyl silicone resin, methyl vinyl silicone resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin Rubber containing copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer, polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elasto
  • polyvinylcarbazole and a photoconductive polymer containing polysilane examples include polyvinylcarbazole and a photoconductive polymer containing polysilane, a conductive polymer containing polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and Chemistry of Materials, 2014, 26, 647.
  • the binder polymer preferably has a structure that does not contain a polar group in consideration of charge mobility.
  • the polar group means a functional group having a hetero atom other than a carbon atom and a hydrogen atom.
  • Polystyrene or poly ( ⁇ -methylstyrene) is preferable as the binder polymer because it has a structure containing no polar group.
  • semiconductor polymers are preferred.
  • the glass transition temperature of the binder polymer is not particularly limited and is appropriately set according to the application. For example, when imparting strong mechanical strength to an organic semiconductor film, it is preferable to raise the glass transition temperature. On the other hand, when imparting flexibility to the organic semiconductor film, it is preferable to lower the glass transition temperature.
  • the binder polymer may be used alone or in combination of two or more.
  • the weight average molecular weight of the binder polymer is not particularly limited, but is preferably 10 to 10 million, more preferably 30 to 5 million, and even more preferably 50 to 3 million.
  • the weight average molecular weight of the binder polymer can be determined by gel permeation chromatography (GPC).
  • the content is not particularly limited, but the lower limit is preferably 10% by mass or more, preferably 20% by mass or more, for the reason that the effect of the present invention is more excellent. It is more preferable, and the upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, for the reason that the effect of the present invention is more excellent.
  • optional ingredients other than the binder polymer include additives usually used for organic semiconductor membranes, and more specifically, surfactants, antioxidants, crystallization control agents, and crystal orientation control agents. Can be mentioned. As the surfactant and the antioxidant, paragraphs 0136 and 0137 of JP2015-195362A can be incorporated, and the contents thereof are incorporated in the present specification.
  • the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass because the effects of the present invention are more excellent. The following is more preferable.
  • the film thickness of the film of the present invention is not particularly limited, but 5 to 500 nm is preferable, and 5 to 200 nm is more preferable for the reason that the effect of the present invention is more excellent.
  • the application of the film of the present invention is not limited to the organic semiconductor film for organic TFTs, and can be used as the organic semiconductor film included in each of the above-mentioned organic semiconductor devices.
  • the method for producing the film of the present invention is not particularly limited, and examples thereof include a method of preparing a composition (organic semiconductor composition) containing the compound of the present invention described above and then applying the composition to a substrate or the like.
  • composition of the present invention is a composition (organic semiconductor composition) containing the above-mentioned compound of the present invention.
  • the composition of the present invention is preferably a composition (organic semiconductor composition) containing the above-mentioned compound of the present invention and at least one kind of solvent.
  • the composition of the present invention may contain components other than the above-mentioned compounds of the present invention.
  • the composition of the present invention preferably contains a solvent from the viewpoint of improving the coatability.
  • a solvent is not particularly limited as long as it dissolves or disperses the above-mentioned compound, and examples thereof include an inorganic solvent and an organic solvent, and an organic solvent is preferable.
  • the solvent may be used alone or in combination of two or more.
  • the organic solvent is not particularly limited, but hexane, octane, decane, toluene, xylene, mecitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetraline can be used.
  • Examples thereof include a phosphate ester solvent containing trimethyl, a nitrile solvent containing acetonitrile and benzonitrile, and a nitro solvent containing nitromethane and nitrobenzene.
  • a hydrocarbon solvent, a ketone solvent, a halogenated hydrocarbon solvent, a heterocyclic solvent, a halogenated heterocyclic solvent, an ester solvent, an alcohol solvent, an alkoxyalcohol solvent, an ether solvent, or a nitrile solvent is preferable, and toluene, xylene, and mesitylene are preferable.
  • a solvent having a boiling point of 100 ° C. or higher is preferable in terms of film quality and the ability to enlarge the crystals of the above-mentioned compounds.
  • toluene xylene, mesitylene, tetraline, acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3 -Methylanisole, 4-methylanisole, 1-methoxy-2-propanol, 2-methoxyethanol, 2-butoxyethanol, and benzonitrile can be mentioned.
  • toluene, xylene, tetraline, acetophenone, propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, or 2-butoxyethanol are more suitable.
  • a non-halogen solvent solvent having no halogen atom in the molecule
  • the solvent having a boiling point of 100 ° C. or higher is preferable as the solvent having a boiling point of 100 ° C. or higher.
  • the content of the solvent is preferably 90 to 99.9% by mass, more preferably 95 to 99.9% by mass, based on the total mass of the composition of the present invention. , 96-99.5% by mass, more preferably.
  • the viscosity of the composition of the present invention is preferably 10 mPa ⁇ s or more in terms of printability.
  • the method for preparing the composition of the present invention is not particularly limited, and a usual preparation method can be adopted. For example, a method of mixing the compound of the present invention with a solvent can be mentioned. If necessary, each component can be heated during or after stirring.
  • the heating temperature is not particularly limited and is determined, for example, in the range of 40 to 150 ° C. When a solvent is used, the temperature is determined to be within the above range and below the boiling point of the solvent.
  • the structure of the present invention is a structure including a substrate and the film (organic semiconductor film) of the present invention described above.
  • the substrate is the same as that of the organic thin film transistor described later.
  • the electronic device of the present invention is an electronic device including the above-described structure of the present invention.
  • the organic thin film transistor of the present invention is the above-mentioned electronic device of the present invention, which is an organic thin film transistor (organic TFT).
  • the organic TFT includes the above-mentioned organic semiconductor film. As a result, the organic TFT exhibits high carrier mobility, and is effectively suppressed from decreasing with time even in the atmosphere, and is stably driven.
  • the ambient temperature and humidity in the atmosphere are not particularly limited as long as they are the temperature and humidity in the environment in which the organic TFT is used. For example, the temperature is room temperature (20 ° C.) and the humidity is 10 to 90 RH%.
  • the organic TFT is preferably used as an organic field effect transistor (FET), and more preferably used as an insulated gate type FET in which the gate and the channel are insulated.
  • the thickness of the organic TFT is not particularly limited, but in the case of a thinner transistor, for example, the thickness of the entire organic TFT is preferably 0.1 to 0.5 ⁇ m.
  • the organic TFT has the above-mentioned organic semiconductor film (also referred to as an organic semiconductor layer or a semiconductor active layer), and may further have a source electrode, a drain electrode, a gate electrode, and a gate insulating film.
  • the organic TFT is provided on the substrate in contact with the gate electrode, the organic semiconductor film, the gate insulating film provided between the gate electrode and the organic semiconductor film, and the organic semiconductor film, and is connected via the organic semiconductor film. It is preferable to have a source electrode and a drain electrode.
  • an organic semiconductor film and a gate insulating film are provided adjacent to each other.
  • the structure of the organic TFT is not particularly limited as long as it includes each of the above layers.
  • the organic TFT may have any structure of bottom gate-bottom contact type, top gate-bottom contact type, bottom gate-top contact type, and top gate-top contact type.
  • a bottom gate type bottom gate-bottom contact type or bottom gate-top contact type in which a gate electrode is provided between the substrate and the organic semiconductor film is preferable.
  • an example of the organic TFT will be described with reference to the drawings.
  • FIG. 1 is a schematic cross-sectional view showing the structure of a bottom gate-bottom contact type organic TFT 10 which is an example of an organic TFT.
  • the organic TFT 10 includes a substrate (base material) 1, a gate electrode 2, a gate insulating film 3, a source electrode 4A, a drain electrode 4B, an organic semiconductor film 5, and a sealing layer 6.
  • a substrate (base material), a gate electrode, a gate insulating film, a source electrode, a drain electrode, an organic semiconductor film, a sealing layer, and a method for producing each of them will be described.
  • the substrate serves to support the gate electrode, the source electrode, the drain electrode, and other layers.
  • the type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a silicon substrate, a glass substrate, and a ceramic substrate. Above all, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
  • the thickness of the substrate is not particularly limited.
  • the upper limit of the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and further preferably 1.5 mm or less.
  • the lower limit of the thickness of the substrate is preferably 0.01 mm or more, more preferably 0.05 mm or more.
  • a normal electrode used as a gate electrode of an organic TFT can be applied without particular limitation.
  • the material (electrode material) for forming the gate electrode is not particularly limited, and is, for example, a metal containing gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, and sodium. , InO 2 , SnO 2 , and conductive oxides including indium tin oxide (ITO), polyaniline, polypyrrole, polythiophene, polyacetylene, and conductive polymers containing polydiacetylene, silicon, germanium, and gallium.
  • ITO indium tin oxide
  • Examples include semiconductors containing arsenic, and carbon materials containing fullerene, carbon nanotubes, and graphite. Among them, the above metal is preferable, and silver or aluminum is more preferable.
  • the thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.
  • the gate electrode may function as the substrate, and in this case, the substrate may be omitted.
  • the method for forming the gate electrode is not particularly limited, and for example, a method of vacuum-depositing (hereinafter, simply referred to as “vapor deposition”) or sputtering of the above-mentioned electrode material on a substrate, and an electrode containing the above-mentioned electrode material. Examples thereof include a method of applying or printing the forming composition.
  • vapor deposition a method of vacuum-depositing
  • examples of the patterning method include a printing method including inkjet printing, screen printing, offset printing, and letterpress printing (flexographic printing), a photolithography method, and a mask vapor deposition method. ..
  • the gate insulating film is not particularly limited as long as it is a layer having an insulating property, and may be a single layer or a multilayer.
  • the material for forming the gate insulating film is not particularly limited, and for example, polymethylmethacrylate, polystyrene, polyvinylphenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinylacetate, polyurethane, polysulphon, and polybenzoxa. Examples thereof include polymers containing sol, polyvinyl sesquioxane, epoxy resins and phenolic resins, silicon dioxide, aluminum oxide, inorganic oxides containing titanium oxide, and nitrides containing silicon nitride.
  • the polymer is preferable from the viewpoint of compatibility with the organic semiconductor film
  • the inorganic oxide is preferable from the viewpoint of film uniformity
  • silicon dioxide is more preferable.
  • the film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.
  • the method for forming the gate insulating film is not particularly limited, and for example, a method of applying a gate insulating film forming composition containing the above material on a substrate on which a gate electrode is formed, and a method of depositing or depositing the above material. A method of sputtering can be mentioned.
  • a source electrode is an electrode into which a current flows from the outside through wiring.
  • the drain electrode is an electrode that sends an electric current to the outside through wiring.
  • the material for forming the source electrode and the drain electrode the same material as the electrode material for forming the gate electrode described above can be used. Among them, metal is preferable, and gold or silver is more preferable.
  • the thickness of the source electrode and the drain electrode is not particularly limited, but is preferably 1 nm or more, and more preferably 10 nm or more, respectively.
  • the upper limit of the thickness of the source electrode and the drain electrode is preferably 500 nm or less, more preferably 300 nm or less.
  • the distance (gate length L) between the source electrode and the drain electrode can be appropriately determined, but is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the gate width W can be appropriately determined, but is preferably 5000 ⁇ m or less, and more preferably 1000 ⁇ m or less.
  • the ratio of the gate width W to the gate length L is not particularly limited, but for example, the ratio W / L is preferably 10 or more, and more preferably 20 or more.
  • the method of forming the source electrode and the drain electrode is not particularly limited, and for example, a method of vacuum-depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film are formed, and an electrode forming composition. Examples include a method of applying or printing.
  • the patterning method for patterning the source electrode and the drain electrode is the same as the above-described gate electrode patterning method.
  • Organic semiconductor film is the film of the present invention described above.
  • the entire organic TFT may be sealed with a metal sealing can, or a sealing layer may be formed using a sealing agent.
  • a sealing agent composition for forming a sealing layer usually used for organic TFTs can be used.
  • the sealing agent include an inorganic material containing glass and silicon nitride, a polymer material containing parylene, and a low molecular weight material.
  • the sealing layer can be formed by a usual method such as coating and drying using the above-mentioned sealing agent.
  • the thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 ⁇ m.
  • FIG. 2 is a schematic cross-sectional view showing the structure of a bottom gate-top contact type organic TFT 20 which is an example of an organic TFT.
  • the organic TFT 20 has a substrate 1, a gate electrode 2, a gate insulating film 3, an organic semiconductor film 5, a source electrode 4A, a drain electrode 4B, and a sealing layer 6 in this order. Be prepared.
  • the organic TFT 20 is the same as the organic TFT 10 except that the layer structure (lamination mode) is different. Therefore, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are the same as those in the bottom gate-bottom contact type organic TFT described above. Is omitted.
  • the organic TFT of the present invention is not particularly limited in its use, and can be used for, for example, electronic paper, display devices, sensors, and electronic tags.
  • Comparative compound (1) was synthesized by the method described in paragraphs [0130] to [0133] of Japanese Patent No. 6219314.
  • Comparative compound (2) was synthesized by the method described in paragraph [0228] of Japanese Patent No. 4945757.
  • the obtained solid was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (4-1) (245 mg, yield 55%).
  • a thermal oxide film (thickness ) of SiO 2 is formed on the surface of a p-type silicon substrate (thickness: 0.4 mm, corresponding to a substrate 1 provided with a gate electrode 2) 1.
  • a substrate (size: 25 mm ⁇ 25 mm) having (s: 200 nm) was prepared.
  • the surface of the thermal oxide film (gate insulating film 3) of this substrate was washed with ultraviolet rays (UV) -ozone and then treated with ⁇ -phenetiltrimethoxysilane.
  • UV ultraviolet rays
  • the organic semiconductor film 5 was formed by the following three types of film forming methods.
  • Mobility ratio (maximum carrier mobility in 10 organic thin film transistors) / (minimum carrier mobility in 10 organic thin film transistors) Then, it was evaluated according to the following evaluation criteria. The results are shown in Table 1. Practically, it is preferable that A or B is used in any of the film forming methods. (Evaluation criteria) ⁇ A: Mobility ratio is less than 1.5 ⁇ B: Mobility ratio is 1.5 or more and less than 1.8 ⁇ C: Mobility ratio is 1.8 or more and less than 2.1 ⁇ D: Mobility ratio is 2. 1 or more
  • Examples 1 to 9 which are organic thin films using certain compounds (1) to (9) for the organic semiconductor film, showed excellent performance reproducibility.
  • Examples 1 to 8 in which the compound of the present invention is a compound represented by the general formula (5) showed better performance reproducibility (spin coating) and higher carrier mobility.
  • Examples 1 to 5 and Examples 7 to 8 in which the number of conjugated rings of A in the general formula (5) is 3 or more showed higher carrier mobility.
  • the compound of the present invention is a compound represented by the general formula (1), and L in the general formula (1) is the above-mentioned * -CH 2 Z-**.
  • One Example 1 showed better performance reproducibility (dropcast) and higher carrier mobility.
  • Substrate 2 Gate electrode 3 Gate insulating film 4A Source electrode 4B Drain electrode 5 Organic semiconductor film (organic semiconductor layer) 6 Sealing layer 10, 20 Organic thin film transistor (organic TFT)

Abstract

The purpose of the present invention is to provide: a compound that, when being formed into a film, provides excellent reproducibility of carrier mobility regardless of the film-forming method; a composition containing the compound; a film containing the compound; a structural body provided with the film; and an electronic device including the structural body. The compound according to the present invention is represented by general formula (1) or (2).

Description

化合物、組成物、膜、構造体及び電子デバイスCompounds, compositions, membranes, structures and electronic devices
　本発明は、化合物、膜、構造体及び電子デバイスに関する。 The present invention relates to compounds, membranes, structures and electronic devices.
　軽量化、低コスト化、及び、柔軟化が可能であることから、液晶ディスプレイ、及び、有機ＥＬ（Electric Luminescence）ディスプレイに用いられるＦＥＴ（電界効果トランジスタ）、ＲＦＩＤ（radio frequency identifier：ＲＦタグ）、及び、メモリを含む論理回路を用いる装置等に、有機半導体膜（有機半導体層）を有する有機薄膜トランジスタ（有機ＴＦＴ：Thin Film Transistor）の利用が検討されている。 FETs (field effect transistors), RFIDs (radio frequency identifiers: RF tags), which are used in liquid crystal displays and organic EL (Electric Luminescence) displays, because they can be made lighter, cheaper, and more flexible. Further, the use of an organic thin film transistor (organic TFT: Thin Film Transistor) having an organic semiconductor film (organic semiconductor layer) is being studied for an apparatus or the like using a logic circuit including a memory.
　このような有機半導体膜を形成するための化合物として、特許文献１には、トリプチセン骨格を有する有機半導体化合物が開示されている。 As a compound for forming such an organic semiconductor film, Patent Document 1 discloses an organic semiconductor compound having a triptycene skeleton.
特許第６２１９３１４号公報Japanese Patent No. 6219314
　このようななか、本発明者らが特許文献１の実施例に記載の化合物を用いて有機薄膜トランジスタを作製したところ、有機半導体膜の成膜方法によってはキャリア移動度の再現性（以下、「キャリア移動度の再現性」を「性能再現性」とも言う）が不十分となることが明らかになった。 Under these circumstances, when the present inventors produced an organic thin film transistor using the compound described in Examples of Patent Document 1, the reproducibility of carrier mobility (hereinafter, “carrier mobility” was determined depending on the method of forming the organic semiconductor film. It became clear that "reproducibility of degree" is also called "performance reproducibility").
　そこで、本発明は、上記実情に鑑みて、成膜方法によらず、膜にしたときにキャリア移動度の再現性に優れる化合物、上記膜を備える構造体、及び、上記構造体を含む電子デバイスを提供することを目的とする。 Therefore, in view of the above circumstances, the present invention relates to a compound having excellent reproducibility of carrier mobility when formed into a film, a structure provided with the film, and an electronic device containing the structure, regardless of the film forming method. The purpose is to provide.
　本発明者らは、上記課題について鋭意検討した結果、特定の構造を有するトリプチセン骨格の化合物を用いること、上記課題を解決できることを見出した。
　すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of diligent studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a compound having a triptycene skeleton having a specific structure.
That is, the present inventors have found that the above problems can be solved by the following configuration.
（１）　後述する一般式（１）又は（２）で表される化合物。
（２）　上記一般式（１）で表される、上記（１）に記載の化合物。
（３）　後述する一般式（３）で表される、上記（２）に記載の化合物。
（４）　上記一般式（３）中のｍ及びｎが、いずれも１である、上記（３）に記載の化合物。
（５）　後述する一般式（４）で表される、上記（１）に記載の化合物。
（６）　上記一般式（４）中、ｍ及びｎが、いずれも１である、上記（５）に記載の化合物。
（７）　後述する一般式（５）で表される、上記（２）に記載の化合物。
（８）　Ｂが、置換基を有していてもよい炭素数１２～１８のアルキル基である、上記（１）～（７）のいずれかに記載の化合物。ここで、上記アルキル基を構成する炭素原子は、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ、又は、－ＮＲ１－で置換されていてもよい。Ｘは、酸素原子又は硫黄原子を表す。Ｒ１は、水素原子、又は、置換基を有していてもよい脂肪族炭化水素基を表す。
（９）　Ｌにおいて、部分構造同士を直線的につなぐ原子数が偶数である、上記（１）～（８）のいずれかに記載の化合物。ただし、置換基は上記原子数に含まれない。
（１０）　Ｌが、単結合、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨ－、－ＣＨ２ＣＨ２－、－（ＣＨ２）４－又は、＊－ＣＨ２Ｚ－＊＊である、上記（１）～（９）のいずれかに記載の化合物。ここで、Ｚは、酸素原子、硫黄原子、セレン原子、又は、－ＮＲ２－を表す。Ｒ２は、水素原子又はアルキル基を表す。また、＊は、上記一般式中のＡ、Ｂ又はＱとの結合部位を表し、＊＊は、上記一般式中のベンゼン環との結合部位を表す。
（１１）　Ｙが、水素原子である、上記（１）～（１０）のいずれかに記載の化合物。
（１２）　Ｑが、水素原子、又はフッ素原子である、上記（１）～（１１）のいずれかに記載の化合物。
（１３）　Ａが、カルコゲン原子を含む縮合多環共役複素環である、上記（１）～（１２）のいずれかに記載の化合物。
（１４）　Ａが、電荷輸送基である、上記（１）～（１３）のいずれかに記載の化合物。
（１５）　Ａが、後述する一般式（Ａ１）で表される基、後述する一般式（Ａ２）で表される基、又は、これらの組み合わせである、上記（１）～（１４）のいずれかに記載の化合物。
（１６）　上記（１）～（１５）のいずれかに記載の化合物と、少なくとも１種類の溶剤とを含有する組成物。
（１７）　上記（１）～（１５）のいずれかに記載の化合物を含有する膜。
（１８）　基板と、上記基板の表面に配置された上記（１７）に記載の膜とを備える、構造体。
（１９）　上記（１８）に記載の構造体を含む、電子デバイス。
（２０）　有機薄膜トランジスタである、上記（１９）に記載の電子デバイス。 (1) A compound represented by the general formula (1) or (2) described later.
(2) The compound according to the above (1), which is represented by the above general formula (1).
(3) The compound according to (2) above, which is represented by the general formula (3) described later.
(4) The compound according to (3) above, wherein m and n in the general formula (3) are both 1.
(5) The compound according to (1) above, which is represented by the general formula (4) described later.
(6) The compound according to (5) above, wherein m and n are both 1 in the general formula (4).
(7) The compound according to (2) above, which is represented by the general formula (5) described later.
(8) The compound according to any one of (1) to (7) above, wherein B is an alkyl group having 12 to 18 carbon atoms which may have a substituent. Here, the carbon atom constituting the alkyl group may be substituted with an oxygen atom, a sulfur atom, a silicon atom,> C = X, or −NR 1 −. X represents an oxygen atom or a sulfur atom. R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
(9) The compound according to any one of (1) to (8) above, wherein the number of atoms linearly connecting the partial structures in L is an even number. However, the substituent is not included in the above number of atoms.
(10) L is a single bond, -C≡C -, - CH = CH -, - CH 2 CH 2 -, - (CH 2) 4 - or, * - CH 2 Z - is a **, the ( The compound according to any one of 1) to (9). Here, Z represents an oxygen atom, a sulfur atom, a selenium atom, or -NR 2- . R 2 represents a hydrogen atom or an alkyl group. Further, * represents a binding site with A, B or Q in the above general formula, and ** represents a binding site with a benzene ring in the above general formula.
(11) The compound according to any one of (1) to (10) above, wherein Y is a hydrogen atom.
(12) The compound according to any one of (1) to (11) above, wherein Q is a hydrogen atom or a fluorine atom.
(13) The compound according to any one of (1) to (12) above, wherein A is a condensed polycyclic conjugated heterocycle containing a chalcogen atom.
(14) The compound according to any one of (1) to (13) above, wherein A is a charge transport group.
(15) Any of the above (1) to (14), wherein A is a group represented by the general formula (A1) described later, a group represented by the general formula (A2) described later, or a combination thereof. The compound described in Crab.
(16) A composition containing the compound according to any one of (1) to (15) above and at least one solvent.
(17) A film containing the compound according to any one of (1) to (15) above.
(18) A structure comprising a substrate and the film according to (17) above, which is arranged on the surface of the substrate.
(19) An electronic device comprising the structure according to (18) above.
(20) The electronic device according to (19) above, which is an organic thin film transistor.
　以下に示すように、本発明によれば、成膜方法によらず、膜にしたときにキャリア移動度の再現性に優れる化合物、上記膜を備える構造体、及び、上記構造体を含む電子デバイスを提供することができる。 As shown below, according to the present invention, a compound having excellent reproducibility of carrier mobility when formed into a film, a structure provided with the film, and an electronic device containing the structure, regardless of the film forming method. Can be provided.
有機薄膜トランジスタの一例であるボトムゲート－ボトムコンタクト型の有機薄膜トランジスタの構造を示す断面模式図である。It is sectional drawing which shows the structure of the bottom gate-bottom contact type organic thin film transistor which is an example of an organic thin film transistor. 有機薄膜トランジスタの他の例であるボトムゲート－トップコンタクト型の有機薄膜トランジスタの構造を示す断面模式図である。It is sectional drawing which shows the structure of the bottom gate-top contact type organic thin film transistor which is another example of an organic thin film transistor.
　以下、本発明について説明する。
　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　また、本明細書において、「脂肪族炭化水素基」、「アルキル基」、「アルケニル基」、及び、「アルケニル基」は、特に断りの無い限り、直鎖状、分岐鎖状、及び、環状のいずれの構造を有するものも含むものとする。
　また、本発明において、各成分は、１種を単独でも用いても、２種以上を併用してもよい。ここで、各成分について２種以上を併用する場合、その成分について含有量とは、特段の断りが無い限り、合計の含有量を指す。
　また、一般式中に同じ記号（アルファベット）がある場合、特段の断りが無い限り、それらは同一であっても異なっていてもよい。 Hereinafter, the present invention will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, the "aliphatic hydrocarbon group", "alkyl group", "alkenyl group", and "alkenyl group" are linear, branched, and cyclic unless otherwise specified. It shall include those having any of the above structures.
Further, in the present invention, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.
Further, when the same symbols (alphabets) are present in the general formula, they may be the same or different unless otherwise specified.
［化合物］
　本発明の化合物は、後述する一般式（１）又は（２）で表される化合物である。
　本発明の化合物はこのような構成をとるため、上述した効果が得られるものと考えらえる。その理由は明らかではないが、およそ以下のとおりと推測される。
　本発明の化合物は後述する一般式（１）及び（２）に示されるように、Ｂ（置換基を有していてもよい炭素数５～２２の脂肪族炭化水素基）とトリプチセン骨格を有する。そのため、本発明の化合物を用いて膜（有機半導体膜）を形成した場合、Ｂ（置換基を有していてもよい炭素数５～２２の脂肪族炭化水素）によって生じる分子形状の異方性と、歯車のように噛み合うトリプチセン骨格によって３次元方向への自己組織化が生じるものと考えられる。ここで、後述する一般式（１）及び（２）に示されるように、Ａ（２～１０個の共役環を有する２価の共役系連結基）及びＢ（置換基を有していてもよい炭素数５～２２の脂肪族炭化水素）がトリプチセン骨格の特定の位置に結合しているため、これらの基が上述した自己組織化により３次元方向（一方のＹが結合する炭素原子と他方のＹが結合する炭素原子とを結ぶ軸方向、即ち膜厚方向と、これに垂直な平面方向）に大凡配列されるものと考えられる。結果として、成膜方法によらず同様の構造が形成され、優れた性能再現性が達成されるものと推測される。 [Compound]
The compound of the present invention is a compound represented by the general formula (1) or (2) described later.
Since the compound of the present invention has such a structure, it is considered that the above-mentioned effects can be obtained. The reason is not clear, but it is presumed to be as follows.
As shown in the general formulas (1) and (2) described later, the compound of the present invention has B (an aliphatic hydrocarbon group having 5 to 22 carbon atoms which may have a substituent) and a triptycene skeleton. .. Therefore, when a film (organic semiconductor film) is formed using the compound of the present invention, the anisotropy of the molecular shape caused by B (aliphatic hydrocarbon having 5 to 22 carbon atoms which may have a substituent) It is considered that the triptycene skeleton that meshes like a gear causes self-organization in the three-dimensional direction. Here, as shown in the general formulas (1) and (2) described later, A (a divalent conjugated system linking group having 2 to 10 conjugated rings) and B (even if it has a substituent). Since good aliphatic hydrocarbons with 5 to 22 carbon atoms are bonded to specific positions in the trypticene skeleton, these groups are in the three-dimensional direction (one Y-bonded carbon atom and the other) due to the self-assembly described above. It is considered that they are roughly arranged in the axial direction connecting the carbon atoms to which Y is bonded, that is, the film thickness direction and the plane direction perpendicular to this. As a result, it is presumed that the same structure is formed regardless of the film forming method, and excellent performance reproducibility is achieved.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（１）及び（２）中、Ｌは、単結合又は２価の連結基を表す。
　一般式（１）及び（２）中、Ａは、２～１０個の共役環を有する２価の共役系連結基を表す。ここで、Ａ中の任意の環Ｒにおいて、上記環Ｒに縮環する環の数と、上記環Ｒに単結合又は２価の共役系連結基を介して結合するＡ中の環の数との合計は２である。ただし、上記環Ｒが、単結合又は２価の共役系連結基を介して、一般式中のＬ、Ｂ又はＱに結合する場合、上記合計は１である。
　一般式（１）及び（２）中、Ｂは、置換基を有していてもよい炭素数５～２２の脂肪族炭化水素基を表す。ここで、上記脂肪族炭化水素基を構成する炭素原子は、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ（Ｘは、酸素原子又は硫黄原子を表す）、又は、－ＮＲ１－で置換されていてもよい。Ｒ１は、水素原子、又は、置換基を有していてもよい脂肪族炭化水素基を表す。
　一般式（１）及び（２）中、Ｑは、水素原子又はハロゲン原子を表す。
　一般式（１）及び（２）中、ｎは、０又は１を表す。
　一般式（１）及び（２）中、Ｘ１、Ｘ２、Ｘ３及びＸ４は、それぞれ独立に、下記一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基を表す。
　一般式（１）及び（２）中、Ｙは、水素原子又は置換基を表す。
　ただし、一般式（１）中の２つのｎ、及び、一般式（１）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。また、一般式（２）中の２つのｎ、及び、一般式（２）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。 In the general formulas (1) and (2), L represents a single bond or a divalent linking group.
In the general formulas (1) and (2), A represents a divalent conjugate system linking group having 2 to 10 conjugate rings. Here, in any ring R in A, the number of rings fused to the ring R and the number of rings in A bonded to the ring R via a single bond or a divalent conjugated system linking group. The total of is 2. However, when the ring R is bonded to L, B or Q in the general formula via a single bond or a divalent conjugated system linking group, the total is 1.
In the general formulas (1) and (2), B represents an aliphatic hydrocarbon group having 5 to 22 carbon atoms which may have a substituent. Here, the carbon atom constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfur atom, a silicon atom,> C = X (X represents an oxygen atom or a sulfur atom), or -NR 1-. It may have been. R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
In the general formulas (1) and (2), Q represents a hydrogen atom or a halogen atom.
In the general formulas (1) and (2), n represents 0 or 1.
In the general formulas (1) and (2), X 1 , X 2 , X 3 and X 4 independently represent groups represented by the following general formulas (AB) or (BA), respectively.
In the general formulas (1) and (2), Y represents a hydrogen atom or a substituent.
However, the general formula (1) two n in, and, X 1 in the formula (1), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1. In general formula (2) two n in, and, X 1 in the general formula (2), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1.
〔Ｌ〕
　上述のとおり、一般式（１）及び（２）中、Ｌは、単結合又は２価の連結基を表す。
　上記２価の連結基は特に制限されないが、例えば、直鎖状、分岐鎖状若しくは環状の２価の脂肪族炭化水素基（例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基、アルケニレン基、アルキニレン基）、２価の芳香族炭化水素基（例えば、フェニレン基）、－Ｏ－、－Ｓ－、－ＳＯ２－、－ＮＲＬ－、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＲＬ－、－Ｏ－ＣＯ－Ｏ－、－ＳＯ３－、－ＮＨＣＯＯ－、－ＳＯ２ＮＲＬ－、－ＮＨ－ＣＯ－ＮＨ－またはこれらを２種以上組み合わせた基（例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。ここで、ＲＬは、水素原子またはアルキル基（好ましくは炭素数１～１０）を表す。 [L]
As described above, in the general formulas (1) and (2), L represents a single bond or a divalent linking group.
The divalent linking group is not particularly limited, but for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group, or an alkenylene group). , Alquinylene group), divalent aromatic hydrocarbon group (eg, phenylene group), -O-, -S-, -SO 2- , -NR L- , -CO-, -NH-, -COO-, -CONR L- , -O-CO-O-, -SO 3- , -NHCOO-, -SO 2 NR L- , -NH-CO-NH- or a group combining two or more of these (for example, alkyleneoxy Groups, alkyleneoxycarbonyl groups, alkylenecarbonyloxy groups, etc.) and the like. Here, RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
＜好適な態様＞
　性能再現性がより優れ、キャリア移動度がより高くなる理由から、上記Ｌにおいて、部分構造同士を直線的につなぐ原子数が偶数である（ただし、置換基は上記原子数に含まれない）ことが好ましい。
　以下、「性能再現性がより優れ、キャリア移動度がより高くなる」ことを「本発明の効果等がより優れる」とも言う。 <Preferable aspect>
In the above L, the number of atoms connecting the partial structures linearly is an even number (however, the substituent is not included in the above number of atoms) for the reason that the performance reproducibility is better and the carrier mobility is higher. Is preferable.
Hereinafter, "the performance reproducibility is better and the carrier mobility is higher" is also referred to as "the effect of the present invention is more excellent".
　上記Ｌは、本発明の効果等がより優れる理由から、単結合、－（Ｃ≡Ｃ）ｎ－、－（ＣＨ＝ＣＨ）ｎ－、－（ＣＨ２）２ｎ－又は、＊－（ＣＨ２）２ｎ－１Ｚ－＊＊であることが好ましく、
単結合、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨ－、－（ＣＨ２）２ｎ－又は、＊－（ＣＨ２）２ｎ－１Ｚ－＊＊であることがより好ましく、
＊－（ＣＨ２）２ｎ－１Ｚ－＊＊であることが特に好ましい。
　ここで、Ｚは、酸素原子、硫黄原子、セレン原子、又は、－ＮＲ２－を表し、酸素原子、硫黄原子であることが好ましく、酸素原子であることがより好ましい。ｎは１～５の整数を示し、１～３の整数であることがより好ましく、１であることが特に好ましい。Ｒ２は、水素原子又はアルキル基を表す。また、＊は、一般式中のＡ、Ｂ又はＱとの結合部位を表し、＊＊は、一般式中のベンゼン環（トリプチセンを構成するベンゼン環）との結合部位を表す。 The above L is a single bond,-(C≡C) n -,-(CH = CH) n -,-(CH 2 ) 2n-, or *-(CH 2) because the effect of the present invention is more excellent. ) 2n-1 Z-** is preferable.
More preferably, it is a single bond, -C≡C-, -CH = CH-,-(CH 2 ) 2n- or *-(CH 2 ) 2n-1 Z-**.
*-(CH 2 ) 2n-1 Z-** is particularly preferable.
Here, Z is an oxygen atom, a sulfur atom, a selenium atom, or, -NR 2 - represents an oxygen atom, preferably a sulfur atom, more preferably oxygen atom. n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1. R 2 represents a hydrogen atom or an alkyl group. Further, * represents a binding site with A, B or Q in the general formula, and ** represents a binding site with a benzene ring (benzene ring constituting triptycene) in the general formula.
＜具体例＞
　以下に、上記Ｌの具体例を示す。ここで、＊は結合部位を表す。 <Specific example>
A specific example of the above L is shown below. Here, * represents a binding site.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-I000009
〔Ａ〕
　上述のとおり、一般式（１）及び（２）中、Ａは、２～１０個の共役環を有する２価の共役系連結基を表す。 [A]
As described above, in the general formulas (1) and (2), A represents a divalent conjugate system linking group having 2 to 10 conjugate rings.
＜２価の共役系連結基＞
　上述のとおり、上記Ａは２価の共役系連結基である。
　上記２価の共役系連結基とは、一方の結合部位から他方の結合部位まで共役系が繋がる２価の連結基である。 <Divalent conjugated system linking group>
As described above, A is a divalent conjugated system linking group.
The divalent conjugated system linking group is a divalent linking group in which the conjugated system is connected from one binding site to the other binding site.
＜共役環＞
　上記共役環とは、芳香族環又は反芳香族環である。
　上記芳香族環とは、π電子系に含まれる電子の数が４ｎ＋２（ｎは０以上の整数）の環であり、反芳香族環とは、π電子系に含まれる電子の数が４ｎ（ｎは１以上の整数）の環である。
　上記共役環は、本発明の効果等がより優れる理由から、芳香族環が好ましい。 <Conjugated ring>
The conjugated ring is an aromatic ring or an antiaromatic ring.
The aromatic ring is a ring in which the number of electrons contained in the π-electron system is 4n + 2 (n is an integer of 0 or more), and the antiaromatic ring is a ring in which the number of electrons contained in the π-electron system is 4n (n). n is a ring of 1 or more).
The conjugated ring is preferably an aromatic ring because the effects of the present invention are more excellent.
　上記芳香族環としては、例えば、ベンゼン環、ピロール環、チオフェン環、ピリジン環、フラン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、チアゾール環、オキサゾール環、イミダゾール環、ピラゾール環、イソキサゾール環、イソチアゾール環、トリアゾール環、フラザン環、オキサジチアゾール環、チアジアゾール環、ジオキサゾール環、ジチアゾール環、アズレン環等が挙げられる。なかでも、本発明の効果等がより優れる理由から、ベンゼン環、チオフェン環が好ましい。 Examples of the aromatic ring include a benzene ring, a pyrrole ring, a thiophene ring, a pyridine ring, a furan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a selenophene ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyrazole ring, and an isoxazole ring. , Isothiazole ring, triazole ring, flazan ring, oxadithiazole ring, thiathiazole ring, dioxazole ring, dithiazole ring, azulene ring and the like. Of these, a benzene ring and a thiophene ring are preferable because the effects of the present invention are more excellent.
　上記反芳香族環としては、例えば、シクロブタジエン、シクロオクタテトラエン、ペンタレン等が挙げられる。 Examples of the antiaromatic ring include cyclobutadiene, cyclooctatetraene, pentalene and the like.
＜共役環の数＞
　上述のとおり、Ａは、２～１０個の共役環を有する。
　ここで、共役環の数を数える場合、単環としての共役環の数を数える。
　例えば、後述する化合物（１）において、Ａは、４つの共役環が縮環した構造（下記）（ここで、＊は結合部位）であるため、共役環の数は４である。 <Number of conjugated rings>
As mentioned above, A has 2-10 conjugate rings.
Here, when counting the number of conjugate rings, the number of conjugate rings as a single ring is counted.
For example, in compound (1) described later, A has a structure in which four conjugated rings are fused (below) (here, * is a binding site), so the number of conjugated rings is four.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　また、後述する化合物（８）において、Ａは、４つの共役環が縮環した構造とベンゼン環とが単結合で結合した構造（下記）であるため、共役環の数は５である。 Further, in the compound (8) described later, since A has a structure in which four conjugated rings are fused and a benzene ring is bonded by a single bond (below), the number of conjugated rings is 5.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　Ａは、本発明の効果等がより優れる理由から、３～８個の共役環を有するのが好ましく、４～６個の共役環を有するのがより好ましい。 A preferably has 3 to 8 conjugate rings, more preferably 4 to 6, for the reason that the effect of the present invention is more excellent.
＜共役環以外の環＞
　上記Ａは、要件（２価の共役系連結基、共役環の数、縮環する環の数と結合する環の数との合計）を満たせば共役環以外の環を有していてもよい。例えば、２，７－フルオレニレン基は、２つのベンゼン環と１つのペンタジエン環とが縮環した構造であり、共役環以外の環であるペンタジエン環を有するが、上記要件（２価の共役系連結基、共役環の数、縮環する環の数と結合する環の数との合計）を満たすため、上記Ａに該当する。 <Rings other than conjugated rings>
The above-mentioned A may have a ring other than the conjugated ring as long as it satisfies the requirements (divalent conjugated system linking group, number of conjugated rings, total number of rings to be fused and number of rings to be bonded). .. For example, the 2,7-fluorenylene group has a structure in which two benzene rings and one pentadiene ring are fused, and has a pentadiene ring which is a ring other than the conjugated ring. It corresponds to the above A in order to satisfy the group, the number of conjugated rings, the total number of rings to be fused and the number of rings to be bonded).
＜共役環同士の繋がり＞
　上記Ａは、上述のとおり２価の共役系連結基（一方の結合部位から他方の結合部位まで共役系が繋がる２価の連結基）であり、また、後述のとおり一方の結合部位から他方の結合部位まで分岐せずに伸びる形状であるため、共役環（単環の共役環）同士は、縮環するか、又は、単結合若しくは２価の共役系連結基で結合する。
　共役環同士を繋ぐ上記２価の共役系連結基は、一方の結合部位から他方の結合部位まで共役系が繋がる２価の連結基であれば特に制限されないが、本発明の効果等がより優れる理由から、ビニレン基、エチニレン基、アゾ基、イミノ基が好ましい。ここで上記ビニレン基の水素原子は置換されていてもよい。 <Connecting conjugated rings>
As described above, A is a divalent conjugated system linking group (a divalent conjugated group in which the conjugated system is connected from one binding site to the other binding site), and as described later, one binding site to the other. Since the shape extends to the bonding site without branching, the conjugated rings (monocyclic conjugated rings) are fused or bonded by a single bond or a divalent conjugated system linking group.
The divalent conjugated system linking group that connects the conjugated rings to each other is not particularly limited as long as it is a divalent linking group that connects the conjugated system from one bonding site to the other bonding site, but the effect of the present invention is more excellent. For this reason, a vinylene group, an ethynylene group, an azo group, and an imino group are preferable. Here, the hydrogen atom of the vinylene group may be substituted.
＜縮環する環の数と結合する環の数との合計＞
　上述のとおり、Ａ中の任意の環Ｒにおいて、上記環Ｒに縮環する環の数と、上記環Ｒに単結合又は２価の共役系連結基を介して結合するＡ中の環の数との合計は２である。ただし、上記環Ｒが、単結合又は２価の共役系連結基を介して、一般式中のＬ、Ｂ又はＱに結合する場合、上記合計は１である。なお、縮環については縮環を構成する各単環を環Ｒとする。環Ｒは共役環に限られない。
　換言すると、Ａに含まれる環Ｒのうち、結合部位を有する環Ｒについては、環Ｒに縮環する環の数と環Ｒに単結合又は２価の共役系連結基を介して結合するＡ中の環の数との合計（合計Ｘ）は１であり、それ以外の環Ｒについては、環Ｒに縮環する環の数と環Ｒに単結合又は２価の共役系連結基を介して結合するＡ中の環の数との合計（合計Ｙ）は２である。
　結果として、Ａは、一方の結合部位から他方の結合部位まで分岐せずに伸びる形状となる。
　以下、上記合計に関する要件を「要件Ａ」とも言う。 <Total of the number of rings to be fused and the number of rings to be bonded>
As described above, in any ring R in A, the number of rings fused to the ring R and the number of rings in A bonded to the ring R via a single bond or a divalent conjugated system linking group. The total of and is 2. However, when the ring R is bonded to L, B or Q in the general formula via a single bond or a divalent conjugated system linking group, the total is 1. As for the condensed ring, each single ring constituting the condensed ring is referred to as a ring R. Ring R is not limited to conjugated rings.
In other words, among the rings R contained in A, the ring R having a binding site is A that is bound to the ring R via a single bond or a divalent conjugated system linking group and the number of rings fused to the ring R. The total (total X) with the number of rings in the ring is 1, and for the other rings R, the number of rings fused to the ring R and the number of rings fused to the ring R via a single bond or a divalent conjugated system linking group are used. The total (total Y) with the number of rings in A to be bonded is 2.
As a result, A has a shape that extends from one binding site to the other binding site without branching.
Hereinafter, the requirement regarding the above total is also referred to as "requirement A".
　以下に、要件Ａを満たす例（ＯＫ）と要件Ａ満たさない例（ＮＧ）とを示す。
　例えば、下記（２）について見ると、結合部位を有する両端の２つのベンゼン環については、いずれも１つのベンゼン環と縮環し、他に縮環又は結合する環は存在しないため、合計Ｘは１であり、残りの環（真ん中のベンゼン環）については、両端のベンゼン環と縮環し、他に縮環又は結合する環は存在しないため、合計Ｙは２であり、要件Ａを満たす。
　また、例えば、下記（９）について見ると、結合部位を有する２つのベンゼン環は、いずれも２つのベンゼン環と縮環するため、合計Ｘは２であり、要件Ａを満たさない。
　また、例えば、下記（１５）について見ると、結合部位を有する２つのベンゼン環のうち一方は、単結合を介して２つのベンゼン環と結合するため、合計Ｘは２であり、要件Ａを満たさない。 An example of satisfying the requirement A (OK) and an example of not satisfying the requirement A (NG) are shown below.
For example, looking at (2) below, the two benzene rings at both ends that have a binding site are all fused with one benzene ring, and there is no other ring that is fused or bonded, so the total X is The total Y is 2 because the remaining ring (the benzene ring in the middle) is fused with the benzene rings at both ends and there is no other ring to be fused or bonded, which satisfies the requirement A.
Further, for example, looking at (9) below, since the two benzene rings having a binding site are both fused with the two benzene rings, the total X is 2, which does not satisfy the requirement A.
Further, for example, looking at (15) below, since one of the two benzene rings having a binding site is bonded to the two benzene rings via a single bond, the total X is 2, which satisfies the requirement A. Absent.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　また、上述した２，７－フルオレニレン基は、結合部位を有する２つのベンゼン環については、いずれも１つのペンタジエン環と縮環し、他に縮環又は結合する環は存在しないため、合計Ｘは１であり、残りの環（ペンタジエン環）については、両端のベンゼン環と縮環し、他に縮環又は結合する環は存在しないため、合計Ｙは２であり、要件Ａを満たす。 Further, in the above-mentioned 2,7-fluorenylene group, the two benzene rings having a binding site are both fused with one pentadiene ring, and there is no other ring to be condensed or bonded, so that the total X is As for the remaining ring (pentadiene ring), the total Y is 2 because it is fused with the benzene ring at both ends and there is no other ring to be fused or bonded, which satisfies the requirement A.
＜好適な態様＞
　以下に、上記Ａの好適な態様を示す。 <Preferable aspect>
The preferred embodiment of A is shown below.
（第１の態様）
　上記Ａは、本発明の効果等がより優れる理由から、カルコゲン原子（酸素、硫黄、セレン、テルル、ポロニウム、リバモリウム）を含む縮合多環共役複素環（特に縮合芳香族複素環）であることが好ましい。上記縮合多環共役複素環としては、ベンゾチオフェン環、ベンゾチエノベンゾチオフェン環等が挙げられる。 (First aspect)
The above-mentioned A is a condensed polycyclic conjugated heterocycle (particularly a condensed aromatic heterocycle) containing an interchalcogen atom (oxygen, sulfur, selenium, tellurium, polonium, livermorium) because the effect of the present invention is more excellent. preferable. Examples of the condensed polycyclic conjugated heterocycle include a benzothiophene ring and a benzothienobenzothiophene ring.
（第２の態様）
　上記Ａは、本発明の効果等がより優れる理由から、電荷輸送基であることが好ましい。 (Second aspect)
The above-mentioned A is preferably a charge transport group for the reason that the effect of the present invention is more excellent.
（第３の態様）
　上記Ａは、本発明の効果等がより優れる理由から、下記一般式（Ａ１）で表される基、下記一般式（Ａ２）で表される基、又は、これらの組み合わせであることが好ましい。 (Third aspect)
The above-mentioned A is preferably a group represented by the following general formula (A1), a group represented by the following general formula (A2), or a combination thereof, for the reason that the effect of the present invention is more excellent.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（Ａ１）中、Ａｒ１、Ａｒ２及びＡｒ３は、それぞれ独立に、共役環（単環）を表す。ｐは、０～８の整数を表す。＊は、結合部位を表す。共役環（単環）の具体例は上述のとおりである。
　一般式（Ａ２）中、Ａｒは、共役環（単環又は縮環）を表す。Ｍは、単結合、又は、２価の共役系連結基（例えば、ビニレン基、エチニレン基、アゾ基、イミノ基、ここでビニレン基の水素原子は置換されていてもよい）を表す。ｑは、０～８の整数を表す。＊は、結合部位を表す。共役環（単環）の具体例は上述のとおりである。ただし、共役環が縮環の場合、縮環は上述した要件Ａを満たす。また、一般式（Ａ２）に含まれる単環としての共役環の数（縮環については縮環を構成する共役環の数を数える）は最大で１０である。 In the general formula (A1), Ar 1 , Ar 2 and Ar 3 independently represent a conjugated ring (single ring). p represents an integer from 0 to 8. * Represents the binding site. Specific examples of the conjugated ring (monocycle) are as described above.
In the general formula (A2), Ar represents a conjugated ring (monocyclic or condensed ring). M represents a single bond or a divalent conjugated system linking group (for example, a vinylene group, an ethynylene group, an azo group, an imino group, in which the hydrogen atom of the vinylene group may be substituted). q represents an integer from 0 to 8. * Represents the binding site. Specific examples of the conjugated ring (monocycle) are as described above. However, when the conjugated ring is a fused ring, the condensed ring satisfies the above-mentioned requirement A. Further, the number of conjugate rings as a single ring included in the general formula (A2) (for fused rings, the number of conjugated rings constituting the fused rings is counted) is 10 at the maximum.
＜具体例＞
　以下に上記Ａの具体例を示すがこれらに限られるものではない。＊は結合部位を表す。 <Specific example>
Specific examples of A above are shown below, but the present invention is not limited to these. * Represents the binding site.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
〔Ｂ〕
　上述のとおり、一般式（１）及び（２）中、Ｂは、置換基（例えば、後述する置換基群Ｚから選択される基）を有していてもよい炭素数５～２２の脂肪族炭化水素基を表す。ここで、上記脂肪族炭化水素基を構成する炭素原子は、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ（Ｘは、酸素原子又は硫黄原子を表す）、又は、－ＮＲ１－で置換されていてもよい。Ｒ１は、水素原子、又は、置換基を有していてもよい脂肪族炭化水素基を表す。 [B]
As described above, in the general formulas (1) and (2), B is an aliphatic group having 5 to 22 carbon atoms which may have a substituent (for example, a group selected from the substituent group Z described later). Represents a hydrocarbon group. Here, the carbon atom constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfur atom, a silicon atom,> C = X (X represents an oxygen atom or a sulfur atom), or -NR 1-. It may have been. R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
　なお、上記Ｂが「置換基を有する」炭素数５～２２の脂肪族炭化水素基である場合、上記炭素数の中に置換基中の炭素原子は数えない。また、上記Ｂにおいて脂肪族炭化水素基を構成する炭素原子が、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ（Ｘは、酸素原子又は硫黄原子を表す）、又は、－ＮＲ１－で置換されている場合、置換される前の脂肪族炭化水素基の炭素数が５～２２であればよい。 When the B is an aliphatic hydrocarbon group having 5 to 22 carbon atoms that "has a substituent", the carbon atom in the substituent is not counted in the carbon number. Further, in the above B, the carbon atom constituting the aliphatic hydrocarbon group is an oxygen atom, a sulfur atom, a silicon atom,> C = X (X represents an oxygen atom or a sulfur atom), or -NR 1- . When substituted, the aliphatic hydrocarbon group before substitution may have 5 to 22 carbon atoms.
　上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状、分岐鎖状若しくは環状の、アルキル基、アルケニル基、又は、アルキニル基などが挙げられる。なかでも、本発明の効果等がより優れる理由から、直鎖状のアルキル基が好ましい。 The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group and the like. Among them, a linear alkyl group is preferable because the effect of the present invention is more excellent.
＜好適な態様＞
　上記Ｂで表される脂肪族炭化水素基は、炭素数８～２０であることが好ましく、炭素数１０～２０であることがより好ましく、炭素数１２から１８であることが特に好ましい。
　また、本発明の効果等がより優れる理由から、Ｂで表される脂肪族炭化水素基は、無置換のアルキル基、ハロゲン化アルキル基、無置換のアルケニル基、ハロゲン化アルケニル基、無置換のアルキニル基、ハロゲン化アルケニル基、酸素原子で置換されたアルキル基、酸素原子で置換されたアルケニル基、酸素原子で置換されたアルキニル基であることが好ましく、
無置換のアルキル基、ハロゲン化アルキル基、無置換のアルケニル基、無置換のアルキニル基、酸素原子で置換されたアルキル基であることがより好ましく、
無置換のアルキル基、酸素原子で置換されたアルキル基であることが特に好ましい。 <Preferable aspect>
The aliphatic hydrocarbon group represented by B is preferably 8 to 20 carbon atoms, more preferably 10 to 20 carbon atoms, and particularly preferably 12 to 18 carbon atoms.
Further, for the reason that the effect of the present invention is more excellent, the aliphatic hydrocarbon group represented by B is an unsubstituted alkyl group, a halogenated alkyl group, an unsubstituted alkenyl group, a halogenated alkenyl group, or an unsubstituted alkenyl group. It is preferably an alkynyl group, an alkenyl halide group, an alkyl group substituted with an oxygen atom, an alkenyl group substituted with an oxygen atom, or an alkynyl group substituted with an oxygen atom.
More preferably, it is an unsubstituted alkyl group, a halogenated alkyl group, an unsubstituted alkenyl group, an unsubstituted alkynyl group, or an alkyl group substituted with an oxygen atom.
It is particularly preferable that the alkyl group is unsubstituted or an alkyl group substituted with an oxygen atom.
＜具体例＞
　以下に上記Ｂの具体例を示すがこれらに限られるものではない。＊は結合部位を表す。 <Specific example>
Specific examples of B above are shown below, but the present invention is not limited to these. * Represents the binding site.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000017
〔Ｑ〕
　一般式（１）及び（２）中、Ｑは、水素原子又はハロゲン原子を表す。
　上記Ｑは、本発明の効果等がより優れる理由から、水素原子又はフッ素原子であることが好ましい。 [Q]
In the general formulas (1) and (2), Q represents a hydrogen atom or a halogen atom.
The above Q is preferably a hydrogen atom or a fluorine atom for the reason that the effect of the present invention is more excellent.
〔ｎ〕
　一般式（１）及び（２）中、ｎは、０又は１を表す。
　一般式（１）及び（２）中のｎのうち少なくとも１つは、本発明の効果等がより優れる理由から、１であることが好ましい。
　一般式（１）中の２つのｎは、本発明の効果等がより優れる理由から、いずれも１であることが好ましい。
　一般式（２）中の２つのｎは、本発明の効果等がより優れる理由から、いずれも１であることが好ましい。 [N]
In the general formulas (1) and (2), n represents 0 or 1.
At least one of n in the general formulas (1) and (2) is preferably 1 for the reason that the effect of the present invention is more excellent.
The two n in the general formula (1) are preferably 1 for the reason that the effect of the present invention is more excellent.
The two n in the general formula (2) are preferably 1 for the reason that the effect of the present invention is more excellent.
〔Ｘ１、Ｘ２、Ｘ３及びＸ４〕
　一般式（１）及び（２）中、Ｘ１、Ｘ２、Ｘ３及びＸ４は、それぞれ独立に、下記一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基を表す。 [X 1 , X 2 , X 3 and X 4 ]
In the general formulas (1) and (2), X 1 , X 2 , X 3 and X 4 independently represent groups represented by the following general formulas (AB) or (BA), respectively.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中のＬ、Ａ、Ｂ及びＱの定義、具体例及び好適な態様は、一般式（１）及び（２）中のＬ、Ａ、Ｂ及びＱとそれぞれ同じである。
　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中、＊は、結合部位を表す。 Definitions, specific examples and preferred embodiments of L, A, B and Q in the general formulas (AB) and (BA) include L, A, B and in the general formulas (1) and (2). It is the same as Q.
In the general formulas (AB) and (BA), m and n independently represent 0 or 1, respectively.
In the general formulas (AB) and (BA), * represents a binding site.
　上記Ｘ１である一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基において、ｍは、本発明の効果等がより優れる理由から、１であることが好ましい。
　上記Ｘ１である一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基において、ｎは、本発明の効果等がより優れる理由から、１であることが好ましい。
　本発明の化合物が一般式（１）で表される化合物である場合、上記Ｘ１は、本発明の効果等がより優れる理由から、一般式（Ａ－Ｂ）で表される基であることが好ましい。
　本発明の化合物が一般式（２）で表される化合物である場合、上記Ｘ１は、本発明の効果等がより優れる理由から、一般式（Ｂ－Ａ）で表される基であることが好ましい。 In the group represented by the general formula (AB) or (BA) of X 1 , m is preferably 1 for the reason that the effect of the present invention is more excellent.
In the group represented by the general formula (AB) or (BA) of X 1 , n is preferably 1 for the reason that the effect of the present invention is more excellent.
When the compound of the present invention is a compound represented by the general formula (1), the above X 1 is a group represented by the general formula (AB) for the reason that the effect of the present invention is more excellent. Is preferable.
When the compound of the present invention is a compound represented by the general formula (2), the above X 1 is a group represented by the general formula (BA) for the reason that the effect of the present invention is more excellent. Is preferable.
　上記Ｘ２、Ｘ３及びＸ４である一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基において、ｎは、本発明の効果等がより優れる理由から、１であることが好ましい。 In the group represented by X 2, X 3 and X 4 is a general formula (A-B) or (B-A), n is the reason that the effect or the like of the present invention is more excellent, it is 1 preferable.
〔Ｙ〕
　上述のとおり、一般式（１）及び（２）中、Ｙは、水素原子又は置換基（例えば、後述する置換基群Ｚから選択される基）を表す。
　上記置換基は、上述した一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基であってもよい。
　上記Ｙは、本発明の効果等がより優れる理由から、水素原子であることが好ましい。 [Y]
As described above, in the general formulas (1) and (2), Y represents a hydrogen atom or a substituent (for example, a group selected from the substituent group Z described later).
The above-mentioned substituent may be a group represented by the above-mentioned general formula (AB) or (BA).
The Y is preferably a hydrogen atom because the effect of the present invention is more excellent.
〔合計６つのｎのうち少なくとも１つは１〕
　上述のとおり、一般式（１）中の２つのｎ、及び、一般式（１）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。また、一般式（２）中の２つのｎ、及び、一般式（２）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。すなわち、本発明の化合物は、上記Ｂで表される基を少なくとも１つ有する。
　なお、一般式（１）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎとは、一般式（１）中のＸ１、Ｘ２、Ｘ３及びＸ４である一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基中の各ｎ（合計４つのｎ）を表す。同様に、一般式（２）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎとは、一般式（２）中のＸ１、Ｘ２、Ｘ３及びＸ４である一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基中の各ｎ（合計４つのｎ）を表す。
　上記合計６つのｎのうち、本発明の効果等がより優れる理由から、３～６つのｎが１であることが好ましい。 [At least one of the total of six n is 1]
As described above, the general formula (1) two n in, and, X 1 in the formula (1), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one One is 1. In general formula (2) two n in, and, X 1 in the general formula (2), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1. That is, the compound of the present invention has at least one group represented by B above.
In addition, each n contained in X 1 , X 2 , X 3 and X 4 in the general formula (1) is a general formula X 1 , X 2 , X 3 and X 4 in the general formula (1). Represents each n (4 n in total) in the group represented by (AB) or (BA). Similarly, each n contained in X 1 , X 2 , X 3 and X 4 in the general formula (2) is a general X 1 , X 2 , X 3 and X 4 in the general formula (2). It represents each n (a total of four n) in the group represented by the formula (AB) or (BA).
Of the total of 6 n, 3 to 6 n are preferably 1 for the reason that the effect of the present invention is more excellent.
〔好適な態様〕
　以下に、本発明の化合物の好適な態様を示す。 [Preferable mode]
The preferred embodiments of the compounds of the present invention are shown below.
＜その１＞
　本発明の化合物は、本発明の効果等がより優れる理由から、上述した一般式（１）で表される化合物であることが好ましい。 <Part 1>
The compound of the present invention is preferably a compound represented by the above-mentioned general formula (1) for the reason that the effects of the present invention are more excellent.
＜その２＞
　上述した一般式（１）で表される化合物は、本発明の効果等がより優れる理由から、下記一般式（３）で表される化合物であることが好ましい。 <Part 2>
The compound represented by the general formula (1) described above is preferably a compound represented by the following general formula (3) because the effects of the present invention and the like are more excellent.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　一般式（３）中のＬ、Ａ、Ｂ、Ｑ及びＹの定義、具体例及び好適な態様は、上述した一般式（１）中のＬ、Ａ、Ｂ、Ｑ及びＹとそれぞれ同じである。
　一般式（３）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
　ただし、一般式（３）中の３つのｎのうち、少なくとも１つは１である。 The definitions, specific examples and preferred embodiments of L, A, B, Q and Y in the general formula (3) are the same as those of L, A, B, Q and Y in the general formula (1) described above. ..
In the general formula (3), m and n independently represent 0 or 1, respectively.
However, at least one of the three n in the general formula (3) is 1.
　一般式（３）中のｍは、本発明の効果等がより優れる理由から、１であることが好ましい。
　一般式（３）中のｍ及びｎは、本発明の効果等がより優れる理由から、いずれも１であることが好ましい。 The m in the general formula (3) is preferably 1 for the reason that the effect of the present invention is more excellent.
It is preferable that m and n in the general formula (3) are both 1 for the reason that the effect of the present invention is more excellent.
＜その３＞
　本発明の化合物は、本発明の効果等がより優れる理由から、下記一般式（４）で表される化合物であることが好ましい。 <Part 3>
The compound of the present invention is preferably a compound represented by the following general formula (4) for the reason that the effects of the present invention are more excellent.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　一般式（４）中のＬ、Ａ、Ｂ、Ｑ及びＹの定義、具体例及び好適な態様は、上述した一般式（１）及び（２）中のＬ、Ａ、Ｂ、Ｑ及びＹとそれぞれ同じである。
　一般式（４）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
　ただし、一般式（４）中の３つのｎのうち、少なくとも１つは１である。 The definitions, specific examples and preferred embodiments of L, A, B, Q and Y in the general formula (4) are the same as L, A, B, Q and Y in the general formulas (1) and (2) described above. Each is the same.
In the general formula (4), m and n independently represent 0 or 1, respectively.
However, at least one of the three n in the general formula (4) is 1.
　一般式（４）中のｍは、本発明の効果等がより優れる理由から、１であることが好ましい。
　一般式（４）中のｍ及びｎは、本発明の効果等がより優れる理由から、いずれも１であることが好ましい。 The m in the general formula (4) is preferably 1 for the reason that the effect of the present invention is more excellent.
It is preferable that m and n in the general formula (4) are both 1 for the reason that the effect of the present invention is more excellent.
＜その４＞
　本発明の化合物は、本発明の効果等がより優れる理由から、下記一般式（５）で表される化合物であることが好ましい。 <Part 4>
The compound of the present invention is preferably a compound represented by the following general formula (5) for the reason that the effects of the present invention are more excellent.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　一般式（５）中のＬ、Ａ、Ｂ、Ｑ、Ｘ２、Ｘ３、Ｘ４及びＹの定義、具体例及び好適な態様は、上述した一般式（１）中のＬ、Ａ、Ｂ、Ｑ、Ｘ２、Ｘ３、Ｘ４及びＹとそれぞれ同じである。
　一般式（５）中、ｎは、０又は１を表す。
　ただし、一般式（５）中の３つのｎ、及び、一般式（５）中のＸ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。 Definitions, specific examples and suitable embodiments of L, A, B, Q, X 2 , X 3 , X 4 and Y in the general formula (5) are described in L, A, B in the general formula (1) described above. , Q, X 2 , X 3 , X 4 and Y, respectively.
In the general formula (5), n represents 0 or 1.
However, three of n in the general formula (5) and, each n is included in the general formula (5) X 2, X 3 and X 4 in, out of the total of six n, at least one is 1 ..
　一般式（５）中のｎのうち少なくとも１つは、本発明の効果等がより優れる理由から、１であることが好ましい。
　一般式（５）中の３つのｎは、本発明の効果等がより優れる理由から、いずれも１であることが好ましい。 At least one of n in the general formula (5) is preferably 1 for the reason that the effect of the present invention is more excellent.
The three n in the general formula (5) are preferably 1 for the reason that the effect of the present invention is more excellent.
〔具体例〕
　以下、本発明の化合物の具体例を挙げるが、これらに限られるものではない。Ｌ、Ａ、Ｂ、Ｙ、及びＱについては上述のとおりである。 〔Concrete example〕
Specific examples of the compound of the present invention will be given below, but the present invention is not limited thereto. L, A, B, Y, and Q are as described above.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
〔合成方法〕
　本発明の化合物の合成方法は、特に限定されず、通常の方法を参照して、合成することができる。例えば、後述する実施例のとおり合成することができる。 [Synthesis method]
The method for synthesizing the compound of the present invention is not particularly limited, and the compound can be synthesized with reference to a usual method. For example, it can be synthesized as in the examples described later.
〔置換基群Ｚ〕
　以下、本明細書における置換基群Ｚについて説明する。
　置換基群Ｚは、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シリル基、アルコキシ基、アミノ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シリルオキシ基、ヘテロ環オキシ基、カルバモイル基、カルバモイルオキシ基、ヘテロ環チオ基、スルファモイル基、アリールアゾ基、ヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ヒドラジノ基、イミノ基、シアノ基、ヒドロキシ基、ニトロ基、メルカプト基、スルホ基、カルボキシ基、ヒドロキサム酸基、スルフィノ基、ボロン酸基（－Ｂ（ＯＨ）２）、ホスファト基（－ＯＰＯ（ＯＨ）２）、ホスホノ基（－ＰＯ（ＯＨ）２）、及び、スルファト基（－ＯＳＯ３Ｈ）を含む。
　上記の置換基群Ｚから選択される基は、更に置換基を有してもよい。 [Substituent group Z]
Hereinafter, the substituent group Z in the present specification will be described.
Substituent group Z includes halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, silyl group, alkoxy group, amino group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, Acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, Arylsulfonyl group, silyloxy group, heterocyclic oxy group, carbamoyl group, carbamoyloxy group, heterocyclic thio group, sulfamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, Phosphinylamino group, hydrazino group, imino group, cyano group, hydroxy group, nitro group, mercapto group, sulfo group, carboxy group, hydroxamic acid group, sulfino group, boronate group (-B (OH) 2 ), phosphat group (-OPO (OH) 2), a phosphono group (-PO (OH) 2), and comprises a sulfato group (-OSO 3 H).
The group selected from the above-mentioned Substituent Group Z may further have a Substituent.
　置換基群Ｚに含まれるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられ、フッ素原子、又は、塩素原子が好ましい。 Examples of the halogen atom contained in the substituent group Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
　置換基群Ｚに含まれるアルキル基は、特に制限されないが、炭素数１（３）～３０のアルキル基が好ましく、炭素数１（３）～２０のアルキル基がより好ましく、炭素数４～２０のアルキル基が更に好ましい。なお、括弧内の数字はシクロアルキル基の場合の炭素数を表す。
　置換基群Ｚに含まれる置換基を有してもよいアルキル基としては、例えば、メチル基、エチル基、プロピル基、２－メチルプロピル基、ブチル基、アミル基、ペンチル基、１－メチルペンチル基、２，２－ジメチルプロピル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基、３，７－ジメチルオクチル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、２，６－ジメチルオクチル基、イコシル基、２－デシルテトラデシル基、２－ヘキシルドデシル基、２－エチルオクチル基、２－デシルテトラデシル基、２－ブチルデシル基、１－オクチルノニル基、２－エチルオクチル基、２－オクチルデシル基、２－オクチルドデシル基、７－ヘキシルペンタデシル基、２－オクチルテトラデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、アダマンチル基、ベンジル基、２-シクロヘキシルエチル基、ｐ－クロロベンジル基、２－フェニルエチル基、トリフルオロメチル基、パーフルオロエチル基、２，２，３，３，４，４，４－ヘプタフルオロブチル基、Ｃ５Ｆ１１Ｃ２Ｈ４－、Ｃ６Ｆ１３Ｃ２Ｈ４－、３－アミノプロピル基、４－アミノブチル基、５－エトキシペンチル基、（メタ）アクリロキシプロピル基、（メタ）アクリロキシペンチル基、４－ヒドロキシブチル基、４－スルホブチル基、１０－ホスホノデシル基、２－ヒドロキシエトキシメチル基、２－イミダゾリルエトキシメチル基、４－（Ｎ，Ｎ－ジメチルアミノ）ブチル基、及び、５－ノルボルネンメチル基が挙げられる。 The alkyl group contained in the substituent group Z is not particularly limited, but an alkyl group having 1 (3) to 30 carbon atoms is preferable, an alkyl group having 1 (3) to 20 carbon atoms is more preferable, and an alkyl group having 4 to 20 carbon atoms is more preferable. Alkyl groups of are more preferred. The numbers in parentheses represent the number of carbon atoms in the case of a cycloalkyl group.
Examples of the alkyl group which may have a substituent contained in the substituent group Z include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, an amyl group, a pentyl group, and a 1-methylpentyl group. Group, 2,2-dimethylpropyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl group, 2,6-dimethyloctyl group, icosyl group, 2-decyltetradecyl group, 2-hexyldodecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group , 2-Ethyloctyl group, 2-octyldecyl group, 2-octyldodecyl group, 7-hexylpentadecyl group, 2-octyltetradecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, benzyl Group, 2-cyclohexylethyl group, p-chlorobenzyl group, 2-phenylethyl group, trifluoromethyl group, perfluoroethyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, C 5 F 11 C 2 H 4 - , C 6 F 13 C 2 H 4 -, 3- aminopropyl group, 4-aminobutyl group, 5-ethoxypentyl group, (meth) acryloxy propyl group, (meth) acryloxy Pentyl group, 4-hydroxybutyl group, 4-sulfobutyl group, 10-phosphonodecyl group, 2-hydroxyethoxymethyl group, 2-imidazolylethoxymethyl group, 4- (N, N-dimethylamino) butyl group, and 5- Norbornen methyl group can be mentioned.
　置換基群Ｚに含まれるアルケニル基は、特に制限されないが、炭素数２～２０のアルケニル基が好ましく、炭素数２～１２のアルケニル基がより好ましく、炭素数２～８のアルケニル基が更に好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアルケニル基としては、例えば、ビニル基、アリル基、２－ブテニル基、１－ペンテニル基、及び、４－ペンテニル基が挙げられる。 The alkenyl group contained in the substituent group Z is not particularly limited, but an alkenyl group having 2 to 20 carbon atoms is preferable, an alkenyl group having 2 to 12 carbon atoms is more preferable, and an alkenyl group having 2 to 8 carbon atoms is further preferable. ..
Examples of the alkenyl group which may have a substituent contained in the substituent group Z include a vinyl group, an allyl group, a 2-butenyl group, a 1-pentenyl group, and a 4-pentenyl group.
　置換基群Ｚに含まれるアルキニル基は、特に制限されないが、炭素数２～２０のアルキニル基が好ましく、炭素数２～１２のアルキニル基がより好ましく、炭素数２～８のアルキニル基が更に好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアルキニル基としては、例えば、エチニル基、プロパルギル基、１－ペンチニル基、トリメチルシリルエチニル基、トリエチルシリルエチニル基、トリ－ｉ－プロピルシリルエチニル基、及び、２－ｐ－プロピルフェニルエチニル基が挙げられる。 The alkynyl group contained in the substituent group Z is not particularly limited, but an alkynyl group having 2 to 20 carbon atoms is preferable, an alkynyl group having 2 to 12 carbon atoms is more preferable, and an alkynyl group having 2 to 8 carbon atoms is further preferable. ..
Examples of the alkynyl group which may have a substituent contained in the substituent group Z include an ethynyl group, a propargyl group, a 1-pentynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group and a tri-i-propylsilylethynyl group. , And 2-p-propylphenylethynyl groups.
　置換基群Ｚに含まれるアリール基は、特に制限されないが、炭素数６～２０のアリール基が好ましく、炭素数６～１２のアリール基がより好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアリール基としては、例えば、フェニル基、ナフチル基、２，４，６－トリメチルフェニル基、ｐ－（ｔ－ブチル）フェニル基、４－メチル－２，６－ジプロピルフェニル基、４－フルオロフェニル基、４－トリフルオロメチルフェニル基、ｐ－ペンチルフェニル基、３，４－ジペンチルフェニル基、ｐ－ヘプトキシフェニル基、及び、３，４－ジヘプトキシフェニル基が挙げられる。 The aryl group contained in the substituent group Z is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
Examples of the aryl group which may have a substituent contained in the substituent group Z include a phenyl group, a naphthyl group, a 2,4,6-trimethylphenyl group, a p- (t-butyl) phenyl group, and 4-. Methyl-2,6-dipropylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, and 3, Examples include 4-dihepptoxyphenyl group.
　置換基群Ｚに含まれる複素環基としては、例えば、環を構成する原子数が３個以上であり、環を構成する原子として、少なくとも１個以上のヘテロ原子と、１～３０個の炭素原子とを含む複素環基が挙げられる。また、複素環基は、芳香族複素環基（ヘテロアリール基）、及び、脂肪族複素環基を含む。
　環を構成するヘテロ原子としては、例えば、窒素原子、酸素原子、及び、硫黄原子が挙げられ、その数は、特に制限されないが、例えば、１～２個である。環を構成する炭素原子の数は、３～２０個が好ましく、５～１２個がより好ましい。
　複素環基としては、５員環、もしくは、６員環、又は、これらの縮合環の基が好ましい。
　置換基群Ｚに含まれる複素環基としては、例えば、チエニル基、チアゾリル基、イミダゾリル基、ピリジル基、ピリミジニル基、キノリル基、フラニル基、セレノフェニル基、ピペリジル基、モルホリノ基、ベンゾオキサゾリル基、ベンズイミダゾリル基、ベンズチアゾリル基、２－ヘキシルフラニル基、及び、ピラニル基が挙げられる。 The heterocyclic group contained in the substituent group Z includes, for example, three or more atoms constituting the ring, and at least one heteroatom and 1 to 30 carbon atoms as the atoms constituting the ring. Examples include heterocyclic groups containing atoms. Further, the heterocyclic group includes an aromatic heterocyclic group (heteroaryl group) and an aliphatic heterocyclic group.
Examples of the hetero atom constituting the ring include a nitrogen atom, an oxygen atom, and a sulfur atom, and the number thereof is not particularly limited, but is, for example, one or two. The number of carbon atoms constituting the ring is preferably 3 to 20, more preferably 5 to 12.
As the heterocyclic group, a 5-membered ring, a 6-membered ring, or a group of these fused rings is preferable.
Examples of the heterocyclic group contained in the substituent group Z include a thienyl group, a thiazolyl group, an imidazolyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, a furanyl group, a selenophyl group, a piperidyl group, a morpholino group and a benzoxazolyl. Examples thereof include a group, a benzimidazolyl group, a benzthiazolyl group, a 2-hexylfuranyl group, and a pyranyl group.
　置換基群Ｚに含まれる置換基を有してもよいシリル基は、特に制限されないが、置換基としてアルキル基及びアリール基から選択される基を有し、炭素数が３～４０（より好ましくは３～３０、更に好ましくは３～２４）であるシリル基が好ましい。
　置換基群Ｚに含まれる置換基を有してもよいシリル基としては、例えば、トリメチルシリル基、トリフェニルシリル基、及び、ジメチルフェニルシリル基が挙げられる。 The silyl group which may have a substituent contained in the substituent group Z is not particularly limited, but has a group selected from an alkyl group and an aryl group as the substituent and has 3 to 40 carbon atoms (more preferably). Is 3 to 30, more preferably 3 to 24), and a silyl group is preferable.
Examples of the silyl group which may have a substituent contained in the substituent group Z include a trimethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group.
　置換基群Ｚに含まれるアルコキシ基としては、特に制限されないが、炭素数１～２０のアルコキシ基が好ましく、炭素数１～１２のアルコキシ基がより好ましく、炭素数１～８のアルコキシ基が更に好ましい。
　置換基群Ｚに含まれるアルコキシ基としては、例えば、メトキシ基、エトキシ基、及び、ブトキシ基が挙げられる。 The alkoxy group contained in the substituent group Z is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 12 carbon atoms is more preferable, and an alkoxy group having 1 to 8 carbon atoms is further preferable. preferable.
Examples of the alkoxy group contained in the substituent group Z include a methoxy group, an ethoxy group, and a butoxy group.
　置換基群Ｚに含まれる置換基を有してもよいアミノ基としては、特に制限されないが、アミノ基、又は、置換基としてアルキル基及びアリール基から選択される基を有し、炭素数が１～２０（より好ましくは１～１０、更に好ましくは１～６）であるアミノ基が好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアミノ基としては、例えば、アミノ基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基、及び、アニリノ基が挙げられる。 The amino group which may have a substituent contained in the substituent group Z is not particularly limited, but has an amino group or a group selected from an alkyl group and an aryl group as a substituent and has a carbon number of carbons. Amino groups of 1 to 20 (more preferably 1 to 10, still more preferably 1 to 6) are preferred.
Examples of the amino group which may have a substituent contained in the substituent group Z include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, and an anilino group.
　置換基群Ｚに含まれるアリールオキシ基は、特に制限されないが、炭素数６～２０のアリールオキシ基が好ましく、炭素数６～１６のアリールオキシ基がより好ましく、炭素数６～１２のアリールオキシ基が更に好ましい。
　置換基群Ｚに含まれるアリールオキシ基としては、例えば、フェニルオキシ基、及び、２－ナフチルオキシが挙げられる。 The aryloxy group contained in the substituent group Z is not particularly limited, but an aryloxy group having 6 to 20 carbon atoms is preferable, an aryloxy group having 6 to 16 carbon atoms is more preferable, and an aryloxy group having 6 to 12 carbon atoms is more preferable. Groups are even more preferred.
Examples of the aryloxy group contained in the substituent group Z include a phenyloxy group and 2-naphthyloxy.
　置換基群Ｚに含まれるアシル基は、特に制限されないが、炭素数１～２０のアシル基が好ましく、炭素数１～１６のアシル基がより好ましく、炭素数１～１２のアシル基が更に好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアシル基としては、例えば、アセチル基、ヘキサノイル基、ベンゾイル基、ホルミル基、及び、ピバロイル基が挙げられる。 The acyl group contained in the substituent group Z is not particularly limited, but an acyl group having 1 to 20 carbon atoms is preferable, an acyl group having 1 to 16 carbon atoms is more preferable, and an acyl group having 1 to 12 carbon atoms is further preferable. ..
Examples of the acyl group which may have a substituent contained in the substituent group Z include an acetyl group, a hexanoyl group, a benzoyl group, a formyl group, and a pivaloyl group.
　置換基群Ｚに含まれるアルコキシカルボニル基は、特に制限されないが、炭素数２～２０のアルコキシカルボニル基が好ましく、炭素数２～１６のアルコキシカルボニル基がより好ましく、炭素数２～１２のアルコキシカルボニル基が更に好ましく、メトキシカルボニル基、又は、エトキシカルボニル基が特に好ましい。
　置換基群Ｚに含まれるアリールオキシカルボニル基は、特に制限されないが、炭素数７～２０のアリールオキシカルボニル基が好ましく、炭素数７～１６のアリールオキシカルボニル基がより好ましく、炭素数７～１０のアリールオキシカルボニル基が更に好ましく、フェニルオキシカルボニル基が特に好ましい。 The alkoxycarbonyl group contained in the substituent group Z is not particularly limited, but an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable, an alkoxycarbonyl group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonyl group having 2 to 12 carbon atoms is more preferable. The group is more preferable, and the methoxycarbonyl group or the ethoxycarbonyl group is particularly preferable.
The aryloxycarbonyl group contained in the substituent group Z is not particularly limited, but an aryloxycarbonyl group having 7 to 20 carbon atoms is preferable, an aryloxycarbonyl group having 7 to 16 carbon atoms is more preferable, and an aryloxycarbonyl group having 7 to 10 carbon atoms is more preferable. The aryloxycarbonyl group of the above is more preferable, and the phenyloxycarbonyl group is particularly preferable.
　置換基群Ｚに含まれるアシルオキシ基は、特に制限されないが、炭素数２～２０のアシルオキシ基が好ましく、炭素数２～１６のアシルオキシ基がより好ましく、炭素数２～１０のアシルオキシ基が更に好ましい。
　置換基群Ｚに含まれる置換基を有してもよいアシルオキシ基としては、例えば、アセトキシ基、ベンゾイルオキシ基、及び、（メタ）アクリロイルオキシ基が挙げられる。 The acyloxy group contained in the substituent group Z is not particularly limited, but an acyloxy group having 2 to 20 carbon atoms is preferable, an acyloxy group having 2 to 16 carbon atoms is more preferable, and an acyloxy group having 2 to 10 carbon atoms is further preferable. ..
Examples of the acyloxy group which may have a substituent contained in the substituent group Z include an acetoxy group, a benzoyloxy group, and a (meth) acryloyloxy group.
　置換基群Ｚに含まれるアシルアミノ基は、特に制限されないが、炭素数２～２０のアシルアミノ基が好ましく、炭素数２～１６のアシルアミノ基がより好ましく、炭素数２～１０のアシルアミノ基が更に好ましい。
　置換基群Ｚに含まれるアシルアミノ基としては、例えば、アセチルアミノ基、及び、ベンゾイルアミノ基が挙げられる。 The acylamino group contained in the substituent group Z is not particularly limited, but an acylamino group having 2 to 20 carbon atoms is preferable, an acylamino group having 2 to 16 carbon atoms is more preferable, and an acylamino group having 2 to 10 carbon atoms is further preferable. ..
Examples of the acylamino group contained in the substituent group Z include an acetylamino group and a benzoylamino group.
　置換基群Ｚに含まれるアミノカルボニルアミノ基は、特に制限されないが、炭素数２～２０のアミノカルボニルアミノ基が好ましく、炭素数２～１６のアミノカルボニルアミノ基がより好ましく、炭素数２～１２のアミノカルボニルアミノ基が更に好ましく、ウレイド基が特に好ましい。 The aminocarbonylamino group contained in the substituent group Z is not particularly limited, but an aminocarbonylamino group having 2 to 20 carbon atoms is preferable, an aminocarbonylamino group having 2 to 16 carbon atoms is more preferable, and an aminocarbonylamino group having 2 to 12 carbon atoms is more preferable. Aminocarbonylamino groups are more preferred, and ureido groups are particularly preferred.
　置換基群Ｚに含まれるアルコキシカルボニルアミノ基は、特に制限されないが、炭素数２～２０のアルコキシカルボニルアミノ基が好ましく、炭素数２～１６のアルコキシカルボニルアミノ基がより好ましく、炭素数２～１２のアルコキシカルボニルアミノ基が更に好ましく、メトキシカルボニルアミノ基が特に好ましい。
　置換基群Ｚに含まれるアリールオキシカルボニルアミノ基は、特に制限されないが、炭素数７～２０のアリールオキシカルボニルアミノ基が好ましく、炭素数７～１６のアリールオキシカルボニルアミノ基がより好ましく、炭素数７～１２のアリールオキシカルボニルアミノ基が更に好ましく、フェニルオキシカルボニルアミノ基が特に好ましい。 The alkoxycarbonylamino group contained in the substituent group Z is not particularly limited, but an alkoxycarbonylamino group having 2 to 20 carbon atoms is preferable, an alkoxycarbonylamino group having 2 to 16 carbon atoms is more preferable, and an alkoxycarbonylamino group having 2 to 12 carbon atoms is more preferable. The alkoxycarbonylamino group of the above is more preferable, and the methoxycarbonylamino group is particularly preferable.
The aryloxycarbonylamino group contained in the substituent group Z is not particularly limited, but an aryloxycarbonylamino group having 7 to 20 carbon atoms is preferable, an aryloxycarbonylamino group having 7 to 16 carbon atoms is more preferable, and an aryloxycarbonylamino group having 7 to 16 carbon atoms is more preferable. 7-12 aryloxycarbonylamino groups are more preferred, and phenyloxycarbonylamino groups are particularly preferred.
　置換基群Ｚに含まれるアルキルチオ基は、特に制限されないが、炭素数１～２０のアルキルチオ基が好ましく、炭素数１～１６のアルキルチオ基がより好ましく、炭素数１～１２のアルキルチオ基が更に好ましい。置換基群Ｚに含まれるアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、及び、オクチルチオ基が挙げられる。
　置換基群Ｚに含まれるアリールチオ基は、特に制限されないが、炭素数６～２０のアリールチオ基が好ましく、炭素数６～１６のアリールチオ基がより好ましく、炭素数６～１２のアリールチオ基が更に好ましく、フェニルチオ基が特に好ましい。 The alkylthio group contained in the substituent group Z is not particularly limited, but an alkylthio group having 1 to 20 carbon atoms is preferable, an alkylthio group having 1 to 16 carbon atoms is more preferable, and an alkylthio group having 1 to 12 carbon atoms is further preferable. .. Examples of the alkylthio group contained in the substituent group Z include a methylthio group, an ethylthio group, and an octylthio group.
The arylthio group contained in the substituent group Z is not particularly limited, but an arylthio group having 6 to 20 carbon atoms is preferable, an arylthio group having 6 to 16 carbon atoms is more preferable, and an arylthio group having 6 to 12 carbon atoms is further preferable. , Phenylthio groups are particularly preferred.
　上述の、置換基群Ｚから選択される基は、更に置換基を有していてもよい。このような置換基としては、置換基群Ｚから選択される基が挙げられる。
　更に置換基を有する基（組み合わせてなる基ともいう）において、更に有していてもよい置換基数は、特に限定されないが、例えば、１～６個が好ましく、１～３個がより好ましい。
　組み合わせてなる基としては、特に限定されず、例えば、上記の、置換基群Ｚから選択される基として好ましい上記各基を、置換基群Ｚから選択される他の基で置換した基が挙げられる。具体的には、ハロゲン原子、アルキル基、アリール基、複素環基（ヘテロアリール基）、アルコキシ基（ヒドロキシアルコキシ基、ハロゲン化アルコキシ基、ヘテロアリールアルコキシ基を含む）、アミノ基、アシルオキシ基、ヒドロキシ基、スルファト基、及び、ホスホノ基からなる群より選択される基を置換基として有するアルキル基、ハロゲン化アリール基若しくは（フッ化）アルキルアリール基、又は、シリル基を置換基として有するアルキニル基等が挙げられる。
　組み合わせてなる基としては、上記の中でも、ハロゲン原子を置換基として有するアルキル基（ハロゲン化アルキル基）又はアリール基を置換基として有するアルキル基が好ましく、フッ素原子を置換基として有するアルキル基（フッ化アルキル基）、又は、アリール基を置換基として有するアルキル基がより好ましく、アリール基を置換基として有するアルキル基が更に好ましい。 The group selected from the substituent group Z described above may further have a substituent. Examples of such a substituent include a group selected from the substituent group Z.
Further, the number of substituents having a substituent (also referred to as a combined group) is not particularly limited, but for example, 1 to 6 is preferable, and 1 to 3 is more preferable.
The group to be combined is not particularly limited, and examples thereof include the above-mentioned groups in which each of the above-mentioned groups preferable as the group selected from the substituent group Z is substituted with another group selected from the substituent group Z. Be done. Specifically, halogen atom, alkyl group, aryl group, heterocyclic group (heteroaryl group), alkoxy group (including hydroxyalkoxy group, halogenated alkoxy group, heteroarylalkoxy group), amino group, acyloxy group, hydroxy An alkyl group having a group selected from the group consisting of a group, a sulfato group, and a phosphono group as a substituent, an aryl halide group or a (fluorinated) alkylaryl group, an alkynyl group having a silyl group as a substituent, etc. Can be mentioned.
As the group to be combined, among the above, an alkyl group having a halogen atom as a substituent (alkyl halide group) or an alkyl group having an aryl group as a substituent is preferable, and an alkyl group having a fluorine atom as a substituent (huh). Alkyl compound group) or an alkyl group having an aryl group as a substituent is more preferable, and an alkyl group having an aryl group as a substituent is further preferable.
〔用途〕
　本発明の化合物は、例えば、電流量又は電圧量を制御する有機薄膜トランジスタ、光エネルギーを電力に変換する有機光電変換素子（例えば、光センサ用途の固体撮像素子、及び、エネルギー変換用途の太陽電池）、ＯＬＥＤ（有機発光ダイオード）、フォトトランジスタ、ＯＬＥＴ（有機発光トランジスタ）、熱エネルギーを電力に変換する有機熱電変換素子、ガスセンサ、有機整流素子、有機インバータ、並びに、情報記録素子に使用される。 [Use]
The compound of the present invention is, for example, an organic thin film that controls the amount of current or voltage, an organic photoelectric conversion element that converts light energy into electric power (for example, a solid-state imaging device for optical sensors, and a solar cell for energy conversion). , OLED (organic light emitting diode), phototransistor, OLET (organic light emitting transistor), organic thermoelectric conversion element that converts heat energy into electric power, gas sensor, organic rectifying element, organic inverter, and information recording element.
［膜］
　本発明の膜は、上述した本発明の化合物を含有する膜（有機半導体膜）である。 [film]
The film of the present invention is a film (organic semiconductor film) containing the above-mentioned compound of the present invention.
〔化合物〕
　上述のとおり、本発明の膜は上述した本発明の化合物を含有する。
　本発明の膜は、単分子膜であっても、積層膜であってもよい。 〔Compound〕
As described above, the membrane of the present invention contains the above-mentioned compound of the present invention.
The film of the present invention may be a monolayer film or a laminated film.
　本発明の膜中の本発明の化合物の含有量は特に制限されないが、本発明の効果等がより優れる理由から、１０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、５０質量％以上であることがさらに好ましく、９０質量％以上であることが特に好ましい。上限は特に制限されず、１００質量％である。 The content of the compound of the present invention in the film of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, for the reason that the effect of the present invention is more excellent. , 50% by mass or more, and particularly preferably 90% by mass or more. The upper limit is not particularly limited and is 100% by mass.
　本発明の膜が本発明の化合物以外の成分を含有する場合、本発明の膜中の本発明の化合物の含有量の上限は、本発明の効果等がより優れる理由から、９０質量％以下であることが好ましく、８０質量％以下であることがより好ましい。 When the film of the present invention contains a component other than the compound of the present invention, the upper limit of the content of the compound of the present invention in the film of the present invention is 90% by mass or less because the effect of the present invention is more excellent. It is preferably present, and more preferably 80% by mass or less.
〔任意成分〕
　本発明の膜は、上述した本発明の化合物以外の成分（任意成分）を含有していてもよい。 [Arbitrary component]
The film of the present invention may contain a component (arbitrary component) other than the above-mentioned compound of the present invention.
＜バインダーポリマー＞
　本発明の膜は、バインダーポリマーを含有していてもよい。バインダーポリマーを含有することで膜質が向上する場合がある。
　本発明の膜において、本発明の化合物及びバインダーポリマーの含有状態は特に制限されないが、キャリア移動度の点で、膜厚方向に沿って、本発明の化合物とバインダーポリマーとが互いに相分離していることが好ましい。 <Binder polymer>
The film of the present invention may contain a binder polymer. The film quality may be improved by containing the binder polymer.
In the film of the present invention, the content of the compound of the present invention and the binder polymer is not particularly limited, but the compound of the present invention and the binder polymer are phase-separated from each other along the film thickness direction in terms of carrier mobility. It is preferable to have.
　バインダーポリマーの種類は、特に制限されず、公知のバインダーポリマーを用いることができる。バインダーポリマーとしては、例えば、ポリスチレン、ポリ（α－メチルスチレン）、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリイミド、ポリウレタン、ポリシロキサン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース、ポリエチレン、及び、ポリプロピレンを含む絶縁性ポリマー、並びに、これらの共重合体が挙げられる。
　これら以外にも、例えば、エチレン－プロピレンゴム、アクリロニトリル－ブタジエンゴム、水素化されたニトリルゴム、フッ素ゴム、パーフルオロエラストマー、テトラフルオロエチレンプロピレン共重合体、エチレン－プロピレン－ジエン共重合体、スチレン－ブタジエンゴム、ポリクロロプレン、ポリネオプレン、ブチルゴム、メチルフェニルシリコーン樹脂、メチルフェニルビニルシリコーン樹脂、メチルビニルシリコーン樹脂、フルオロシリコーン樹脂、アクリルゴム、エチレンアクリルゴム、クロロスルホン化ポリエチレン、クロロポリエチレン、エピクロロヒドリン共重合体、ポリイソプレン－天然ゴム共重合体、ポリイソプレンゴム、スチレン－イソプレンブロック共重合体、ポリエステルウレタン共重合体、ポリエーテルウレタン共重合体、ポリエーテルエステル熱可塑性エラストマー及びポリブタジエンゴムを含むゴム、並びに、熱可塑性エラストマー重合体が挙げられる。
　更には、例えば、ポリビニルカルバゾール、及び、ポリシランを含む光伝導性ポリマー、ポリチオフェン、ポリピロール、ポリアニリン、及び、ポリパラフェニレンビニレンを含む導電性ポリマー、並びに、Ｃｈｅｍｉｓｔｒｙ　ｏｆ　Ｍａｔｅｒｉａｌｓ，２０１４，２６，６４７．に記載の半導体ポリマーが挙げられる。 The type of the binder polymer is not particularly limited, and a known binder polymer can be used. Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, and. Insulating polymers containing polypropylene and copolymers thereof are mentioned.
In addition to these, for example, ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroepolymer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene- Butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, methylphenyl vinyl silicone resin, methyl vinyl silicone resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin Rubber containing copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer, polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elastomer and polybutadiene rubber , And thermoplastic elastomer polymers.
Further, for example, polyvinylcarbazole and a photoconductive polymer containing polysilane, a conductive polymer containing polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and Chemistry of Materials, 2014, 26, 647. Examples of the semiconductor polymer described in.
　バインダーポリマーは、電荷移動度を考慮すると、極性基を含まない構造を有することが好ましい。ここで、極性基とは、炭素原子及び水素原子以外のヘテロ原子を有する官能基をいう。極性基を含まない構造を有するため、バインダーポリマーとしては、ポリスチレン、又は、ポリ（α－メチルスチレン）が好ましい。また、半導体ポリマーも好ましい。 The binder polymer preferably has a structure that does not contain a polar group in consideration of charge mobility. Here, the polar group means a functional group having a hetero atom other than a carbon atom and a hydrogen atom. Polystyrene or poly (α-methylstyrene) is preferable as the binder polymer because it has a structure containing no polar group. Also, semiconductor polymers are preferred.
　バインダーポリマーのガラス転移温度は、特に制限されず、用途に応じて適宜設定される。例えば、有機半導体膜に強固な機械的強度を付与する場合、ガラス転移温度を高くすることが好ましい。一方、有機半導体膜にフレキシビリティーを付与する場合、ガラス転移温度を低くすることが好ましい。 The glass transition temperature of the binder polymer is not particularly limited and is appropriately set according to the application. For example, when imparting strong mechanical strength to an organic semiconductor film, it is preferable to raise the glass transition temperature. On the other hand, when imparting flexibility to the organic semiconductor film, it is preferable to lower the glass transition temperature.
　バインダーポリマーは、１種単独で用いてもよいし、２種以上併用してもよい。
　バインダーポリマーの重量平均分子量は、特に制限されないが、１，０００～１，０００万が好ましく、３，０００～５００万がより好ましく、５，０００～３００万が更に好ましい。バインダーポリマーの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により求めることができる。 The binder polymer may be used alone or in combination of two or more.
The weight average molecular weight of the binder polymer is not particularly limited, but is preferably 10 to 10 million, more preferably 30 to 5 million, and even more preferably 50 to 3 million. The weight average molecular weight of the binder polymer can be determined by gel permeation chromatography (GPC).
　本発明の膜がバインダーポリマーを含有する場合の含有量は特に制限されないが、下限は、本発明の効果等がより優れる理由から、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、上限は、本発明の効果等がより優れる理由から、９０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 When the film of the present invention contains a binder polymer, the content is not particularly limited, but the lower limit is preferably 10% by mass or more, preferably 20% by mass or more, for the reason that the effect of the present invention is more excellent. It is more preferable, and the upper limit is preferably 90% by mass or less, more preferably 70% by mass or less, for the reason that the effect of the present invention is more excellent.
＜その他の任意成分＞
　バインダーポリマー以外の任意成分としては、例えば、有機半導体膜に通常用いられる添加剤が挙げられ、より具体的には、界面活性剤、酸化防止剤、結晶化制御剤、及び、結晶配向制御剤が挙げられる。界面活性剤及び酸化防止剤としては、特開２０１５－１９５３６２号公報の段落０１３６及び０１３７が援用でき、これらの内容は本明細書に組み込まれる。 <Other optional ingredients>
Examples of optional components other than the binder polymer include additives usually used for organic semiconductor membranes, and more specifically, surfactants, antioxidants, crystallization control agents, and crystal orientation control agents. Can be mentioned. As the surfactant and the antioxidant, paragraphs 0136 and 0137 of JP2015-195362A can be incorporated, and the contents thereof are incorporated in the present specification.
　本発明の膜がバインダーポリマー以外の任意成分を含有する場合、その含有量は、本発明の効果等がより優れる理由から、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下がさらに好ましい。 When the film of the present invention contains an arbitrary component other than the binder polymer, the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass because the effects of the present invention are more excellent. The following is more preferable.
〔膜厚〕
　本発明の膜の膜厚は特に制限されないが、本発明の効果等がより優れる理由から、５～５００ｎｍが好ましく、５～２００ｎｍがより好ましい。 [Film thickness]
The film thickness of the film of the present invention is not particularly limited, but 5 to 500 nm is preferable, and 5 to 200 nm is more preferable for the reason that the effect of the present invention is more excellent.
　なお、本発明の膜の用途は、有機ＴＦＴ用の有機半導体膜に制限されず、上述した各有機半導体デバイスが備える有機半導体膜として使用できる。 The application of the film of the present invention is not limited to the organic semiconductor film for organic TFTs, and can be used as the organic semiconductor film included in each of the above-mentioned organic semiconductor devices.
〔製造方法〕
　本発明の膜の製造方法は特に制限されないが、例えば、上述した本発明の化合物を含有する組成物（有機半導体組成物）を調製してから基板等に塗布する方法等が挙げられる。 〔Production method〕
The method for producing the film of the present invention is not particularly limited, and examples thereof include a method of preparing a composition (organic semiconductor composition) containing the compound of the present invention described above and then applying the composition to a substrate or the like.
＜組成物＞
　本発明の組成物は、上述した本発明の化合物を含有する組成物（有機半導体組成物）である。
　本発明の組成物は、上述した本発明の化合物と、少なくとも１種類の溶剤とを含有する組成物（有機半導体組成物）であることが好ましい。 <Composition>
The composition of the present invention is a composition (organic semiconductor composition) containing the above-mentioned compound of the present invention.
The composition of the present invention is preferably a composition (organic semiconductor composition) containing the above-mentioned compound of the present invention and at least one kind of solvent.
（任意成分）
　本発明の組成物は、上述した本発明の化合物以外の成分を含有していてもよい。
　本発明の組成物は、その塗布性を向上させる観点から、溶媒を含有するのが好ましい。
　このような溶媒としては、上述の化合物を溶解又は分散させるものであれば特に制限されず、無機溶媒又は有機溶媒が挙げられ、有機溶媒が好ましい。溶媒は、１種単独で使用してもよいし、２種以上を併用してもよい。 (Arbitrary ingredient)
The composition of the present invention may contain components other than the above-mentioned compounds of the present invention.
The composition of the present invention preferably contains a solvent from the viewpoint of improving the coatability.
Such a solvent is not particularly limited as long as it dissolves or disperses the above-mentioned compound, and examples thereof include an inorganic solvent and an organic solvent, and an organic solvent is preferable. The solvent may be used alone or in combination of two or more.
　有機溶媒としては、特に制限されないが、ヘキサン、オクタン、デカン、トルエン、キシレン、メシチレン、エチルベンゼン、アミルベンゼン、デカリン、１－メチルナフタレン、１－エチルナフタレン、１，６－ジメチルナフタレン、及び、テトラリンを含む炭化水素溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、アセトフェノン、プロピオフェノン、イソホロン、及び、ブチロフェノンを含むケトン溶媒、ジクロロメタン、クロロホルム、テトラクロロメタン、ジクロロエタン、トリクロロエタン、テトラクロロエタン、クロロベンゼン、１，２－ジクロロベンゼン、１，２，４－トリクロロベンゼン、クロロトルエン、及び、１－フルオロナフタレンを含むハロゲン化炭化水素溶媒、ピリジン、ピコリン、キノリン、チオフェン、３－ブチルチオフェン、及び、チエノ［２，３－ｂ］チオフェンを含む複素環溶媒、２－クロロチオフェン、３－クロロチオフェン、２，５－ジクロロチオフェン、３，４－ジクロロチオフェン、２－ブロモチオフェン、３－ブロモチオフェン、２，３－ジブロモチオフェン、２，４－ジブロモチオフェン、２，５－ジブロモチオフェン、３，４－ジブロモチオフェン、及び、３，４－ジクロロ－１，２，５－チアジアゾールを含むハロゲン化複素環溶媒、酢酸エチル、酢酸ブチル、酢酸アミル、酢酸－２－エチルヘキシル、γ－ブチロラクトン、及び、酢酸フェニルを含むエステル溶媒、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、及び、エチレングリコールを含むアルコール溶媒、１－メトキシ－２－プロパノール、２－メトキシエタノール、２－イソプロポキシエタノール、及び、２－ブトキシエタノールを含むアルコキシアルコール溶媒、ジブチルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン、アニソール、エトキシベンゼン、プロポキシベンゼン、イソプロポキシベンゼン、ブトキシベンゼン、２－メチルアニソール、３－メチルアニソール、４－メチルアニソール、４－エチルアニソール、ジメチルアニソール（２，３－、２，４－、２，５－、２，６－、３，４－、３，５－及び３，６－のいずれか）、及び、１，４－ベンゾジオキサンを含むエーテル溶媒、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、１－メチル－２－ピロリドン、１－メチル－２－イミダゾリジノン、及び、１，３－ジメチル－２－イミダゾリジノンを含むアミド又はイミド溶媒、ジメチルスルホキシドを含むスルホキシド溶媒、リン酸トリメチルを含むリン酸エステル溶媒、アセトニトリル、及び、ベンゾニトリルを含むニトリル溶媒、並びに、ニトロメタン、及び、ニトロベンゼンを含むニトロ溶媒が挙げられる。 The organic solvent is not particularly limited, but hexane, octane, decane, toluene, xylene, mecitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetraline can be used. Carbone solvent containing hydrocarbon solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, isophorone, and ketone solvent containing butyrophenone, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1, Halogenized hydrocarbon solvents containing 2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, and 1-fluoronaphthalene, pyridine, picolin, quinoline, thiophene, 3-butylthiophene, and thieno [2. 3-b] Heterocyclic solvent containing thiophene, 2-chlorothiophene, 3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromo Halogened heterocyclic solvent containing thiophene, 2,4-dibromothiophene, 2,5-dibromothiophene, 3,4-dibromothiophene, and 3,4-dichloro-1,2,5-thiazazole, ethyl acetate, acetate. Estel solvents containing butyl, amyl acetate, -2-ethylhexyl acetate, γ-butyrolactone, and phenyl acetate, methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol Alcohol solvent containing 1-methoxy-2-propanol, 2-methoxyethanol, 2-isopropoxyethanol, and alkoxy alcohol solvent containing 2-butoxyethanol, dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane, anisole, ethoxybenzene. , Propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 4-ethylanisole, dimethylanisole (2,3-, 2,4-, 2,5-, 2) , 6-, 3,4-, 3,5- and 3,6-), and ether solvent containing 1,4-benzodioxane, N, N-dimethylformamide, N, N-dime An amide or imide solvent containing tylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and 1,3-dimethyl-2-imidazolidinone, a sulfoxide solvent containing dimethyl sulfoxide, and a phosphoric acid. Examples thereof include a phosphate ester solvent containing trimethyl, a nitrile solvent containing acetonitrile and benzonitrile, and a nitro solvent containing nitromethane and nitrobenzene.
　中でも、炭化水素溶媒、ケトン溶媒、ハロゲン化炭化水素溶媒、複素環溶媒、ハロゲン化複素環溶媒、エステル溶媒、アルコール溶媒、アルコキシアルコール溶媒、エーテル溶媒、又は、ニトリル溶媒が好ましく、トルエン、キシレン、メシチレン、アミルベンゼン、テトラリン、アセトフェノン、プロピオフェノン、ブチロフェノン、ジクロロベンゼン、アニソール、エトキシベンゼン、プロポキシベンゼン、イソプロポキシベンゼン、ブトキシベンゼン、２－メチルアニソール、３－メチルアニソール、４－メチルアニソール、１－フルオロナフタレン、３－クロロチオフェン、２，５－ジブロモチオフェン、酢酸エチル、酢酸ブチル、プロパノール、ブタノール、１－メトキシ－２－プロパノール、２－メトキシエタノール、２－ブトキシエタノール、又は、ベンゾニトリルがより好ましく、トルエン、キシレン、テトラリン、アセトフェノン、プロピオフェノン、ブチロフェノン、アニソール、エトキシベンゼン、プロポキシベンゼン、ブトキシベンゼン、２－メチルアニソール、３－メチルアニソール、４－メチルアニソール、１－フルオロナフタレン、３－クロロチオフェン、２，５－ジブロモチオフェン、酢酸ブチル、プロパノール、ブタノール、又は、２－ブトキシエタノールが更に好ましい。 Among them, a hydrocarbon solvent, a ketone solvent, a halogenated hydrocarbon solvent, a heterocyclic solvent, a halogenated heterocyclic solvent, an ester solvent, an alcohol solvent, an alkoxyalcohol solvent, an ether solvent, or a nitrile solvent is preferable, and toluene, xylene, and mesitylene are preferable. , Amilbenzene, tetraline, acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoro Naphthalene, 3-chlorothiophene, 2,5-dibromothiophene, ethyl acetate, butyl acetate, propanol, butanol, 1-methoxy-2-propanol, 2-methoxyethanol, 2-butoxyethanol, or benzonitrile are more preferred. Toluene, xylene, tetraline, acetophenone, propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 1-fluoronaphthalene, 3-chlorothiophene, 2,5-Dibromothiophene, butyl acetate, propanol, butanol, or 2-butoxyethanol are more preferred.
　有機半導体組成物に含有される溶媒としては、膜質の点、及び、上述の化合物の結晶を大きくできる点で、沸点が１００℃以上の溶媒が好ましい。
　沸点が１００℃以上の溶媒としては、トルエン、キシレン、メシチレン、テトラリン、アセトフェノン、プロピオフェノン、ブチロフェノン、ジクロロベンゼン、アニソール、エトキシベンゼン、プロポキシベンゼン、イソプロポキシベンゼン、ブトキシベンゼン、２－メチルアニソール、３－メチルアニソール、４－メチルアニソール、１－メトキシ－２－プロパノール、２－メトキシエタノール、２－ブトキシエタノール、及び、ベンゾニトリルが挙げられる。中でも、トルエン、キシレン、テトラリン、アセトフェノン、プロピオフェノン、ブチロフェノン、アニソール、エトキシベンゼン、プロポキシベンゼン、ブトキシベンゼン、２－メチルアニソール、３－メチルアニソール、４－メチルアニソール、又は、２－ブトキシエタノールがより好ましい。
　また、環境負荷や人への毒性の点で、沸点が１００℃以上の溶媒としては、非ハロゲン溶媒（分子中にハロゲン原子を有しない溶媒）が好ましい。 As the solvent contained in the organic semiconductor composition, a solvent having a boiling point of 100 ° C. or higher is preferable in terms of film quality and the ability to enlarge the crystals of the above-mentioned compounds.
Solvents having a boiling point of 100 ° C. or higher include toluene, xylene, mesitylene, tetraline, acetophenone, propiophenone, butyrophenone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3 -Methylanisole, 4-methylanisole, 1-methoxy-2-propanol, 2-methoxyethanol, 2-butoxyethanol, and benzonitrile can be mentioned. Among them, toluene, xylene, tetraline, acetophenone, propiophenone, butyrophenone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, or 2-butoxyethanol are more suitable. preferable.
Further, from the viewpoint of environmental load and toxicity to humans, a non-halogen solvent (solvent having no halogen atom in the molecule) is preferable as the solvent having a boiling point of 100 ° C. or higher.
　本発明の組成物が溶媒を含有する場合、溶媒の含有量は、本発明の組成物の全質量に対して、９０～９９．９質量％が好ましく、９５～９９．９質量％がより好ましく、９６～９９．５質量％が更に好ましい。 When the composition of the present invention contains a solvent, the content of the solvent is preferably 90 to 99.9% by mass, more preferably 95 to 99.9% by mass, based on the total mass of the composition of the present invention. , 96-99.5% by mass, more preferably.
　溶媒以外の任意成分の具体例は、上述した本発明の膜における任意成分と同じである。 Specific examples of the optional components other than the solvent are the same as those of the optional components in the membrane of the present invention described above.
　本発明の組成物の粘度は、印刷適性の点で、１０ｍＰａ・ｓ以上が好ましい。 The viscosity of the composition of the present invention is preferably 10 mPa · s or more in terms of printability.
（調製方法）
　本発明の組成物の調製方法は、特に制限されず、通常の調製方法を採用できる。例えば、溶媒に本発明の化合物等を混合する方法等が挙げられる。
　必要により、各成分の攪拌中又は攪拌後に加熱することもできる。加熱温度は、特に制限されず、例えば、４０～１５０℃の範囲内で決定される。溶媒を用いる場合は、上記の範囲内であって溶媒の沸点未満の温度に決定される。 (Preparation method)
The method for preparing the composition of the present invention is not particularly limited, and a usual preparation method can be adopted. For example, a method of mixing the compound of the present invention with a solvent can be mentioned.
If necessary, each component can be heated during or after stirring. The heating temperature is not particularly limited and is determined, for example, in the range of 40 to 150 ° C. When a solvent is used, the temperature is determined to be within the above range and below the boiling point of the solvent.
［構造体］
　本発明の構造体は、基板と、上述した本発明の膜（有機半導体膜）とを備える構造体である。基板については、後述する有機薄膜トランジスタにおける基板と同じである。 [Structure]
The structure of the present invention is a structure including a substrate and the film (organic semiconductor film) of the present invention described above. The substrate is the same as that of the organic thin film transistor described later.
［電子デバイス］
　本発明の電子デバイスは、上述した本発明の構造体を含む電子デバイスである。 [Electronic device]
The electronic device of the present invention is an electronic device including the above-described structure of the present invention.
［有機薄膜トランジスタ］
　本発明の有機薄膜トランジスタは、有機薄膜トランジスタ（有機ＴＦＴ）である上述した本発明の電子デバイスである。 [Organic thin film transistor]
The organic thin film transistor of the present invention is the above-mentioned electronic device of the present invention, which is an organic thin film transistor (organic TFT).
　有機ＴＦＴは、上述した有機半導体膜を備える。これにより、有機ＴＦＴは、高いキャリア移動度を示し、しかも大気下においても経時による低下を効果的に抑えられ、安定駆動する。大気下での周辺温度及び湿度は、有機ＴＦＴの使用環境での温度及び湿度であれば特に制限されず、例えば温度としては室温（２０℃）、湿度としては１０～９０ＲＨ％が挙げられる。
　有機ＴＦＴは、有機電界効果トランジスタ（ＦＥＴ：Field Effect Transistor）として用いられることが好ましく、ゲート－チャンネル間が絶縁されている絶縁ゲート型ＦＥＴとして用いられることがより好ましい。
　有機ＴＦＴの厚みは、特に制限されないが、より薄いトランジスタとする場合には、例えば、有機ＴＦＴ全体の厚みを０．１～０．５μｍとすることが好ましい。 The organic TFT includes the above-mentioned organic semiconductor film. As a result, the organic TFT exhibits high carrier mobility, and is effectively suppressed from decreasing with time even in the atmosphere, and is stably driven. The ambient temperature and humidity in the atmosphere are not particularly limited as long as they are the temperature and humidity in the environment in which the organic TFT is used. For example, the temperature is room temperature (20 ° C.) and the humidity is 10 to 90 RH%.
The organic TFT is preferably used as an organic field effect transistor (FET), and more preferably used as an insulated gate type FET in which the gate and the channel are insulated.
The thickness of the organic TFT is not particularly limited, but in the case of a thinner transistor, for example, the thickness of the entire organic TFT is preferably 0.1 to 0.5 μm.
　有機ＴＦＴは、上述した有機半導体膜（有機半導体層又は半導体活性層ともいう）を有し、更に、ソース電極と、ドレイン電極と、ゲート電極と、ゲート絶縁膜とを有することができる。
　有機ＴＦＴは、基板上に、ゲート電極と、有機半導体膜と、ゲート電極及び有機半導体膜の間に設けられたゲート絶縁膜と、有機半導体膜に接して設けられ、有機半導体膜を介して連結されたソース電極及びドレイン電極とを有することが好ましい。この有機ＴＦＴにおいては、有機半導体膜とゲート絶縁膜が隣接して設けられる。
　有機ＴＦＴは、上記各層を備えていればその構造については特に制限されない。例えば、ボトムゲート－ボトムコンタクト型、トップゲート－ボトムコンタクト型、ボトムゲート－トップコンタクト型、及び、トップゲート－トップコンタクト型のいずれの構造を有してもよい。有機ＴＦＴとしては、ゲート電極が基板及び有機半導体膜の間に設けられているボトムゲート型（ボトムゲート－ボトムコンタクト型又はボトムゲート－トップコンタクト型）が好ましい。
　以下、有機ＴＦＴの一例について、図面を参照して説明する。 The organic TFT has the above-mentioned organic semiconductor film (also referred to as an organic semiconductor layer or a semiconductor active layer), and may further have a source electrode, a drain electrode, a gate electrode, and a gate insulating film.
The organic TFT is provided on the substrate in contact with the gate electrode, the organic semiconductor film, the gate insulating film provided between the gate electrode and the organic semiconductor film, and the organic semiconductor film, and is connected via the organic semiconductor film. It is preferable to have a source electrode and a drain electrode. In this organic TFT, an organic semiconductor film and a gate insulating film are provided adjacent to each other.
The structure of the organic TFT is not particularly limited as long as it includes each of the above layers. For example, it may have any structure of bottom gate-bottom contact type, top gate-bottom contact type, bottom gate-top contact type, and top gate-top contact type. As the organic TFT, a bottom gate type (bottom gate-bottom contact type or bottom gate-top contact type) in which a gate electrode is provided between the substrate and the organic semiconductor film is preferable.
Hereinafter, an example of the organic TFT will be described with reference to the drawings.
〔ボトムゲート－ボトムコンタクト型有機ＴＦＴ〕
　図１は、有機ＴＦＴの一例であるボトムゲート－ボトムコンタクト型の有機ＴＦＴ１０の構造を示す断面模式図である。
　有機ＴＦＴ１０は、図１に示すように、基板（基材）１と、ゲート電極２と、ゲート絶縁膜３と、ソース電極４Ａ及びドレイン電極４Ｂと、有機半導体膜５と、封止層６とを、この順に備える。
　以下、基板（基材）、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜、及び、封止層、並びに、それぞれの作製方法について説明する。 [Bottom Gate-Bottom Contact Type Organic TFT]
FIG. 1 is a schematic cross-sectional view showing the structure of a bottom gate-bottom contact type organic TFT 10 which is an example of an organic TFT.
As shown in FIG. 1, the organic TFT 10 includes a substrate (base material) 1, a gate electrode 2, a gate insulating film 3, a source electrode 4A, a drain electrode 4B, an organic semiconductor film 5, and a sealing layer 6. Are prepared in this order.
Hereinafter, a substrate (base material), a gate electrode, a gate insulating film, a source electrode, a drain electrode, an organic semiconductor film, a sealing layer, and a method for producing each of them will be described.
＜基板＞
　基板は、ゲート電極、ソース電極、ドレイン電極、及び、他の層を支持する役割を果たす。
　基板の種類は、特に制限されず、例えば、プラスチック基板、シリコン基板、ガラス基板、及び、セラミック基板が挙げられる。中でも、各デバイスへの適用性及びコストの観点から、ガラス基板又はプラスチック基板が好ましい。
　基板の厚みは、特に制限されない。基板の厚みの上限は、１０ｍｍ以下が好ましく、２ｍｍ以下がより好ましく、１．５ｍｍ以下が更に好ましい。基板の厚みの下限は、０．０１ｍｍ以上が好ましく、０．０５ｍｍ以上がより好ましい。 <Board>
The substrate serves to support the gate electrode, the source electrode, the drain electrode, and other layers.
The type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a silicon substrate, a glass substrate, and a ceramic substrate. Above all, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
The thickness of the substrate is not particularly limited. The upper limit of the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and further preferably 1.5 mm or less. The lower limit of the thickness of the substrate is preferably 0.01 mm or more, more preferably 0.05 mm or more.
＜ゲート電極＞
　ゲート電極は、有機ＴＦＴのゲート電極として用いられている通常の電極を特に制限されることなく適用できる。
　ゲート電極を形成する材料（電極材料）としては、特に制限されず、例えば、金、銀、アルミニウム、銅、クロム、ニッケル、コバルト、チタン、白金、マグネシウム、カルシウム、バリウム、及び、ナトリウムを含む金属、ＩｎＯ２、ＳｎＯ２、及び、インジウム錫酸化物（ＩＴＯ）を含む導電性の酸化物、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、及び、ポリジアセチレンを含む導電性高分子、シリコン、ゲルマニウム、及び、ガリウム砒素を含む半導体、並びに、フラーレン、カーボンナノチューブ、及び、グラファイトを含む炭素材料が挙げられる。中でも、上記金属が好ましく、銀、又は、アルミニウムがより好ましい。
　ゲート電極の厚みは、特に制限されないが、２０～２００ｎｍが好ましい。
　ゲート電極は、上記基板として機能するものでもよく、この場合、上記基板はなくてもよい。 <Gate electrode>
As the gate electrode, a normal electrode used as a gate electrode of an organic TFT can be applied without particular limitation.
The material (electrode material) for forming the gate electrode is not particularly limited, and is, for example, a metal containing gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, and sodium. , InO 2 , SnO 2 , and conductive oxides including indium tin oxide (ITO), polyaniline, polypyrrole, polythiophene, polyacetylene, and conductive polymers containing polydiacetylene, silicon, germanium, and gallium. Examples include semiconductors containing arsenic, and carbon materials containing fullerene, carbon nanotubes, and graphite. Among them, the above metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.
The gate electrode may function as the substrate, and in this case, the substrate may be omitted.
　ゲート電極を形成する方法は、特に制限されないが、例えば、基板上に、上述の電極材料を真空蒸着（以下単に「蒸着」ともいう）又はスパッタする方法、及び、上述の電極材料を含有する電極形成用組成物を塗布又は印刷する方法等が挙げられる。また、ゲート電極をパターニングする場合、パターニング方法としては、例えば、インクジェット印刷、スクリーン印刷、オフセット印刷、及び、凸版印刷（フレキソ印刷）を含む印刷法、フォトリソグラフィー法、並びに、マスク蒸着法が挙げられる。 The method for forming the gate electrode is not particularly limited, and for example, a method of vacuum-depositing (hereinafter, simply referred to as “vapor deposition”) or sputtering of the above-mentioned electrode material on a substrate, and an electrode containing the above-mentioned electrode material. Examples thereof include a method of applying or printing the forming composition. When patterning the gate electrode, examples of the patterning method include a printing method including inkjet printing, screen printing, offset printing, and letterpress printing (flexographic printing), a photolithography method, and a mask vapor deposition method. ..
＜ゲート絶縁膜＞
　ゲート絶縁膜は、絶縁性を有する層であれば特に制限されず、単層であってもよいし、多層であってもよい。
　ゲート絶縁膜を形成する材料としては、特に制限されず、例えば、ポリメチルメタクリレート、ポリスチレン、ポリビニルフェノール、メラミン樹脂、ポリイミド、ポリカーボネート、ポリエステル、ポリビニルアルコール、ポリ酢酸ビニル、ポリウレタン、ポリスルフォン、ポリベンゾキサゾール、ポリシルセスキオキサン、エポキシ樹脂、及び、フェノール樹脂を含むポリマー、二酸化ケイ素、酸化アルミニウム、及び、酸化チタンを含む無機酸化物、並びに、窒化ケイ素を含む窒化物が挙げられる。中でも、有機半導体膜との相性の点では上記ポリマーが好ましく、膜の均一性の点では上記無機酸化物が好ましく、二酸化ケイ素がより好ましい。
　これらの材料は、１種単独で用いてもよいし、２種以上併用してもよい。
　ゲート絶縁膜の膜厚は、特に制限されないが、１００～１０００ｎｍが好ましい。
　ゲート絶縁膜を形成する方法は、特に制限されないが、例えば、ゲート電極が形成された基板上に、上記材料を含有するゲート絶縁膜形成用組成物を塗布する方法、及び、上記材料を蒸着又はスパッタする方法が挙げられる。 <Gate insulating film>
The gate insulating film is not particularly limited as long as it is a layer having an insulating property, and may be a single layer or a multilayer.
The material for forming the gate insulating film is not particularly limited, and for example, polymethylmethacrylate, polystyrene, polyvinylphenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinylacetate, polyurethane, polysulphon, and polybenzoxa. Examples thereof include polymers containing sol, polyvinyl sesquioxane, epoxy resins and phenolic resins, silicon dioxide, aluminum oxide, inorganic oxides containing titanium oxide, and nitrides containing silicon nitride. Among them, the polymer is preferable from the viewpoint of compatibility with the organic semiconductor film, the inorganic oxide is preferable from the viewpoint of film uniformity, and silicon dioxide is more preferable.
These materials may be used alone or in combination of two or more.
The film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.
The method for forming the gate insulating film is not particularly limited, and for example, a method of applying a gate insulating film forming composition containing the above material on a substrate on which a gate electrode is formed, and a method of depositing or depositing the above material. A method of sputtering can be mentioned.
＜ソース電極及びドレイン電極＞
　有機ＴＦＴにおいて、ソース電極は、配線を通じて外部から電流が流入する電極である。また、ドレイン電極は、配線を通じて外部に電流を送り出す電極である。
　ソース電極及びドレイン電極を形成する材料は、上述したゲート電極を形成する電極材料と同じものを用いることができる。中でも、金属が好ましく、金、又は、銀がより好ましい。
　ソース電極及びドレイン電極の厚みは、特に制限されないが、それぞれ、１ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。また、ソース電極及びドレイン電極の厚みの上限は、５００ｎｍ以下が好ましく、３００ｎｍ以下がより好ましい。
　ソース電極とドレイン電極との間の間隔（ゲート長Ｌ）は、適宜に決定できるが、２００μｍ以下が好ましく、１００μｍ以下がより好ましい。また、ゲート幅Ｗは、適宜に決定できるが、５０００μｍ以下が好ましく、１０００μｍ以下がより好ましい。ゲート幅Ｗとゲート長Ｌとの比は、特に制限されないが、例えば、比Ｗ／Ｌが１０以上が好ましく、２０以上がより好ましい。
　ソース電極及びドレイン電極を形成する方法は、特に制限されないが、例えば、ゲート電極とゲート絶縁膜とが形成された基板上に、電極材料を真空蒸着又はスパッタする方法、及び、電極形成用組成物を塗布又は印刷する方法が挙げられる。ソース電極及びドレイン電極をパターニングする場合のパターニング方法は、上述したゲート電極のパターニング方法と同じである。 <Source electrode and drain electrode>
In an organic TFT, a source electrode is an electrode into which a current flows from the outside through wiring. The drain electrode is an electrode that sends an electric current to the outside through wiring.
As the material for forming the source electrode and the drain electrode, the same material as the electrode material for forming the gate electrode described above can be used. Among them, metal is preferable, and gold or silver is more preferable.
The thickness of the source electrode and the drain electrode is not particularly limited, but is preferably 1 nm or more, and more preferably 10 nm or more, respectively. The upper limit of the thickness of the source electrode and the drain electrode is preferably 500 nm or less, more preferably 300 nm or less.
The distance (gate length L) between the source electrode and the drain electrode can be appropriately determined, but is preferably 200 μm or less, more preferably 100 μm or less. The gate width W can be appropriately determined, but is preferably 5000 μm or less, and more preferably 1000 μm or less. The ratio of the gate width W to the gate length L is not particularly limited, but for example, the ratio W / L is preferably 10 or more, and more preferably 20 or more.
The method of forming the source electrode and the drain electrode is not particularly limited, and for example, a method of vacuum-depositing or sputtering an electrode material on a substrate on which a gate electrode and a gate insulating film are formed, and an electrode forming composition. Examples include a method of applying or printing. The patterning method for patterning the source electrode and the drain electrode is the same as the above-described gate electrode patterning method.
＜有機半導体膜＞
　有機半導体膜は、上述した本発明の膜である。 <Organic semiconductor film>
The organic semiconductor film is the film of the present invention described above.
＜封止層＞
　上記の有機半導体膜を備える有機ＴＦＴは大気下においても安定駆動するため、有機ＴＦＴ全体を封止し、大気（酸素ガス）及び水分のいずれかを遮断しなくてもよいが、より長期間の安定駆動を目的として、有機ＴＦＴ全体を金属製の封止缶で封止してもよく、封止剤を用いて封止層を形成してもよい。
　封止層には、有機ＴＦＴに通常用いられる封止剤（封止層形成用組成物）を用いることができる。封止剤としては、例えば、ガラス及び窒化ケイ素を含む無機材料、パリレンを含む高分子材料、並びに、低分子材料が挙げられる。
　封止層は、上記封止剤を用いて、塗布乾燥等の通常の方法により、形成できる。
　封止層の厚みは、特に制限されないが、０．２～１０μｍが好ましい。 <Encapsulation layer>
Since the organic TFT provided with the above-mentioned organic semiconductor film is stably driven even in the atmosphere, it is not necessary to seal the entire organic TFT and block either the atmosphere (oxygen gas) or water, but for a longer period of time. For the purpose of stable driving, the entire organic TFT may be sealed with a metal sealing can, or a sealing layer may be formed using a sealing agent.
As the sealing layer, a sealing agent (composition for forming a sealing layer) usually used for organic TFTs can be used. Examples of the sealing agent include an inorganic material containing glass and silicon nitride, a polymer material containing parylene, and a low molecular weight material.
The sealing layer can be formed by a usual method such as coating and drying using the above-mentioned sealing agent.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
〔ボトムゲート－トップコンタクト型有機ＴＦＴ〕
　図２は、有機ＴＦＴの一例であるボトムゲート－トップコンタクト型の有機ＴＦＴ２０の構造を示す断面模式図である。
　有機ＴＦＴ２０は、図２に示すように、基板１と、ゲート電極２と、ゲート絶縁膜３と、有機半導体膜５と、ソース電極４Ａ及びドレイン電極４Ｂと、封止層６とを、この順に備える。
　有機ＴＦＴ２０は、層構成（積層態様）が異なること以外は、有機ＴＦＴ１０と同じである。したがって、基板、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜、及び、封止層については、上述の、ボトムゲート－ボトムコンタクト型有機ＴＦＴにおけるものと同じであるので、その説明を省略する。 [Bottom Gate-Top Contact Organic TFT]
FIG. 2 is a schematic cross-sectional view showing the structure of a bottom gate-top contact type organic TFT 20 which is an example of an organic TFT.
As shown in FIG. 2, the organic TFT 20 has a substrate 1, a gate electrode 2, a gate insulating film 3, an organic semiconductor film 5, a source electrode 4A, a drain electrode 4B, and a sealing layer 6 in this order. Be prepared.
The organic TFT 20 is the same as the organic TFT 10 except that the layer structure (lamination mode) is different. Therefore, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are the same as those in the bottom gate-bottom contact type organic TFT described above. Is omitted.
〔用途〕
　本発明の有機ＴＦＴは、その用途については特に制限されず、例えば、電子ペーパー、ディスプレイデバイス、センサ、及び、電子タグに使用できる。 [Use]
The organic TFT of the present invention is not particularly limited in its use, and can be used for, for example, electronic paper, display devices, sensors, and electronic tags.
　以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
〔化合物の合成〕
　以下のとおり、比較化合物（１）～（２）及び化合物（１）～（９）を合成した。 [Compound synthesis]
Comparative compounds (1) to (2) and compounds (1) to (9) were synthesized as follows.
＜比較化合物（１）＞
　比較化合物（１）は、特許第６２１９３１４号公報の段落［０１３０］～［０１３３］に記載の方法により合成した。 <Comparative compound (1)>
Comparative compound (1) was synthesized by the method described in paragraphs [0130] to [0133] of Japanese Patent No. 6219314.
＜比較化合物（２）＞
　比較化合物（２）は、特許第４９４５７５７号公報の段落［０２２８］に記載の方法により合成した。 <Comparative compound (2)>
Comparative compound (2) was synthesized by the method described in paragraph [0228] of Japanese Patent No. 4945757.
＜化合物（１）＞
　下記スキームに従い、化合物（１）を合成した。 <Compound (1)>
Compound (1) was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（中間体（１－１））
　ベンゾ［ｂ］ベンゾ［４，５］チエノ［２，３－ｄ］チオフェン（７．０ｇ、２９．１ｍｍｏｌ）と、溶媒としてジクロロメタン（３５０ｍＬ）とを混合し、－１０℃で撹拌したところへ、塩化アルミニウム（１５．５ｇ、１１６．５ｍｍｏｌ）を添加し、－１０℃で１０分間撹拌した。反応溶液を－７８℃まで降温し撹拌したところへ、ラウロイルクロリド（７．０ｇ、３２．０ｍｍｏｌ）のジクロロメタン（５０ｍＬ）溶液を、滴下ロートを用いて滴下した。滴下後、反応溶液を－７８℃で窒素下１時間撹拌した。反応終了後、ジクロロメタンで希釈し、０℃まで昇温させ撹拌しながら、水を滴下ロートで滴下した。滴下後、水層を除去し、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をトルエンから再結晶し、濾過・乾燥させて中間体（１－１）（１２．３ｇ、収率８６％）を得た。 (Intermediate (1-1))
Benzo [b] benzo [4,5] thieno [2,3-d] thiophene (7.0 g, 29.1 mmol) and dichloromethane (350 mL) as a solvent were mixed and stirred at −10 ° C. Aluminum chloride (15.5 g, 116.5 mmol) was added and stirred at −10 ° C. for 10 minutes. A solution of lauroyl chloride (7.0 g, 32.0 mmol) in dichloromethane (50 mL) was added dropwise using a dropping funnel to the place where the reaction solution was cooled to −78 ° C. and stirred. After the dropwise addition, the reaction solution was stirred at −78 ° C. under nitrogen for 1 hour. After completion of the reaction, water was added dropwise with a dropping funnel while diluting with dichloromethane, raising the temperature to 0 ° C. and stirring. After the dropping, the aqueous layer was removed, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained crude product was recrystallized from toluene, filtered and dried to obtain an intermediate (1-1) (12.3 g, yield 86%).
（中間体（１－２））
　中間体（１－１）（５．０ｇ、１１．８ｍｍｏｌ）と、水酸化カリウム（１．９５ｇ、２９．６ｍｍｏｌ）と、ヒドラジン一水和物（３．５５ｇ、７１．０ｍｍｏｌ）と、溶媒としてジエチレングリコール（１６９ｍＬ）とを混合し、１７０℃で４時間撹拌した。反応終了後、クロロホルムで希釈し、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をクロロホルムに溶解させ、メタノールを添加することで析出した固体を濾過・乾燥させて中間体（１－２）（４．５ｇ、収率９３％）を得た。 (Intermediate (1-2))
Intermediate (1-1) (5.0 g, 11.8 mmol), potassium hydroxide (1.95 g, 29.6 mmol), hydrazine monohydrate (3.55 g, 71.0 mmol), as a solvent. Diethylene glycol (169 mL) was mixed and stirred at 170 ° C. for 4 hours. After completion of the reaction, the mixture was diluted with chloroform, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained crude product was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (1-2) (4.5 g, yield 93%).
（中間体（１－３））
　中間体（１－２）（４．０ｇ、９．７９ｍｍｏｌ）と、溶媒としてジクロロメタン（１５０ｍＬ）とを混合し、－７８℃で撹拌したところへ、塩化チタン（８．３５ｇ、４４．０ｍｍｏｌ）を添加し、－７８℃で１０分間撹拌した。反応溶液を－７８℃で撹拌したところへ、ブチルジクロロメチルエーテル（３．１４ｇ、１９．６ｍｍｏｌ）のジクロロメタン（５０ｍＬ）溶液を、滴下ロートを用いて滴下した。滴下後、反応溶液を－７８℃で窒素下１時間撹拌したのち、－１０℃まで昇温しさらに１時間撹拌した。反応終了後、ジクロロメタンで希釈し、０℃まで昇温させ撹拌しながら、水を滴下ロートで滴下した。滴下後、水層を除去し、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～ヘキサン／クロロホルム＝３：７）で精製し固体を得た。得られた固体をクロロホルムに溶解させ、メタノールを添加することで析出した固体を、濾過・乾燥させて中間体（１－３）（１．０６ｇ、収率２５％）を得た。 (Intermediate (1-3))
Intermediate (1-2) (4.0 g, 9.79 mmol) and dichloromethane (150 mL) as a solvent were mixed and stirred at −78 ° C., and titanium chloride (8.35 g, 44.0 mmol) was added. It was added and stirred at −78 ° C. for 10 minutes. A solution of butyl dichloromethyl ether (3.14 g, 19.6 mmol) in dichloromethane (50 mL) was added dropwise to the reaction solution stirred at −78 ° C. using a dropping funnel. After the dropwise addition, the reaction solution was stirred at −78 ° C. under nitrogen for 1 hour, then heated to −10 ° C. and further stirred for 1 hour. After completion of the reaction, water was added dropwise with a dropping funnel while diluting with dichloromethane, raising the temperature to 0 ° C. and stirring. After the dropping, the aqueous layer was removed, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to hexane / chloroform = 3: 7) to obtain a solid. The obtained solid was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (1-3) (1.06 g, yield 25%).
（中間体（１－４））
　中間体（１－３）（９００ｍｇ、２．０６ｍｍｏｌ）と、溶媒としてテトラヒドロフラン／メタノール混合溶媒（２０／１、ｖ／ｖ（体積比））（４２ｍＬ）とを混合し、０℃で撹拌させたところへ、水素化ホウ素ナトリウム（２４０ｍｇ、６．１８ｍｍｏｌ）を添加した。添加後、反応溶液を室温まで昇温し窒素下１時間撹拌した。反応終了後、０℃に降温させ撹拌しながら水を加え、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて、飽和塩化アンモニウム水溶液とブラインで洗浄し、減圧濃縮した。得られた粗生成物をクロロホルムに溶解させ、メタノールを添加することで析出した固体を濾過・乾燥させて中間体（１－４）（７７６ｍｇ、収率８６％）を得た。 (Intermediate (1-4))
The intermediate (1-3) (900 mg, 2.06 mmol) was mixed with a tetrahydrofuran / methanol mixed solvent (20/1, v / v (volume ratio)) (42 mL) as a solvent, and the mixture was stirred at 0 ° C. To this, sodium borohydride (240 mg, 6.18 mmol) was added. After the addition, the reaction solution was heated to room temperature and stirred under nitrogen for 1 hour. After completion of the reaction, the temperature was lowered to 0 ° C., water was added with stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with saturated aqueous ammonium chloride solution and brine using a separating funnel, and concentrated under reduced pressure. The obtained crude product was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (1-4) (776 mg, yield 86%).
（中間体（１－５））
　中間体（１－４）（７５０ｍｇ、１．７１ｍｍｏｌ）と、トリフェニルホスフィン（８９７ｍｇ、３．４２ｍｍｏｌ）と、溶媒としてジクロロメタン（１７ｍＬ）とを混合し、０℃で撹拌させたところへ、Ｎ－ブロモスクシンイミド（６０７ｍｇ、３．４２ｍｍｏｌ）を添加した。添加後、反応液を室温まで昇温し窒素下１時間撹拌した。反応終了後、０℃に降温させ撹拌しながらメタノールを加えることで析出した固体を濾過・乾燥させて中間体（１－５）（７００ｍｇ、収率８２％）を得た。 (Intermediate (1-5))
Intermediate (1-4) (750 mg, 1.71 mmol), triphenylphosphine (897 mg, 3.42 mmol) and dichloromethane (17 mL) as a solvent were mixed and stirred at 0 ° C. to N-. Bromosuccinimide (607 mg, 3.42 mmol) was added. After the addition, the reaction solution was heated to room temperature and stirred under nitrogen for 1 hour. After completion of the reaction, the temperature was lowered to 0 ° C. and methanol was added with stirring to filter and dry the precipitated solid to obtain an intermediate (1-5) (700 mg, yield 82%).
（化合物（１））
　１，８，１３－トリヒドロキシトリプチセン（２０ｍｇ、０．０６６ｍｍｏｌ）と、溶媒としてＮ，Ｎ－ジメチルホルムアミド（１．３２ｍＬ）とを混合し、０℃で撹拌したところへ、水素化ナトリウム（７．９ｍｇ、０．２０ｍｍｏｌ）を添加し、０℃で３０分間撹拌した。０℃で撹拌したところへ、中間体（１－５）（１０６ｍｇ、０．２１ｍｍｏｌ）を添加した。添加後、反応液を７０℃まで昇温し窒素下６時間撹拌した。反応終了後、０℃に降温させ撹拌しながら水を加え、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～クロロホルム）で精製し化合物（１）（１４ｍｇ、収率１４％）を得た。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１５６３．７ (Compound (1))
Sodium hydride (20 mg, 0.066 mmol) and N, N-dimethylformamide (1.32 mL) as a solvent were mixed and stirred at 0 ° C. 7.9 mg (0.20 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes. Intermediate (1-5) (106 mg, 0.21 mmol) was added to the mixture with stirring at 0 ° C. After the addition, the reaction solution was heated to 70 ° C. and stirred under nitrogen for 6 hours. After completion of the reaction, the temperature was lowered to 0 ° C., water was added with stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with water using a separating funnel and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to chloroform) to obtain compound (1) (14 mg, yield 14%). ESI-MS: [M + H] + = 1563.7
＜化合物（２）の合成＞
　下記スキームに従い、化合物（２）を合成した。 <Synthesis of compound (2)>
Compound (2) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（中間体（２－１））
　中間体（２－１）は特許第６２１９３１４号公報の段落［００９８］～［０１０１］に記載の方法により合成した。なお、ＴＢＳは、ｔｅｒｔ－ブチルジメチルシリル基を表す。 (Intermediate (2-1))
The intermediate (2-1) was synthesized by the method described in paragraphs [0998] to [0101] of Japanese Patent No. 6219314. In addition, TBS represents a tert-butyldimethylsilyl group.
（中間体（２－２））
　加熱乾燥したマグネシウム（２６８ｍｇ、１１．０ｍｍｏｌ）と、ヨウ素（４７ｍｇ、０．１８ｍｍｏｌ）と、１，２－ジブロモエタン（８６ｍｇ、０．４６ｍｍｏｌ）と、溶剤としてテトラヒドロフラン（５ｍＬ）を混合し、室温で撹拌しながら、滴下ロートを用いて、１－ブロモドデカン（２．２９ｇ、９．１９ｍｍｏｌ）のテトラヒドロフラン（５ｍＬ）溶液を滴下した。滴下後、１時間窒素下加熱還流した。混合液を室温に降温させ撹拌しながら、塩化亜鉛（１．２５ｇ、９．１９ｍｍｏｌ）を滴下した。滴下後、中間体（２－１）（９００ｍｇ、１．０２ｍｍｏｌ）と、［１，１´－ビス（ジフェニルホスフィノ）フェロセン］パラジウム（II）ジクロリド（ＰｄＣｌ２（ｄｐｐｆ））（８３ｍｇ、０．１０ｍｍｏｌ）とを添加し、１４時間窒素下加熱還流した。反応終了後、メタノールを添加することで析出した固体を濾過した。得られた粗生成物を、シリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～ヘキサン／クロロホルム＝３：７）で精製し中間体（２－２）（５７４ｍｇ、収率４９％）を得た。 (Intermediate (2-2))
Heat-dried magnesium (268 mg, 11.0 mmol), iodine (47 mg, 0.18 mmol), 1,2-dibromoethane (86 mg, 0.46 mmol) and tetrahydrofuran (5 mL) as a solvent were mixed and mixed at room temperature. A solution of 1-bromododecane (2.29 g, 9.19 mmol) in tetrahydrofuran (5 mL) was added dropwise using a dropping funnel with stirring. After the dropping, the mixture was heated under nitrogen for 1 hour and refluxed. Zinc chloride (1.25 g, 9.19 mmol) was added dropwise while the mixed solution was cooled to room temperature and stirred. After dropping, intermediate (2-1) (900 mg, 1.02 mmol) and [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride (PdCl2 (dppf)) (83 mg, 0.10 mmol). ) Was added, and the mixture was heated under nitrogen for 14 hours and refluxed. After completion of the reaction, the solid precipitated by adding methanol was filtered. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to hexane / chloroform = 3: 7) to obtain an intermediate (2-2) (574 mg, yield 49%). Obtained.
（中間体（２－３））
　中間体（２－２）（５００ｍｇ、０．４３ｍｍｏｌ）と、溶剤としてテトラヒドロフラン（５ｍＬ）を混合し、０℃で撹拌したところに、テトラブチルアンモニウムフロリドのテトラヒドロフラン溶液（１Ｍ）（１．７２ｍＬ、１．７２ｍｍｏｌ）を滴下した。滴下後、室温まで昇温させ、室温で窒素下１時間撹拌した。反応終了後、クロロホルムで希釈し、分液ロートを用いて、飽和塩化アンモニウム水溶液とブラインで洗浄し、減圧濃縮した。得られた固体をクロロホルムに溶解させ、メタノールを添加することで析出した固体を、濾過・乾燥させて中間体（２－３）（３１６ｍｇ、収率９１％）を得た。 (Intermediate (2-3))
Intermediate (2-2) (500 mg, 0.43 mmol) and tetrahydrofuran (5 mL) as a solvent were mixed and stirred at 0 ° C., and a solution of tetrabutylammonium fluoride in tetrahydrofuran (1 M) (1.72 mL, 1.72 mmol) was added dropwise. After the dropping, the temperature was raised to room temperature, and the mixture was stirred at room temperature under nitrogen for 1 hour. After completion of the reaction, the mixture was diluted with chloroform, washed with saturated aqueous ammonium chloride solution and brine using a separatory funnel, and concentrated under reduced pressure. The obtained solid was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (2-3) (316 mg, yield 91%).
（中間体（２－４））
　中間体（２－４）は非特許文献Ｃｏｌｌｅｃｔｉｏｎ　ｏｆ　Ｃｚｅｃｈｏｓｌｏｖａｋ、６７、６４５－６６４記載の方法により合成した。 (Intermediate (2-4))
Intermediate (2-4) was synthesized by the method described in Non-Patent Document Collection of Czechoslovakia, 67, 645-664.
（中間体（２－５））
　中間体（２－４）（１．２６ｇ、４．７０ｍｍｏｌ）と、溶剤として溶媒としてテトラヒドロフラン／メタノール混合溶媒（２０／１、ｖ／ｖ）（９４ｍＬ）とを混合し、０℃で撹拌させたところへ、水素化ホウ素ナトリウム（５２７ｍｇ、１４．１ｍｍｏｌ）を添加した。添加後、反応溶液を室温まで昇温し窒素下１時間撹拌した。反応終了後、０℃に降温させ撹拌しながら水を加え、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて、飽和塩化アンモニウム水溶液とブラインで洗浄し、減圧濃縮し、中間体（２－５）（１．０７ｇ、収率８４％）を得た。 (Intermediate (2-5))
Intermediate (2-4) (1.26 g, 4.70 mmol) and tetrahydrofuran / methanol mixed solvent (20/1, v / v) (94 mL) as a solvent were mixed and stirred at 0 ° C. To this, sodium borohydride (527 mg, 14.1 mmol) was added. After the addition, the reaction solution was heated to room temperature and stirred under nitrogen for 1 hour. After completion of the reaction, the temperature was lowered to 0 ° C., water was added with stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with saturated aqueous ammonium chloride solution and brine using a separating funnel and concentrated under reduced pressure to obtain an intermediate (2-5) (1.07 g, yield 84%).
（中間体（２－６））
　中間体（２－５）（１．０ｇ、３．６５ｍｍｏｌ）と、トリフェニルホスフィン（１．９１ｇ、７．３０ｍｍｏｌ）と、溶媒としてジクロロメタン（４０ｍＬ）とを混合し、０℃で撹拌させたところへ、Ｎ－ブロモスクシンイミド（１．３０ｇ、７．３０ｍｍｏｌ）を添加した。添加後、反応液を室温まで昇温し窒素下１時間撹拌した。反応終了後、０℃に降温させ撹拌しながら水を加え、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートと用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝７：３～クロロホルム）で精製し中間体（２－６）（０．９６ｇ、収率７９％）を得た。 (Intermediate (2-6))
Intermediate (2-5) (1.0 g, 3.65 mmol), triphenylphosphine (1.91 g, 7.30 mmol) and dichloromethane (40 mL) as a solvent were mixed and stirred at 0 ° C. N-Bromosuccinimide (1.30 g, 7.30 mmol) was added to the mixture. After the addition, the reaction solution was heated to room temperature and stirred under nitrogen for 1 hour. After completion of the reaction, the temperature was lowered to 0 ° C., water was added with stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with water using a separating funnel and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 7: 3 to chloroform) to obtain an intermediate (2-6) (0.96 g, yield 79%).
（化合物（２））
　化合物（１）の合成法における、１，８，１３－トリヒドロキシトリプチセンの代わりに中間体（２－３）を、中間体（１－５）の代わりに中間体（２－６）を用いて、化合物（１）と同様の方法で合成した（収率２１％）。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１５６３．７ (Compound (2))
In the method for synthesizing compound (1), an intermediate (2-3) is used instead of 1,8,13-trihydroxytrypticene, and an intermediate (2-6) is used instead of the intermediate (1-5). It was synthesized in the same manner as in compound (1) (yield 21%). ESI-MS: [M + H] + = 1563.7
＜化合物（３）の合成＞
　下記スキームに従い、化合物（３）を合成した。なお、Ｔｆはトリフルオロメチルスルホニル基を表し、Ｔｆ２Ｏはトリフルオロメタンスルホン酸無水物を表す。 <Synthesis of compound (3)>
Compound (3) was synthesized according to the scheme below. Incidentally, Tf represents a trifluoromethylsulfonyl group, Tf 2 O represents a triflic anhydride.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（中間体（３－１））
　中間体（３－１）は特許第６２１９３１４号公報の段落［１１８］～［０１２１］に記載の方法により合成した。 (Intermediate (3-1))
The intermediate (3-1) was synthesized by the method described in paragraphs [118] to [0121] of Japanese Patent No. 6219314.
（中間体（３－２））
　中間体（３－２）は非特許文献Ｍｏｌｅｃｕｌａｒ　Ｃｒｙｓｔａｌｓ　ａｎｄ　Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌｓ、６４７、１１９－１２６記載の方法により合成した。 (Intermediate (3-2))
The intermediate (3-2) was synthesized by the method described in Non-Patent Document Molecular Crystals and Liquid Crystals, 647, 119-126.
（中間体（３－３））
　中間体（３－２）（５００ｍｇ、１．０３ｍｍｏｌ）と、溶媒としてテトラヒドロフラン（１０ｍＬ）とを混合し、－７８℃で撹拌したところへ、ｎ－ブチルリチウムヘキサン溶液（１．６Ｍ）（１．２５ｍＬ、２．００ｍｍｏｌ）を滴下し、－７８℃で３０分間撹拌した。反応溶液を－７８℃で撹拌したところへ、ホウ酸トリメチル（３．１４ｇ、１９．６ｍｍｏｌ）のジクロロメタン（５ｍＬ）溶液を、滴下ロートを用いて滴下した。滴下後、反応溶液を－７８℃で窒素下１時間撹拌した。反応終了後、０℃まで昇温させ撹拌しながら、水を滴下ロートで滴下し、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて飽和塩化アンモニウム水溶液とブラインで洗浄し、減圧濃縮した。得られた粗生成物をクロロホルムに溶解させ、メタノールを添加することで析出した固体を、濾過・乾燥させて中間体（３－３）（３９２ｍｇ、収率８５％）を得た。 (Intermediate (3-3))
Intermediate (3-2) (500 mg, 1.03 mmol) and tetrahydrofuran (10 mL) as a solvent were mixed and stirred at −78 ° C., and then n-butyllithium hexane solution (1.6 M) (1. 25 mL, 2.00 mmol) was added dropwise, and the mixture was stirred at −78 ° C. for 30 minutes. A solution of trimethyl borate (3.14 g, 19.6 mmol) in dichloromethane (5 mL) was added dropwise using a dropping funnel to the place where the reaction solution was stirred at −78 ° C. After the dropwise addition, the reaction solution was stirred at −78 ° C. under nitrogen for 1 hour. After completion of the reaction, water was added dropwise with a dropping funnel while raising the temperature to 0 ° C. and stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with saturated aqueous ammonium chloride solution and brine using a separating funnel, and concentrated under reduced pressure. The obtained crude product was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (3-3) (392 mg, yield 85%).
（化合物（３））
　化合物（３－１）（７０ｍｇ、０．１０ｍｍｏｌ）と、化合物（３－３）（２７２ｍｇ、０．６０１ｍｍｏｌ）フッ化セシウム（９１ｍｇ、０．６０１ｍｍｏｌ）と、溶媒としてシクロペンチルメチルエーテル（５ｍＬ）とを混合し、真空脱気をした。脱気後、ＳＰｈｏｓ　Ｐｄ　Ｇ３（７．８ｍｇ、０．０１０ｍｍｏｌ）を添加し、１００℃で窒素下１４時間撹拌した。反応終了後、クロロホルムで希釈し、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～クロロホルム）で精製し化合物（１）（１９ｍｇ、収率１３％）で得た。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１４７３．７ (Compound (3))
Compound (3-1) (70 mg, 0.10 mmol), compound (3-3) (272 mg, 0.601 mmol) cesium fluoride (91 mg, 0.601 mmol), and cyclopentyl methyl ether (5 mL) as a solvent. It was mixed and vacuum degassed. After degassing, SPhos Pd G3 (7.8 mg, 0.010 mmol) was added, and the mixture was stirred at 100 ° C. under nitrogen for 14 hours. After completion of the reaction, the mixture was diluted with chloroform, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to chloroform) to obtain compound (1) (19 mg, yield 13%). ESI-MS: [M + H] + = 1473.7
＜化合物（４）の合成＞
　下記スキームに従い、化合物（４）を合成した。 <Synthesis of compound (4)>
Compound (4) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（中間体（４－１））
　中間体（３－２）（５００ｍｇ、１．０３ｍｍｏｌ）と、トリメチルシリルアセチレン（２０２ｍｇ、２．０６ｍｍｏｌ）と、溶媒としてテトラヒドロフラン／トリエチルアミン（４／１、ｖ／ｖ）（２５ｍＬ）とを混合し、真空脱気した。脱気後、ヨウ化銅（Ｉ）（３９ｍｇ、０．２１ｍｍｏｌ）と、テトラキス（トリフェニルホスフィン）パラジウム（０）（１１５ｍｇ、０．１０ｍｍｏｌ）を添加し、１２時間窒素下加熱還流した。反応終了後、クロロホルムで希釈し、分液ロートを用いて水洗し、減圧濃縮した。得られた固体を、テトラヒドロフラン／メタノール（１／１、ｖ／ｖ）（２５ｍＬ）と混合し、０℃で撹拌したところへ、炭酸カリウム（１４２ｍｇ、３．０９ｍｍｏｌ）を添加した。添加後、室温まで昇温させ１８時間撹拌した。反応終了後、撹拌しながら飽和塩化アンモニウム水溶液を添加し、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～ヘキサン／クロロホルム＝３：７）で精製し固体を得た。得られた固体をクロロホルムに溶解させ、メタノールを添加することで析出した固体を、濾過・乾燥させて中間体（４－１）（２４５ｍｇ、収率５５％）を得た。 (Intermediate (4-1))
Intermediate (3-2) (500 mg, 1.03 mmol), trimethylsilylacetylene (202 mg, 2.06 mmol) and tetrahydrofuran / triethylamine (4/1, v / v) (25 mL) as a solvent are mixed and vacuumed. I degassed. After degassing, copper (I) iodide (39 mg, 0.21 mmol) and tetrakis (triphenylphosphine) palladium (0) (115 mg, 0.10 mmol) were added, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the mixture was diluted with chloroform, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained solid was mixed with tetrahydrofuran / methanol (1/1, v / v) (25 mL) and stirred at 0 ° C., and potassium carbonate (142 mg, 3.09 mmol) was added. After the addition, the temperature was raised to room temperature and the mixture was stirred for 18 hours. After completion of the reaction, saturated aqueous ammonium chloride solution was added with stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with water using a separating funnel and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to hexane / chloroform = 3: 7) to obtain a solid. The obtained solid was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain an intermediate (4-1) (245 mg, yield 55%).
（化合物（４））
　中間体（３－１）（３５ｍｇ、０．０５０ｍｍｏｌ）と、中間体（４－１）（１３０ｍｇ、０．３０１ｍｍｏｌ）と、溶媒としてテトラヒドロフラン／トリエチルアミン（４／１、ｖ／ｖ）（５ｍＬ）とを混合し、真空脱気した。脱気後、ヨウ化銅（Ｉ）（４．８ｍｇ、０．０２５ｍｍｏｌ）と、テトラキス（トリフェニルホスフィン）パラジウム（０）（２９ｍｇ、０．０２５ｍｍｏｌ）を添加し、１２時間窒素下加熱還流した。反応終了後、クロロホルムで希釈し、分液ロートを用いて水洗し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝８：２～クロロホルム）で精製し固体を得た。得られた固体をクロロホルムに溶解させ、メタノールを添加することで析出した固体を、濾過・乾燥させて化合物（４）（１５ｍｇ、収率１８％）を得た。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１５４５．７ (Compound (4))
Intermediate (3-1) (35 mg, 0.050 mmol), intermediate (4-1) (130 mg, 0.301 mmol), and tetrahydrofuran / triethylamine (4/1, v / v) (5 mL) as a solvent. Was mixed and vacuum degassed. After degassing, copper (I) iodide (4.8 mg, 0.025 mmol) and tetrakis (triphenylphosphine) palladium (0) (29 mg, 0.025 mmol) were added, and the mixture was heated under reflux for 12 hours. After completion of the reaction, the mixture was diluted with chloroform, washed with water using a separating funnel, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 8: 2 to chloroform) to obtain a solid. The obtained solid was dissolved in chloroform, and the solid precipitated by adding methanol was filtered and dried to obtain compound (4) (15 mg, yield 18%). ESI-MS: [M + H] + = 1545.7
＜化合物（５）の合成＞
　下記スキームに従い、化合物（５）を合成した。 <Synthesis of compound (5)>
Compound (5) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（中間体（５－１））
　中間体（２－２）の合成法における、１－ブロモドデカンの代わりにトリエチレングリコール－２－ブロモエチルメチルエーテルを用いて、中間体（２－２）と同様の方法で合成した（収率４５％）。 (Intermediate (5-1))
In the method for synthesizing the intermediate (2-2), triethylene glycol-2-bromoethylmethyl ether was used instead of 1-bromododecane, and the mixture was synthesized in the same manner as the intermediate (2-2) (yield). 45%).
（中間体（５－２））
　中間体（２－３）の合成法における、中間体（２－２）の代わりに中間体（５－１）を用いて、中間体（２－３）と同様の方法で合成した（収率９２％）。 (Intermediate (5-2))
In the method for synthesizing the intermediate (2-3), the intermediate (5-1) was used instead of the intermediate (2-2), and the intermediate (2-3) was synthesized in the same manner as the intermediate (2-3) (yield). 92%).
（化合物（５））
　化合物（１）の合成法における、１，８，１３－トリヒドロキシトリプチセンの代わりに中間体（５－２）を、中間体（１－５）の代わりに中間体（２－６）を用いて、化合物（１）と同様の方法で合成した（収率３２％）。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１５８１．５ (Compound (5))
In the method for synthesizing compound (1), an intermediate (5-2) is used instead of 1,8,13-trihydroxytrypticene, and an intermediate (2-6) is used instead of the intermediate (1-5). It was synthesized in the same manner as in compound (1) (yield 32%). ESI-MS: [M + H] + = 1581.5
＜化合物（６）の合成＞
　下記スキームに従い、化合物（６）を合成した。 <Synthesis of compound (6)>
Compound (6) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（中間体（６－１））
　中間体（６－１）は非特許文献Ｊｏｕｒｎａｌ　ｏｆ　Ｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ，６５，７５０１－７５１１記載の方法により合成した。 (Intermediate (6-1))
The intermediate (6-1) was synthesized by the method described in Non-Patent Document Journal of Organic Chemistry, 65, 7501-7511.
（中間体（６－２））
　中間体（１－４）の合成法における、中間体（１－３）の代わりに中間体（６―１）を用いて、中間体（１－４）と同様の方法で合成した（収率９０％）。 (Intermediate (6-2))
In the method for synthesizing the intermediate (1-4), the intermediate (6-1) was used instead of the intermediate (1-3), and the intermediate (1-4) was synthesized in the same manner as the intermediate (1-4) (yield). 90%).
（中間体（６－３））
　中間体（１－５）の合成法における、中間体（１－４）の代わりに中間体（６―２）を用いて、中間体（１－５）と同様の方法で合成した（収率８７％）。 (Intermediate (6-3))
In the method for synthesizing the intermediate (1-5), the intermediate (6-2) was used instead of the intermediate (1-4), and the intermediate (1-5) was synthesized in the same manner as the intermediate (1-5) (yield). 87%).
（化合物（６））
　化合物（１）の合成法における、中間体（１－５）の代わりに中間体（６－３）を用いて、化合物（１）と同様の方法で合成した（収率２２％）ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１２７５．８ (Compound (6))
In the method for synthesizing compound (1), intermediate (6-3) was used instead of intermediate (1-5), and ESI-MS was synthesized by the same method as compound (1) (yield 22%). : [M + H] + = 1275.8
＜化合物（７）の合成＞
　下記スキームに従い、化合物（７）を合成した。 <Synthesis of compound (7)>
Compound (7) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（中間体（７－１））
　チエノ［３，２－Ｆ：４，５－Ｆ］ビス［１］ベンゾチオフェン（１．０ｇ、３．３７ｍｍｏｌ）と、溶媒としてテトラヒドロフラン（３０ｍＬ）を混合し、－７８℃で撹拌したところへ、ｎ－ブチルリチウムヘキサン溶液（１．６Ｍ）（２．１１ｍＬ、３．３７ｍｍｏｌ）を滴下し、－７８℃で３０分間撹拌した。反応溶液を－７８℃で撹拌したところへ、Ｎ，Ｎ－ジメチルホルムアミド（２５９ｍｇ、３．５３ｍｍｏｌ）を添加した。添加後、反応溶液を－７８℃で窒素下１時間撹拌した。反応終了後、０℃まで昇温させ撹拌しながら、水を滴下ロートで滴下し、分液ロートを用いてクロロホルムで抽出した。得られた有機層を、分液ロートを用いて飽和塩化アンモニウム水溶液とブラインで洗浄し、減圧濃縮した。得られた粗生成物をシリカゲルクロマトグラフィー（溶出液：ヘキサン／クロロホルム＝３：７～クロロホルム）で精製し中間体（７－１）（７８７ｍｇ、収率７２％）で得た。 (Intermediate (7-1))
Thieno [3,2-F: 4,5-F] bis [1] benzothiophene (1.0 g, 3.37 mmol) and tetrahydrofuran (30 mL) as a solvent were mixed and stirred at −78 ° C. A solution of n-butyllithium hexane (1.6 M) (2.11 mL, 3.37 mmol) was added dropwise, and the mixture was stirred at −78 ° C. for 30 minutes. N, N-dimethylformamide (259 mg, 3.53 mmol) was added to the reaction solution stirred at −78 ° C. After the addition, the reaction solution was stirred at −78 ° C. under nitrogen for 1 hour. After completion of the reaction, water was added dropwise with a dropping funnel while raising the temperature to 0 ° C. and stirring, and the mixture was extracted with chloroform using a separating funnel. The obtained organic layer was washed with saturated aqueous ammonium chloride solution and brine using a separating funnel, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: hexane / chloroform = 3: 7 to chloroform) to obtain an intermediate (7-1) (787 mg, yield 72%).
（中間体（７－２））
　中間体（２－５）の合成法における、中間体（２－４）の代わりに中間体（７－１）を用いて、中間体（２－５）と同様の方法で合成した（収率８６％）。 (Intermediate (7-2))
In the method for synthesizing the intermediate (2-5), the intermediate (7-1) was used instead of the intermediate (2-4), and the intermediate (2-5) was synthesized in the same manner as the intermediate (2-5) (yield). 86%).
（中間体（７－３））
　中間体（２－６）の合成法における、中間体（２－５）の代わりに中間体（７－２）を用いて、中間体（２－６）と同様の方法で合成した（収率８９％）。 (Intermediate (7-3))
In the method for synthesizing the intermediate (2-6), the intermediate (7-2) was used instead of the intermediate (2-5), and the intermediate (2-6) was synthesized in the same manner as the intermediate (2-6) (yield). 89%).
（化合物（７））
　化合物（１）の合成法における、１，８，１３－トリヒドロキシトリプチセンの代わりに中間体（２－３）を、中間体（１－５）の代わりに中間体（７－３）を用いて、化合物（１）と同様の方法で合成した（収率２０％）。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１７３１．６ (Compound (7))
In the method for synthesizing compound (1), an intermediate (2-3) is used instead of 1,8,13-trihydroxytrypticene, and an intermediate (7-3) is used instead of the intermediate (1-5). It was synthesized in the same manner as in compound (1) (yield 20%). ESI-MS: [M + H] + = 1731.6
＜化合物（８）の合成＞
　下記スキームに従い、化合物（８）を合成した。 <Synthesis of compound (8)>
Compound (8) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（中間体（８－１））
　中間体（８－１）は非特許文献ＲＳＣ　Ａｄｖａｎｃｅ，６，９５１４９－９５１５５記載の方法により合成した。 (Intermediate (8-1))
Intermediate (8-1) was synthesized by the method described in Non-Patent Document RSC Advance, 6,95149-95155.
（中間体（８－２））
　中間体（２－４）の合成における、ベンゾ［ｂ］ベンゾ［４，５］チエノ［２，３－ｄ］チオフェンの代わりに中間体（８－１）を用いて、中間体（２－４）と同様の方法で合成した（収率３２％） (Intermediate (8-2))
Using intermediate (8-1) instead of benzo [b] benzo [4,5] thieno [2,3-d] thiophene in the synthesis of intermediate (2-4), intermediate (2-4) ) Was synthesized by the same method (yield 32%).
（中間体（８－３））
　中間体（２－５）の合成法における、中間体（２－４）の代わりに中間体（８－２）を用いて、中間体（２－５）と同様の方法で合成した（収率８６％）。 (Intermediate (8-3))
In the method for synthesizing the intermediate (2-5), the intermediate (8-2) was used instead of the intermediate (2-4), and the intermediate (2-5) was synthesized in the same manner as the intermediate (2-5) (yield). 86%).
（中間体（８－４））
　中間体（２－６）の合成法における、中間体（２－５）の代わりに中間体（８－３）を用いて、中間体（２－６）と同様の方法で合成した（収率８２％）。 (Intermediate (8-4))
In the method for synthesizing the intermediate (2-6), the intermediate (8-3) was used instead of the intermediate (2-5), and the intermediate (2-6) was synthesized in the same manner as the intermediate (2-6) (yield). 82%).
（化合物（８））
　化合物（１）の合成法における、１，８，１３－トリヒドロキシトリプチセンの代わりに中間体（２－３）を、中間体（１－５）の代わりに中間体（８－４）を用いて、化合物（１）と同様の方法で合成した（収率２３％）。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１７９１．８ (Compound (8))
In the method for synthesizing compound (1), an intermediate (2-3) is used instead of 1,8,13-trihydroxytrypticene, and an intermediate (8-4) is used instead of the intermediate (1-5). It was synthesized in the same manner as in compound (1) (yield 23%). ESI-MS: [M + H] + = 1791.8
＜化合物（９）の合成＞
　下記スキームに従い、化合物（９）を合成した。 <Synthesis of compound (9)>
Compound (9) was synthesized according to the scheme below.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（中間体（９－１））
　中間体（９－１）は非特許文献Ｏｒｇａｎｉｃ　Ｌｅｔｔｅｒｓ，１３，５０５２－５０５５記載の方法により合成した。 (Intermediate (9-1))
Intermediate (9-1) was synthesized by the method described in Non-Patent Document Organic Letters, 13, 5052-5055.
（化合物（９））
　化合物（１）の合成法における、１，８，１３－トリヒドロキシトリプチセンの代わりに中間体（９－１）を用いて、化合物（１）と同様の方法で合成した（収率５３％）。ＥＳＩ－ＭＳ：［Ｍ＋Ｈ］＋＝１１２６．５ (Compound (9))
In the method for synthesizing compound (1), the intermediate (9-1) was used instead of 1,8,13-trihydroxytrypticene, and the compound (1) was synthesized in the same manner as compound (1) (yield 53%). ). ESI-MS: [M + H] + = 1126.5
〔化合物の構造式〕
　以下に、比較化合物（１）～（２）及び化合物（１）～（９）の構造式をまとめて示す。
　なお、比較化合物（１）～（２）は上述した本発明の化合物に該当せず、化合物（１）～（９）は上述した本発明の化合物に該当する。比較化合物（１）は、上述した一般式（１）で表される化合物に近いが、Ｂで表される基を１つも有さないため、上述した本発明の化合物に該当しない。 [Structural formula of compound]
The structural formulas of the comparative compounds (1) to (2) and the compounds (1) to (9) are collectively shown below.
The comparative compounds (1) and (2) do not correspond to the above-mentioned compounds of the present invention, and the compounds (1) to (9) correspond to the above-mentioned compounds of the present invention. The comparative compound (1) is similar to the compound represented by the general formula (1) described above, but does not correspond to the compound of the present invention described above because it does not have any group represented by B.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
〔有機薄膜トランジスタの製造〕
　実施例及び比較例の各化合物を用いて、以下のとおり、図２に示されるようなボトムゲート－トップコンタクト型の有機薄膜トランジスタを製造した。 [Manufacturing of organic thin film transistors]
Using each of the compounds of Examples and Comparative Examples, a bottom gate-top contact type organic thin film transistor as shown in FIG. 2 was produced as follows.
　ＦＥＴ（電界効果トランジスタ）特性測定用基板として、ｐ型シリコン基板（厚さ：０．４ｍｍ、ゲート電極２を備えた基板１に相当する。）１の表面に、ＳｉＯ２の熱酸化膜（厚さ：２００ｎｍ）を有する基板（サイズ：２５ｍｍ×２５ｍｍ）を準備した。この基板の熱酸化膜（ゲート絶縁膜３）の表面を、紫外線（ＵＶ）－オゾン洗浄した後、β－フェネチルトリメトキシシランで処理した。 As a substrate for measuring FET (field effect transistor) characteristics, a thermal oxide film (thickness ) of SiO 2 is formed on the surface of a p-type silicon substrate (thickness: 0.4 mm, corresponding to a substrate 1 provided with a gate electrode 2) 1. A substrate (size: 25 mm × 25 mm) having (s: 200 nm) was prepared. The surface of the thermal oxide film (gate insulating film 3) of this substrate was washed with ultraviolet rays (UV) -ozone and then treated with β-phenetiltrimethoxysilane.
＜有機半導体膜の形成＞
　次いで、以下の３種類の成膜方法で有機半導体膜５を形成した。 <Formation of organic semiconductor film>
Next, the organic semiconductor film 5 was formed by the following three types of film forming methods.
（１）スピンコート
　実施例及び比較例の各化合物のクロロベンゼン溶液（０．２質量％）５０μＬを、回転数１５００ｒｐｍで上記基板上にスピンコートし、その後、１５０℃、２０分間で乾燥・アニーリングすることで有機半導体膜を形成した。ここまでの工程は窒素雰囲気下のグローブボックス内又は大気下で行った。 (1) Spin coating 50 μL of a chlorobenzene solution (0.2 mass%) of each compound of Examples and Comparative Examples is spin-coated on the substrate at a rotation speed of 1500 rpm, and then dried and annealed at 150 ° C. for 20 minutes. As a result, an organic semiconductor film was formed. The steps up to this point were performed in a glove box under a nitrogen atmosphere or in the atmosphere.
（２）ドロップキャスト
　実施例及び比較例の各化合物のクロロベンゼン溶液（０．２質量％）を、９０℃に加熱した基板上にドロップキャストし、その後、１５０℃、２０分間で乾燥・アニーリングすることで有機半導体膜を形成した。ここまでの工程は窒素雰囲気下のグローブボックス内又は大気下で行った。 (2) Dropcast A chlorobenzene solution (0.2% by mass) of each compound of Examples and Comparative Examples is dropcast onto a substrate heated to 90 ° C., and then dried and annealed at 150 ° C. for 20 minutes. To form an organic semiconductor film. The steps up to this point were performed in a glove box under a nitrogen atmosphere or in the atmosphere.
（３）バーコート
　実施例及び比較例の各化合物のクロロベンゼン溶液（０．２質量％）を、基板上にバーコートし（松尾産業株式会社製、Ｋコントロールコーター）、その後、１５０℃、２０分間乾燥・アニーリングすることで有機半導体膜を形成した。ここまでの工程は窒素雰囲気下のグローブボックス内又は大気下で行った。 (3) Barcoat A chlorobenzene solution (0.2% by mass) of each compound of Examples and Comparative Examples is barcoated on a substrate (K Control Coater, manufactured by Matsuo Sangyo Co., Ltd.), and then at 150 ° C. for 20 minutes. An organic semiconductor film was formed by drying and annealing. The steps up to this point were performed in a glove box under a nitrogen atmosphere or in the atmosphere.
＜ソース電極及びドレイン電極の形成＞
　得られた有機半導体膜５上に所定の開口を有するマスクを配置して、金を蒸着することにより、ソース電極４Ａ及びドレイン電極４Ｂ（ともに厚さ：４０ｎｍ、ゲート幅Ｗ＝２ｍｍ、ゲート長Ｌ＝５０μｍ、比Ｗ／Ｌ＝４０）をそれぞれ形成した。このようにして、ＦＥＴ特性測定用の有機薄膜トランジスタを製造した。
　なお、後述する評価のため、各有機薄膜トランジスタを１０個ずつ製造した。 <Formation of source electrode and drain electrode>
By arranging a mask having a predetermined opening on the obtained organic semiconductor film 5 and depositing gold, the source electrode 4A and the drain electrode 4B (both thickness: 40 nm, gate width W = 2 mm, gate length L). = 50 μm, ratio W / L = 40), respectively. In this way, an organic thin film transistor for measuring FET characteristics was manufactured.
For the evaluation described later, 10 organic thin film transistors were manufactured.
〔評価〕
　得られた各有機薄膜トランジスタについて以下の評価を行った。 [Evaluation]
The following evaluations were performed on each of the obtained organic thin film transistors.
＜キャリア移動度＞
　各有機薄膜トランジスタのソース電極－ドレイン電極間に－８０Ｖの電圧を印加し、ゲート電圧を＋２０Ｖ～－１００Ｖの範囲で変化させ、ドレイン電流Ｉｄを表す下記式を用いてキャリア移動度μ（ｃｍ２／Ｖｓ）を算出した。
　Ｉｄ＝（ｗ／２Ｌ）μＣｉ（Ｖｇ－Ｖｔｈ）２
　式中、Ｌはゲート長、ｗはゲート幅、μはキャリア移動度、Ｃｉはゲート絶縁膜の単位面積当たりの容量、Ｖｇはゲート電圧、Ｖｔｈは閾値電圧を、それぞれ、表す。 <Carrier mobility>
A voltage of -80V is applied between the source electrode and the drain electrode of each organic thin film transistor, the gate voltage is changed in the range of + 20V to -100V, and the carrier mobility μ (cm 2 ) is expressed using the following formula representing the drain current Id. / Vs) was calculated.
I d = (w / 2L) μC i (V g −V th ) 2
Wherein, L is a gate length, w is the gate width, mu is the carrier mobility, C i is the capacitance per unit area of the gate insulating film, V g represents the gate voltage, the V th is the threshold voltage, respectively, represent.
＜性能再現性＞
　上述のとおり測定した各１０個の有機薄膜トランジスタのキャリア移動度を基に、以下のとおり移動度比を求めた。移動度比が小さい程、性能再現性に優れることを意味する。
　移動度比＝（１０個の有機薄膜トランジスタ中の最高キャリア移動度）／（１０個の有機薄膜トランジスタ中の最低キャリア移動度）
　そして、下記評価基準にしたがって評価した。結果を表１に示す。
　実用上、いずれの成膜方法でもＡ又はＢであることが好ましい。
（評価基準）
・Ａ：移動度比が１．５未満
・Ｂ：移動度比が１．５以上１．８未満
・Ｃ：移動度比が１．８以上２．１未満
・Ｄ：移動度比が２．１以上 <Performance reproducibility>
Based on the carrier mobility of each of the 10 organic thin film transistors measured as described above, the mobility ratio was determined as follows. The smaller the mobility ratio, the better the performance reproducibility.
Mobility ratio = (maximum carrier mobility in 10 organic thin film transistors) / (minimum carrier mobility in 10 organic thin film transistors)
Then, it was evaluated according to the following evaluation criteria. The results are shown in Table 1.
Practically, it is preferable that A or B is used in any of the film forming methods.
(Evaluation criteria)
・ A: Mobility ratio is less than 1.5 ・ B: Mobility ratio is 1.5 or more and less than 1.8 ・ C: Mobility ratio is 1.8 or more and less than 2.1 ・ D: Mobility ratio is 2. 1 or more
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
＜相対移動度＞
　実施例１～９（化合物（１）～（９）について、上述のとおり測定した各１０個の有機薄膜トランジスタのキャリア移動度を平均して平均移動度を求めた。そして、以下のとおり相対移動度を求めた。
　相対移動度＝（各実施例の平均移動度）／（実施例１の平均移動度）
　そして、下記評価基準にしたがって評価した。結果を表２に示す。
（評価基準）
・Ａ：相対移動度が１．０以上
・Ｂ：相対移動度が０．８以上、１．０未満
・Ｃ：相対移動度が０．６以上０．８未満
　・Ｄ：相対移動度が０．６未満 <Relative mobility>
Examples 1 to 9 (for compounds (1) to (9), the carrier mobilities of each of the 10 organic thin film transistors measured as described above were averaged to obtain the average mobilities, and the relative mobilities were calculated as follows. Asked.
Relative mobility = (average mobility of each embodiment) / (average mobility of Example 1)
Then, it was evaluated according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
・ A: Relative mobility is 1.0 or more ・ B: Relative mobility is 0.8 or more and less than 1.0 ・ C: Relative mobility is 0.6 or more and less than 0.8 ・ D: Relative mobility is 0 Less than .6
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　表１～２から分かるように、本発明の化合物ではない比較化合物（１）～（２）を有機半導体膜に用いた有機薄膜トランジスタである比較例１～２と比較して、本発明の化合物である化合物（１）～（９）を有機半導体膜に用いた有機薄膜トランジスタである実施例１～９は、優れた性能再現性を示した。なかでも、本発明の化合物が一般式（５）で表される化合物である実施例１～８は、より優れた性能再現性（スピンコート）、及び、より高いキャリア移動度を示した。そのなかでも、一般式（５）中のＡが有する共役環の数が３以上である実施例１～５及び実施例７～８は、より高いキャリア移動度を示した。
　実施例１と３と４との対比から、本発明の化合物が一般式（１）で表される化合物であり、一般式（１）中のＬが上述した＊－ＣＨ２Ｚ－＊＊である実施例１は、より優れた性能再現性（ドロップキャスト）、及び、より高いキャリア移動度を示した。 As can be seen from Tables 1 and 2, the compounds of the present invention are compared with Comparative Examples 1 and 2 which are organic thin films using the comparative compounds (1) and (2) which are not the compounds of the present invention for the organic semiconductor film. Examples 1 to 9, which are organic thin films using certain compounds (1) to (9) for the organic semiconductor film, showed excellent performance reproducibility. Among them, Examples 1 to 8 in which the compound of the present invention is a compound represented by the general formula (5) showed better performance reproducibility (spin coating) and higher carrier mobility. Among them, Examples 1 to 5 and Examples 7 to 8 in which the number of conjugated rings of A in the general formula (5) is 3 or more showed higher carrier mobility.
From the comparison between Examples 1, 3 and 4, the compound of the present invention is a compound represented by the general formula (1), and L in the general formula (1) is the above-mentioned * -CH 2 Z-**. One Example 1 showed better performance reproducibility (dropcast) and higher carrier mobility.
　１　基板
　２　ゲート電極
　３　ゲート絶縁膜
　４Ａ　ソース電極
　４Ｂ　ドレイン電極
　５　有機半導体膜（有機半導体層）
　６　封止層
　１０、２０　有機薄膜トランジスタ（有機ＴＦＴ） 1 Substrate 2 Gate electrode 3 Gate insulating film 4A Source electrode 4B Drain electrode 5 Organic semiconductor film (organic semiconductor layer)
6 Sealing layer 10, 20 Organic thin film transistor (organic TFT)

Claims (20)

  1. 　下記一般式（１）又は（２）で表される化合物。
    Figure JPOXMLDOC01-appb-C000001
     　一般式（１）及び（２）中、Ｌは、単結合又は２価の連結基を表す。
    　一般式（１）及び（２）中、Ａは、２～１０個の共役環を有する２価の共役系連結基を表す。ここで、Ａ中の任意の環Ｒにおいて、前記環Ｒに縮環する環の数と、前記環Ｒに単結合又は２価の共役系連結基を介して結合するＡ中の環の数との合計は２である。ただし、前記環Ｒが、単結合又は２価の共役系連結基を介して、一般式中のＬ、Ｂ又はＱに結合する場合、前記合計は１である。
    　一般式（１）及び（２）中、Ｂは、置換基を有していてもよい炭素数５～２２の脂肪族炭化水素基を表す。ここで、前記脂肪族炭化水素基を構成する炭素原子は、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ、又は、－ＮＲ１－で置換されていてもよい。Ｘは、酸素原子又は硫黄原子を表す。Ｒ１は、水素原子、又は、置換基を有していてもよい脂肪族炭化水素基を表す。
    　一般式（１）及び（２）中、Ｑは、水素原子又はハロゲン原子を表す。
    　一般式（１）及び（２）中、ｎは、０又は１を表す。
    　一般式（１）及び（２）中、Ｘ１、Ｘ２、Ｘ３及びＸ４は、それぞれ独立に、下記一般式（Ａ－Ｂ）又は（Ｂ－Ａ）で表される基を表す。
    　一般式（１）及び（２）中、Ｙは、水素原子又は置換基を表す。
    　ただし、一般式（１）中の２つのｎ、及び、一般式（１）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。また、一般式（２）中の２つのｎ、及び、一般式（２）中のＸ１、Ｘ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。
    Figure JPOXMLDOC01-appb-C000002
     　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中のＬ、Ａ、Ｂ及びＱの定義は、一般式（１）及び（２）中のＬ、Ａ、Ｂ及びＱとそれぞれ同じである。
    　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
    　一般式（Ａ－Ｂ）及び（Ｂ－Ａ）中、＊は、結合部位を表す。     A compound represented by the following general formula (1) or (2).
    Figure JPOXMLDOC01-appb-C000001
     In the general formulas (1) and (2), L represents a single bond or a divalent linking group.
    In the general formulas (1) and (2), A represents a divalent conjugate system linking group having 2 to 10 conjugate rings. Here, in any ring R in A, the number of rings fused to the ring R and the number of rings in A bonded to the ring R via a single bond or a divalent conjugated system linking group. The total of is 2. However, when the ring R is bonded to L, B or Q in the general formula via a single bond or a divalent conjugated system linking group, the total is 1.
    In the general formulas (1) and (2), B represents an aliphatic hydrocarbon group having 5 to 22 carbon atoms which may have a substituent. Here, the carbon atom constituting the aliphatic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a silicon atom,> C = X, or −NR 1 −. X represents an oxygen atom or a sulfur atom. R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
    In the general formulas (1) and (2), Q represents a hydrogen atom or a halogen atom.
    In the general formulas (1) and (2), n represents 0 or 1.
    In the general formulas (1) and (2), X 1 , X 2 , X 3 and X 4 independently represent groups represented by the following general formulas (AB) or (BA), respectively.
    In the general formulas (1) and (2), Y represents a hydrogen atom or a substituent.
    However, the general formula (1) two n in, and, X 1 in the formula (1), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1. In general formula (2) two n in, and, X 1 in the general formula (2), X 2, each n is included in X 3 and X 4, out of the total of six n, at least one It is 1.
    Figure JPOXMLDOC01-appb-C000002
     The definitions of L, A, B and Q in the general formulas (AB) and (BA) are the same as those of L, A, B and Q in the general formulas (1) and (2), respectively.
    In the general formulas (AB) and (BA), m and n independently represent 0 or 1, respectively.
    In the general formulas (AB) and (BA), * represents a binding site.
  2. 　前記一般式（１）で表される、請求項１に記載の化合物。 The compound according to claim 1, which is represented by the general formula (1).
  3. 　下記一般式（３）で表される、請求項２に記載の化合物。
    Figure JPOXMLDOC01-appb-C000003
     　一般式（３）中のＬ、Ａ、Ｂ、Ｑ及びＹの定義は、前記一般式（１）中のＬ、Ａ、Ｂ、Ｑ及びＹとそれぞれ同じである。
    　一般式（３）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
    　ただし、一般式（３）中の３つのｎのうち、少なくとも１つは１である。     The compound according to claim 2, which is represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000003
     The definitions of L, A, B, Q and Y in the general formula (3) are the same as those of L, A, B, Q and Y in the general formula (1), respectively.
    In the general formula (3), m and n independently represent 0 or 1, respectively.
    However, at least one of the three n in the general formula (3) is 1.
  4. 　前記一般式（３）中のｍ及びｎが、いずれも１である、請求項３に記載の化合物。 The compound according to claim 3, wherein m and n in the general formula (3) are both 1.
  5. 　下記一般式（４）で表される、請求項１に記載の化合物。
    Figure JPOXMLDOC01-appb-C000004
     　一般式（４）中のＬ、Ａ、Ｂ、Ｑ及びＹの定義は、前記一般式（１）及び（２）中のＬ、Ａ、Ｂ、Ｑ及びＹとそれぞれ同じである。
    　一般式（４）中、ｍ及びｎは、それぞれ独立に、０又は１を表す。
    　ただし、一般式（４）中の３つのｎのうち、少なくとも１つは１である。     The compound according to claim 1, which is represented by the following general formula (4).
    Figure JPOXMLDOC01-appb-C000004
     The definitions of L, A, B, Q and Y in the general formula (4) are the same as those of L, A, B, Q and Y in the general formulas (1) and (2), respectively.
    In the general formula (4), m and n independently represent 0 or 1, respectively.
    However, at least one of the three n in the general formula (4) is 1.
  6. 　前記一般式（４）中、ｍ及びｎが、いずれも１である、請求項５に記載の化合物。 The compound according to claim 5, wherein m and n are both 1 in the general formula (4).
  7. 　下記一般式（５）で表される、請求項２に記載の化合物。
    Figure JPOXMLDOC01-appb-C000005
     　一般式（５）中のＬ、Ａ、Ｂ、Ｑ、Ｘ２、Ｘ３、Ｘ４及びＹの定義は、前記一般式（１）中のＬ、Ａ、Ｂ、Ｑ、Ｘ２、Ｘ３、Ｘ４及びＹとそれぞれ同じである。
    　一般式（５）中、ｎは、０又は１を表す。
    　ただし、一般式（５）中の３つのｎ、及び、一般式（５）中のＸ２、Ｘ３及びＸ４に含まれる各ｎ、合計６つのｎのうち、少なくとも１つは１である。     The compound according to claim 2, which is represented by the following general formula (5).
    Figure JPOXMLDOC01-appb-C000005
     L in the general formula (5), A, B, Q, X 2, X 3, the definition of X 4 and Y, L in the general formula (1), A, B, Q, X 2, X 3 , respectively and X 4 and Y same.
    In the general formula (5), n represents 0 or 1.
    However, three of n in the general formula (5) and, each n is included in the general formula (5) X 2, X 3 and X 4 in, out of the total of six n, at least one is 1 ..
  8. 　前記Ｂが、置換基を有していてもよい炭素数１２～１８のアルキル基である、請求項１～７のいずれか１項に記載の化合物。ここで、前記アルキル基を構成する炭素原子は、酸素原子、硫黄原子、ケイ素原子、＞Ｃ＝Ｘ、又は、－ＮＲ１－で置換されていてもよい。Ｘは、酸素原子又は硫黄原子を表す。Ｒ１は、水素原子、又は、置換基を有していてもよい脂肪族炭化水素基を表す。 The compound according to any one of claims 1 to 7, wherein B is an alkyl group having 12 to 18 carbon atoms which may have a substituent. Here, the carbon atom constituting the alkyl group may be substituted with an oxygen atom, a sulfur atom, a silicon atom,> C = X, or −NR 1 −. X represents an oxygen atom or a sulfur atom. R 1 represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent.
  9. 　前記Ｌにおいて、部分構造同士を直線的につなぐ原子数が偶数である、請求項１～８のいずれか１項に記載の化合物。ただし、置換基は前記原子数に含まれない。 The compound according to any one of claims 1 to 8, wherein the number of atoms linearly connecting the partial structures in L is an even number. However, the substituent is not included in the number of atoms.
  10. 　前記Ｌが、単結合、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨ－、－ＣＨ２ＣＨ２－、－（ＣＨ２）４－又は、＊－ＣＨ２Ｚ－＊＊である、請求項１～９のいずれか１項に記載の化合物。ここで、Ｚは、酸素原子、硫黄原子、セレン原子、又は、－ＮＲ２－を表す。Ｒ２は、水素原子又はアルキル基を表す。また、＊は、前記一般式中のＡ、Ｂ又はＱとの結合部位を表し、＊＊は、前記一般式中のベンゼン環との結合部位を表す。 Wherein L is a single bond, -C≡C -, - CH = CH -, - CH 2 CH 2 -, - (CH 2) 4 - or, * - CH 2 Z - is a **, claim 1 The compound according to any one of 9. Here, Z represents an oxygen atom, a sulfur atom, a selenium atom, or -NR 2- . R 2 represents a hydrogen atom or an alkyl group. Further, * represents a binding site with A, B or Q in the general formula, and ** represents a binding site with a benzene ring in the general formula.
  11. 　前記Ｙが、水素原子である、請求項１～１０のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 10, wherein Y is a hydrogen atom.
  12. 　前記Ｑが、水素原子、又はフッ素原子である、請求項１～１１のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 11, wherein the Q is a hydrogen atom or a fluorine atom.
  13. 　前記Ａが、カルコゲン原子を含む縮合多環共役複素環である、請求項１～１２のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 12, wherein A is a condensed polycyclic conjugated heterocycle containing a chalcogen atom.
  14. 　前記Ａが、電荷輸送基である、請求項１～１３のいずれか１項に記載の化合物。 The compound according to any one of claims 1 to 13, wherein A is a charge transport group.
  15. 　前記Ａが、下記一般式（Ａ１）で表される基、下記一般式（Ａ２）で表される基、又は、これらの組み合わせである、請求項１～１４のいずれか１項に記載の化合物。
    Figure JPOXMLDOC01-appb-C000006
     　一般式（Ａ１）中、Ａｒ１、Ａｒ２及びＡｒ３は、それぞれ独立に、共役環を表す。ｐは、０～８の整数を表す。＊は、結合部位を表す。
    　一般式（Ａ２）中、Ａｒは、共役環を表す。Ｍは、単結合、又は、２価の共役系連結基を表す。ｑは、０～８の整数を表す。＊は、結合部位を表す。     The compound according to any one of claims 1 to 14, wherein A is a group represented by the following general formula (A1), a group represented by the following general formula (A2), or a combination thereof. ..
    Figure JPOXMLDOC01-appb-C000006
     In the general formula (A1), Ar 1 , Ar 2 and Ar 3 each independently represent a conjugated ring. p represents an integer from 0 to 8. * Represents the binding site.
    In the general formula (A2), Ar represents a conjugated ring. M represents a single bond or a divalent conjugated system linking group. q represents an integer from 0 to 8. * Represents the binding site.
  16. 　請求項１～１５のいずれか１項に記載の化合物と、少なくとも１種類の溶剤とを含有する組成物。 A composition containing the compound according to any one of claims 1 to 15 and at least one solvent.
  17. 　請求項１～１５のいずれか１項に記載の化合物を含有する膜。 A membrane containing the compound according to any one of claims 1 to 15.
  18. 　基板と、前記基板の表面に配置された請求項１７に記載の膜とを備える、構造体。 A structure comprising a substrate and the film according to claim 17 arranged on the surface of the substrate.
  19. 　請求項１８に記載の構造体を含む、電子デバイス。 An electronic device comprising the structure according to claim 18.
  20. 　有機薄膜トランジスタである、請求項１９に記載の電子デバイス。 The electronic device according to claim 19, which is an organic thin film transistor.
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