WO2016194517A1 - Organic thin film transistor and organic semiconductor layer-forming composition - Google Patents

Organic thin film transistor and organic semiconductor layer-forming composition Download PDF

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Publication number
WO2016194517A1
WO2016194517A1 PCT/JP2016/062893 JP2016062893W WO2016194517A1 WO 2016194517 A1 WO2016194517 A1 WO 2016194517A1 JP 2016062893 W JP2016062893 W JP 2016062893W WO 2016194517 A1 WO2016194517 A1 WO 2016194517A1
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group
formula
atom
organic semiconductor
represented
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PCT/JP2016/062893
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French (fr)
Japanese (ja)
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和公 横井
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富士フイルム株式会社
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • 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
    • 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
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]

Definitions

  • the present invention relates to an organic thin film transistor and a composition for forming an organic semiconductor layer.
  • organic TFT Field Effect Transistor
  • RFID Radio Frequency Identifier, RF tag
  • memory used for liquid crystal display or organic electroluminescence (organic EL) display
  • organic TFT thin film transistor
  • organic semiconductor film organic semiconductor film
  • Patent Document 1 states that “in a transistor, a semiconductor layer, a channel disposed on or in the semiconductor layer, a source disposed on or in the semiconductor layer, on or in the semiconductor layer.
  • a drain disposed on the semiconductor layer, a gate electrically coupled to the semiconductor layer, and a photoactive material comprising: (a) adjacent to the semiconductor layer and in contact with the semiconductor layer; and (b) the semiconductor layer Or (c) a photoactive material disposed within one or more of the source, the drain and the gate, wherein molecules, protons and / or ions are from the photoactive material.
  • a transistor characterized in that it diffuses into the semiconductor material.
  • the present inventor made an organic thin film transistor by referring to the method described in Patent Document 1, and the manufactured organic thin film transistor was organic after the organic semiconductor material constituting the organic semiconductor layer was crystallized. Since the photoacid generator disposed in or near the semiconductor layer is decomposed by light irradiation and the decomposed fragments are diffused into the organic semiconductor layer, it is possible to dope without disturbing the crystallinity relatively. It was confirmed. However, since all of the photoacid generators described in the cited document 1 are low molecular photoacid generators, the diffusibility is excellent, but in some cases, the insulation performance of the organic thin film transistor is reduced due to diffusion, that is, It was found that the ON / OFF ratio tends to decrease. In view of recent demands for improving mobility (particularly carrier mobility) with respect to organic thin film transistors, organic thin film transistors having higher carrier mobility are desired.
  • an object of the present invention is to provide an organic thin film transistor excellent in carrier mobility and insulation reliability, and an organic semiconductor layer forming composition capable of producing the same.
  • the present inventor in an organic thin film transistor, first, an organic semiconductor material and a resin having a repeating unit containing a structural site that generates an acid anion by irradiation with actinic rays or radiation in the side chain, An organic semiconductor layer precursor layer is formed, and the organic semiconductor layer precursor layer is irradiated with actinic rays or radiation, and the resin is decomposed to form a dopant (preferably an acid anion polymer) in the system.
  • a dopant preferably an acid anion polymer
  • An organic thin film transistor having a source electrode and a drain electrode, The organic semiconductor layer comprises an organic semiconductor material and an organic semiconductor layer precursor containing an organic semiconductor material and a resin having a repeating unit containing a structural site that generates acid anions upon irradiation with active light or radiation.
  • An organic thin film transistor which is a layer obtained by irradiation with radiation.
  • the organic semiconductor material has a condensed polycyclic aromatic group, the number of rings in the condensed polycyclic aromatic group is 4 or more, and at least two rings in the condensed polycyclic aromatic group Includes at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and as a partial structure in the condensed polycyclic aromatic group, a benzene ring, a naphthalene ring, and a phenanthrene ring
  • the organic thin film transistor according to (4), wherein the condensed polycyclic aromatic group in the organic semiconductor material has 4 to 6 rings.
  • the condensed polycyclic aromatic group of the organic semiconductor material contains at least two heterocycles, and each of the heterocycles is a heterocycle having only one heteroatom, (4) or (5 ) Organic thin film transistor.
  • a composition for forming an organic semiconductor layer comprising: an organic semiconductor material; and a resin having a repeating unit containing a structure that generates acid anions upon irradiation with actinic rays or radiation in the side chain.
  • the term “compound” is used to mean not only the compound itself but also its salt and its ion.
  • substituents or linking groups or the like when there are a plurality of substituents or linking groups or the like (hereinafter referred to as substituents or the like) indicated by a specific symbol, or when a plurality of substituents or the like are defined simultaneously, Means the same or different. The same applies to the definition of the number of substituents and the like.
  • substituents or the like when a plurality of substituents and the like are close (particularly adjacent), it means that they may be connected to each other or condensed to form a ring.
  • a substituent or the like that does not clearly indicate substitution / unsubstitution means that the group may further have a substituent as long as the intended effect is not impaired. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • an organic thin film transistor excellent in carrier mobility and insulation reliability it is possible to provide an organic semiconductor layer forming composition capable of producing the same.
  • Organic thin film transistor The structure of the organic thin film transistor of the present invention (hereinafter simply referred to as “OTFT of the present invention”) will be described below.
  • the OTFT of the present invention is provided on a substrate in contact with an organic semiconductor layer, a gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and the organic semiconductor layer. And a source electrode and a drain electrode connected to each other.
  • a current flow channel channel is formed at the interface between the organic semiconductor layer between the source electrode and the drain electrode and the adjacent layer. That is, the current flowing between the source electrode and the drain electrode is controlled according to the input voltage applied to the gate electrode.
  • FIGS. 1A and 1B are longitudinal sectional views each schematically showing a typical preferable structure of an OTFT of the present invention.
  • 1A to 1D each include an organic semiconductor layer 1, a gate insulating layer 2, a source electrode 3, a drain electrode 4, a gate electrode 5, and a substrate 6.
  • 1A shows a bottom gate / bottom contact structure
  • FIG. 1B shows a bottom gate / top contact structure
  • FIG. 1C shows a top gate / bottom contact structure
  • FIG. 1D shows a top gate / top contact structure OTFT.
  • the OTFT of the present invention includes all of the above four forms. Although not shown, an overcoat layer may be formed on the top of each OTFT in the drawing (the side opposite to the substrate 6).
  • the organic semiconductor layer 1 is a resin (hereinafter simply referred to as “photoacid generation”) having an organic semiconductor material and a repeating unit containing a structural site that generates an acid anion upon irradiation with actinic rays or radiation. It is also formed by irradiating an actinic ray or radiation to an organic semiconductor layer precursor layer containing a resin.
  • photoacid generation a resin having an organic semiconductor material and a repeating unit containing a structural site that generates an acid anion upon irradiation with actinic rays or radiation. It is also formed by irradiating an actinic ray or radiation to an organic semiconductor layer precursor layer containing a resin.
  • photoacid generation a resin having an organic semiconductor material and a repeating unit containing a structural site that generates an acid anion upon irradiation with actinic rays or radiation. It is also formed by irradiating an actinic ray or radiation to an organic semiconductor layer precursor layer containing a resin
  • the above-mentioned organic semiconductor layer forming composition is first prepared, and this is used as the lower gate insulating layer 2.
  • the organic semiconductor layer precursor layer is formed by coating on the source electrode 3 and the drain electrode 4.
  • a predetermined organic semiconductor layer can be formed by irradiating the organic semiconductor layer precursor layer with actinic rays or radiation.
  • the organic semiconductor layer precursor layer it is presumed that the organic semiconductor material having high crystallinity and the photoacid-generating resin are present in phase separation from each other.
  • the photoacid-generating resin absorbs energy and cleaves, and mainly decomposes into a main chain portion having an acid anion in the side chain and a cation portion.
  • the main chain portion having an acid anion in the side chain as a dopant has a large molecular weight compared with a low molecular acid anion formed by a low molecular photoacid generator as described in Patent Document 1. It is considered that it remains in a state separated from the organic semiconductor material in the organic semiconductor layer because of its poor property.
  • the organic thin film transistor of the present invention has an excellent ON / OFF ratio because a decrease in insulating performance caused by diffusion of the dopant into the gate insulating layer is suppressed.
  • the main chain portion having an acid anion in the side chain which is a dopant and the crystal of the organic semiconductor material are phase-separated, compared with the case of using a low molecular photoacid generator rich in diffusibility There is little damage to the crystallinity of the organic semiconductor material, and the carrier mobility is excellent.
  • the organic semiconductor layer 1 includes an organic semiconductor material containing an organic semiconductor material in addition to the method using the organic semiconductor layer forming composition containing the organic semiconductor material and the photoacid generating resin as described above.
  • an organic semiconductor layer precursor layer as at least two layers of a semiconductor material layer and a photoacid generating resin layer containing a photoacid generating resin, and irradiating the organic semiconductor layer precursor layer with actinic rays or radiation It may be formed.
  • the stacking order of the organic semiconductor material layer and the photoacid generating resin layer is not particularly limited, but the organic semiconductor material layer is disposed on the gate insulating layer side in that the effect of the present invention is more excellent.
  • the photogenerating resin layer is located away from the gate insulating layer.
  • an organic semiconductor material layer is formed on the lower gate insulating layer 2, the source electrode 3, and the drain electrode 4, and then the organic semiconductor material layer is formed.
  • An organic semiconductor layer precursor layer is formed by laminating a photoacid-generating resin layer on all or part of the surface of the semiconductor material layer, and the organic semiconductor layer precursor layer is irradiated with actinic rays or radiation.
  • the organic semiconductor material and the dopant generated by the cleavage of the photoacid-generating resin are present in phase separation, As a result, the organic thin film transistor is excellent in carrier mobility and insulation reliability.
  • the organic semiconductor layer is a layer that exhibits semiconductor properties and can accumulate carriers.
  • the organic semiconductor layer in the present invention is formed by irradiating the organic semiconductor layer precursor containing the organic semiconductor material and the photoacid generating resin with actinic rays or radiation.
  • the film thickness (whole) of an organic-semiconductor layer is not specifically limited, 1 nm or more is preferable and 10 nm or more is more preferable. Moreover, 10 micrometers or less are preferable, 1 micrometer or less is more preferable, and 500 nm or less is especially preferable.
  • the film thickness of the organic semiconductor material layer or the film thickness of the photoacid generating resin layer in the formed organic semiconductor layer are not particularly limited as long as the thickness of the entire organic semiconductor layer is within the above range.
  • the content of the photoacid-generating resin is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the organic semiconductor material. More preferably, the content is 0.1 to 5 parts by mass. By setting it as said range, it can be set as the organic thin-film transistor more excellent in carrier mobility and insulation reliability.
  • the content of the photoacid generating resin is 100000: 1 to 10: 1 in a mass ratio of the total solid content of the organic semiconductor layer to the photoacid generating resin with respect to the total solid content of the organic semiconductor layer. It is preferably 10000: 1 to 100: 5, more preferably 1000: 1 to 100: 1.
  • the composition for forming an organic semiconductor layer includes an organic semiconductor material and a photoacid generating resin, but may further include other additives such as a solvent, a surfactant, or a binder resin.
  • the photoacid-generating resin is not particularly limited as long as it is a resin having a repeating unit containing a structural site that generates an acid anion in the side chain upon irradiation with actinic rays or radiation, either alone or in combination of two or more. Also good.
  • active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, or electron beams.
  • light means actinic rays or radiation.
  • repeating unit containing in its side chain a structural moiety that generates an acid anion upon irradiation with actinic rays or radiation
  • a repeating unit represented by any one of the following general formulas (III) to (V) is preferable.
  • A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
  • R 04 , R 05 and R 07 to R 09 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 06 represents a cyano group, a carboxyl group, —CO—OR 25 or —CO—N (R 26 ) (R 27 ).
  • R 26 and R 27 may combine to form a ring with the nitrogen atom.
  • X 1 to X 3 each independently represents a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R 33 ) —, or a combination thereof.
  • R 25 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • R 26 , R 27 and R 33 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • the alkyl group may be linear or branched, preferably a methyl group which may have a substituent
  • Examples include an alkyl group having 20 or less carbon atoms, such as an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and more preferably a carbon number of 8
  • alkyl groups are mentioned.
  • the cycloalkyl group may be monocyclic or polycyclic, and may further have a substituent. Preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is more preferable.
  • the alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R 04 to R 05 and R 07 to R 09 .
  • the alkenyl group is preferably a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group which may have a substituent. And those having 2 to 6 carbon atoms.
  • the aryl group is preferably a monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms which may have a substituent. Specifically, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, A naphthyl group etc. are mentioned.
  • Aryl groups may be bonded to each other to form a double ring.
  • aralkyl group examples include those having 7 to 15 carbon atoms which may have a substituent such as a benzyl group, a phenethyl group or a cumyl group.
  • the ring that can be formed by combining R 26 and R 27 together with the nitrogen atom is preferably a ring that forms a 5- to 8-membered ring. Specific examples include pyrrolidine, piperidine, and piperazine.
  • the arylene group of X 1 to X 3 is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group.
  • the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.
  • Examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
  • each group may have a substituent.
  • the alkylene group is preferably substituted with a halogen atom from the viewpoint of more excellent effects of the present invention.
  • each of these groups may further have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R 04 to R 05 , R 07 -R 09 , R 25 -R 27 and R 33 , an alkyl group, an methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an alkoxy group such as a butoxy group, a methoxycarbonyl group or Examples include an alkoxycarbonyl group such as ethoxycarbonyl group, an acyl group such as formyl group, acetyl group or benzoyl group, an acyloxy group such as acetoxy group or butyryloxy group, or a carboxy group.
  • the number of carbon atoms is preferably 8 or less.
  • A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion, specifically, photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecolorant for dyes, Examples thereof include a structural portion possessed by a compound that generates an acid anion by known light used in a photochromic agent or a microresist.
  • structural sites that generate acid anions upon irradiation with actinic rays or radiation include, for example, diazonium salt structures, ammonium salt structures, phosphonium salt structures, iodonium salt structures, sulfonium salt structures, selenonium salt structures, or arsonium salt structures.
  • part can be mentioned.
  • A is more preferably an ionic structure site containing a sulfonium salt structure or an iodonium salt structure from the viewpoint of degradability and storage stability. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.
  • Examples of the ring structure formed by combining two of R 201 to R 203 include cycloalkanes such as cyclobutane and cyclopentane.
  • Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion.
  • the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
  • a non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the stability of the resin over time.
  • Examples of the organic group represented by R 201 , R 202 and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • the aryl group, alkyl group or cycloalkyl group represented by R 201 , R 202 and R 203 is represented by the above-mentioned R 04 to R 05 , R 07 to R 09 , R 25 to R 27 and R 33.
  • at least one of R 201 , R 202 and R 203 is preferably an aryl group, and more preferably all three are aryl groups.
  • aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue or a pyrrole residue is also possible.
  • These aryl groups may further have a substituent.
  • substituents include halogen atoms such as nitro group or fluorine atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms).
  • An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), or an alkoxycarbonyloxy group (preferably having a carbon number) 2-7) and the like, but are not limited thereto.
  • Preferred structures when at least one of R 201 , R 202 and R 203 is not an aryl group include paragraphs 0047 to 0048 of JP-A No. 2004-233661, paragraphs 0040 to 0046 of JP-A No. 2003-35948, Compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003/0224288 or Formula (IA-1) in U.S. Patent Application Publication No. 2003/0077540. ) To (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).
  • R 204 to R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • These aryl group, alkyl group and cycloalkyl group are the same as the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 205 may have a substituent. Examples of the substituent include the same substituents that the aryl group, alkyl group, or cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
  • Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁇ in formula (ZI).
  • produces an acid anion by irradiation of actinic light or a radiation
  • part used as the sulfonic acid precursor which the following photoacid generator has can also be mentioned, for example.
  • repeating unit represented by any one of the above general formulas (III) to (V) more preferably, the following general formulas (III-1) to (III-6), general formulas (IV-1) to Examples thereof include (IV-4) and those represented by general formulas (V-1) to (V-2).
  • Ar 1a represents an arylene group which may have a substituent.
  • the arylene group which may have a substituent include the arylene groups represented by the above X 1 to X 3 and the same substituents as the substituent which may be substituted on the arylene group.
  • Ar 2a to Ar 4a represent an aryl group which may have a substituent.
  • the aryl group which may have a substituent the aryl group represented by R 201 to R 203 and R 204 to R 205 in the above general formulas (ZI) and (ZII) and the above aryl group are substituted. The thing similar to the substituent which may be mentioned is mentioned.
  • R 01 represents a hydrogen atom, a methyl group, a chloromethyl group, a trifluoromethyl group, or a cyano group.
  • R 02 and R 021 are a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, CO—, —N (R 33 ) —, or a divalent linkage in which a plurality of these are combined. Represents a group. These are the same as those shown for X 1 to X 3 .
  • R 03 and R 019 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
  • alkyl group and cycloalkyl group include those similar to the alkyl group and cycloalkyl group represented by R 04 described above.
  • aryl group for example, an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group and the like can be preferably exemplified.
  • the aralkyl group include 6 to 20 carbon atoms and a benzyl group or phenethyl group.
  • an acid anion is generated.
  • the structural site is an ionic structural site including a sulfonium salt structure or an iodonium salt structure
  • the structural site that generates an acid anion may be a nonionic structural site that does not include a salt structure.
  • the repeating unit represented by any one of the general formulas (III) to (V) preferably includes those represented by the following general formula. it can.
  • Ar 1 represents an arylene group which may have a substituent.
  • the arylene group which may have a substituent include the arylene groups represented by the above X 1 to X 3 and the same substituents as the substituent which may be substituted on the arylene group.
  • Ar 6 and Ar 7 represent an aryl group which may have a substituent. Examples of the aryl group which may have a substituent include the aryl groups represented by R 25 to R 27 described above and the same substituents that may be substituted on the aryl group.
  • R 01 represents a hydrogen atom, a methyl group, a chloromethyl group or a cyano group.
  • R 02 and R 021 each represents an arylene group, an alkylene group or a cycloalkylene group.
  • Examples of the arylene group, alkylene group, or cycloalkylene group include the same groups as those represented by X 1 to X 3 .
  • R 03 , R 05 to R 010 , R 013 , R 015 and R 022 each represents an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and these are represented by R 25 to R 27 above.
  • the alkyl group in the haloalkyl group has the same meaning as the alkyl group represented by R 25 to R 27 ).
  • R 04 represents an arylene group, an alkylene group, or an alkenylene group having 2 to 6 carbon atoms which may have a substituent.
  • the arylene group or alkylene group include the same groups as those represented by X 1 to X 3 .
  • the alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms, such as an ethynylene group, a propenylene group, or a butenylene group, which may have a substituent.
  • the substituent include the substituents that may be further included.
  • R 011 and R 014 are a hydrogen atom, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), or an alkyl group, an alkoxy group, an alkoxycarbonyl group, or Represents an acyloxy group.
  • R 012 represents a nitro group, a cyano group, a trifluoromethyl group, or a perfluoroalkyl group such as a pentafluoroethyl group.
  • the photoacid generator resin preferably has a low acid dissociation index pKa, and is a unit having a structural site that generates an acid anion of the photoacid generator resin (a repeating unit represented by formulas (III) to (V)).
  • Monomer preferably has a pKa of 6 or less, more preferably ⁇ 4 or less, and most preferably ⁇ 10 or less.
  • the pKa value in the present invention is a value calculated by commercially available software ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
  • repeating unit represented by any one of the general formulas (III) to (V) are shown below, but the present invention is not limited thereto.
  • the resin side chain in the examples (a1) to (a196) in JP-A No. 10-221852 is disclosed.
  • those having a structure generating an acid anion are also included.
  • the content of repeating units (III) to (V) in the photoacid-generating resin is preferably in the range of 10 to 100 mol%, preferably in the range of 30 to 100 mol%, based on all repeating units. More preferably, it is particularly preferably contained in the range of 40 to 100 mol%.
  • a known polymerizable monomer can be copolymerized as a copolymerization component.
  • the monomer to be copolymerized is preferably a radical polymerizable compound, preferably (meth) acrylic acid esters, styrene derivatives, vinyl acetate, crotonic acid or maleic anhydride.
  • the method for synthesizing the monomers corresponding to the repeating units (III) to (V) is not particularly limited.
  • an acid anion having a polymerizable unsaturated bond corresponding to the above repeating unit is exchanged with a known onium salt halide. And a synthesis method.
  • a metal ion salt of an acid having a polymerizable unsaturated bond corresponding to the above repeating unit for example, sodium ion or potassium ion
  • ammonium salt ammonium or triethylammonium salt etc.
  • a halogen ion Onium salt having chloride ion, bromide ion or iodide ion
  • anion exchange reaction such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone or tetrahydroxyfuran.
  • a monomer corresponding to the target repeating unit By performing a liquid separation / washing operation with an organic solvent and water, a monomer corresponding to the target repeating unit can be synthesized.
  • an organic solvent that can be separated from water such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, or tetrahydroxyfuran, and water
  • the solution is separated with water. It can also be synthesized by a washing operation.
  • the molecular weight of the photoacid generator resin is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 70000, and particularly preferably in the range of 3000 to 50000. preferable.
  • the weight average molecular weight of the photoacid-generating resin indicates a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC / carrier: tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP)).
  • the dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.
  • the concentration of the photoacid generating resin in the composition for forming an organic semiconductor layer is not particularly limited, but is preferably 0.0001 to 5% by weight, preferably 0.001 to 3% with respect to the total weight of the composition for forming an organic semiconductor layer. % By mass is more preferable, and 0.01 to 1% by mass is particularly preferable.
  • the organic semiconductor layer of the present invention contains an organic semiconductor material.
  • An organic semiconductor material is a material exhibiting properties as a semiconductor.
  • the organic semiconductor material is preferably P-type.
  • organic semiconductor material examples include pentacenes such as 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS pentacene), tetramethylpentacene, or perfluoropentacene, and 5,11-bis (triethylsilylethynyl) an Anthradithiophenes such as tradithiophene (TES-ADT) or 2,8-difluoro-5,11-bis (triethylsilylethynyl) anthradithiophene (diF-TES-ADT), diphenylbenzothienobenzothiophene (DPh) -BTBT), or benzothienobenzothiophenes such as alkylbenzothienobenzothiophene (Cn-BTBT), dinaphthothienothiophenes such as alkyldinaphthothienothiophene (Cn-DN
  • the specific organic semiconductor material (component A) has a condensed polycyclic aromatic group, the number of rings in the condensed polycyclic aromatic group is 4 or more, and the condensed polycyclic aromatic group At least two of the rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and the partial structure in the condensed polycyclic aromatic group includes a benzene ring, naphthalene An organic semiconductor material containing at least one structure selected from the group consisting of a ring and a phenanthrene ring.
  • the condensed polycyclic aromatic group is a group obtained by condensing a plurality of aromatic rings.
  • the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring) and an aromatic heterocyclic ring (for example, a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, or an imidazole ring).
  • Component A contains a condensed polycyclic aromatic group (condensed polycyclic aromatic structure), and this group is preferably contained as a main component.
  • the main component means that the molecular weight content of the condensed polycyclic aromatic group is 30% or more with respect to the total molecular weight of Component A, and is preferably 40% or more.
  • the upper limit is not particularly limited, but is preferably 80% or less from the viewpoint of solubility.
  • the condensed polycyclic aromatic group is a ring structure formed by condensing a plurality of rings, and exhibits aromaticity.
  • the number of rings in the condensed polycyclic aromatic group in Component A is 4 or more, preferably 4 to 9, more preferably 4 to 7, and still more preferably 4 to 6 from the viewpoint of carrier mobility of the organic thin film transistor.
  • at least two rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and the carrier mobility of the organic thin film transistor From the viewpoint, it is preferable that 2 to 6 rings include the above atoms, and it is more preferable that 2 to 4 rings include the above atoms.
  • each heterocycle has one heteroatom.
  • the kind of the hetero atom is not particularly limited, and examples thereof include an O atom (oxygen atom), an S atom (sulfur atom), an N atom (nitrogen atom), or an Se atom (selenium atom).
  • the condensed polycyclic aromatic group in Component A includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure.
  • the partial structure preferably does not include an anthracene ring.
  • Component A preferably has at least a thiophene ring structure and / or a selenophene ring structure, more preferably at least a thiophene ring structure, from the viewpoint of carrier mobility of the organic thin film transistor, and a heterocyclic structure of component A It is more preferable that all have a thiophene ring structure.
  • the condensed polycyclic aromatic group includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure from the viewpoint of carrier mobility of an organic thin film transistor,
  • a condensed polycyclic aromatic group containing the above thiophene ring and having 4 or more rings is preferable.
  • a condensed polycyclic aromatic group containing a benzene ring, 2 or more thiophene rings, and 4 or more rings is more preferable as the partial structure.
  • the number of thiophene rings in the condensed polycyclic aromatic group is preferably 3 or more, more preferably 3 to 5, Three to four are more preferable, and three are particularly preferable. Further, from the viewpoint of carrier mobility of the organic thin film transistor, the number of rings in the condensed polycyclic aromatic group is preferably 4 to 6, more preferably 5 to 6, and still more preferably 5.
  • the condensed polycyclic aromatic group is particularly preferably a condensed polycyclic aromatic group containing two benzene rings and three thiophene rings and having 5 rings.
  • the condensed polycyclic aromatic group includes a ring (heterocycle, preferably a thiophene ring) containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and benzene.
  • a ring is alternately condensed (condensed) (a group formed by condensation) is preferable.
  • Component A preferably contains at least one compound represented by any one of formulas (1) to (16) from the viewpoint of carrier mobility of the organic thin film transistor, and includes formula (1) to formula (16). It is more preferable that it is 1 or more types of compounds represented by either.
  • the organic semiconductor layer may contain only one type of component A or two or more types of component A.
  • a 1a and A 1b each independently represents an S atom, an O atom or a Se atom
  • R 1a to R 1f each independently represents a hydrogen atom or a substituent
  • R 1a to R 1f At least one of them is a group represented by the following formula (W).
  • L W represents a divalent linking group represented by any of the following formulas (L-1) to (L-25), or two or more of the following formulas (L-1) to (L- represents a divalent linking group is a divalent linking group represented by any one bound of 25)
  • R W is an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number of oxyethylene units v represents an oligooxyethylene group having 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.
  • X 2a and X 2b each independently represent NR 2i , O atom or S atom
  • a 2a represents CR 2g or N atom
  • a 2b represents CR 2h or N atom
  • R 2 2i represents a hydrogen atom
  • an alkyl group an alkenyl group, an alkynyl group or an acyl group
  • R 2a to R 2h each independently represents a hydrogen atom or a substituent
  • at least one of R 2a to R 2h is represented by the above formula ( W).
  • X 3a and X 3b each independently represent an S atom, an O atom or NR 3g
  • a 3a and A 3b each independently represent a CR 3h or an N atom.
  • R 3a to R 3h each independently represents a hydrogen atom or a substituent, and at least one of R 3a to R 3h is a group represented by the above formula (W).
  • X 4a and X 4b each independently represent an O atom, an S atom or a Se atom
  • 4p and 4q each independently represents an integer of 0 to 2
  • R 4a to R 4j , R 4k and R 4m each independently represent a hydrogen atom, a halogen atom or a group represented by the above formula (W)
  • at least one of R 4a to R 4j , R 4k and R 4m is represented by the above formula ( a group represented by W)
  • L W is a divalent linking group represented by the above formula (L-2) or (L-3).
  • X 5a and X 5b each independently represent NR 5i , O atom or S atom
  • a 5a represents CR 5g or N atom
  • a 5b represents CR 5h or N atom
  • R 5 5i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group
  • R 5a to R 5h each independently represents a hydrogen atom or a substituent
  • R 5a to R 5h At least one of them is a group represented by the above formula (W).
  • X 6a to X 6d each independently represents NR 6g , O atom or S atom
  • R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl
  • R 6a to R 6f each independently represents a hydrogen atom or a substituent, and at least one of R 6a to R 6f is a group represented by the above formula (W).
  • X 7a and X 7c each independently represents an S atom, O atom, Se atom or NR 7i
  • X 7b and X 7d each independently represent an S atom, O atom or Se atom.
  • R 7a to R 7i each independently represents a hydrogen atom or a substituent, and at least one of R 7a to R 7i is a group represented by the above formula (W).
  • X 8a and X 8c each independently represent an S atom, O atom, Se atom or NR 8i
  • X 8b and X 8d each independently represent an S atom, O atom or Se atom.
  • R 8a to R 8i each independently represents a hydrogen atom or a substituent, and at least one of R 8a to R 8i is a group represented by the above formula (W).
  • X 9a and X 9b each independently represent an O atom, an S atom or a Se atom
  • R 9c , R 9d and R 9g to R 9j each independently represent a hydrogen atom, a halogen atom or the above
  • the group represented by the formula (W) is represented, and R 9a , R 9b , R 9e and R 9f each independently represent a hydrogen atom or a substituent.
  • R 10a to R 10h each independently represents a hydrogen atom or a substituent, and at least one of R 10a to R 10h represents a substituent represented by the above formula (W), 10a and X 10b each independently represent an S atom, an O atom, a Se atom or NR 10i , and R 10i each independently represents a hydrogen atom or a group represented by the above formula (W).
  • X 11a and X 11b each independently represent an S atom, O atom, Se atom or NR 11n
  • R 11a to R 11k , R 11m and R 11n each independently represent a hydrogen atom or a substituent
  • at least one of R 11a to R 11k , R 11m and R 11n is a group represented by the above formula (W).
  • X 12a and X 12b each independently represent an S atom, an O atom, a Se atom or NR 12n
  • R 12a to R 12k , R 12m and R 12n each independently represent a hydrogen atom or a substituent
  • at least one of R 12a to R 12k , R 12m and R 12n is a group represented by the above formula (W).
  • X 13a and X 13b each independently represent an S atom, an O atom, a Se atom or NR 13n
  • R 13a to R 13k , R 13m and R 13n each independently represent a hydrogen atom or a substituent
  • at least one of R 13a to R 13k , R 13m and R 13n is a group represented by the above formula (W).
  • X 14a to X 14c each independently represents an S atom, O atom, Se atom or NR 14i
  • R 14a to R 14i each independently represents a hydrogen atom or a substituent
  • R 14a At least one of ⁇ R 14i is a group represented by the above formula (W).
  • X 15a to X 15d each independently represents an S atom, an O atom, a Se atom, or NR 15g
  • R 15a to R 15g each independently represents a hydrogen atom or a substituent
  • R 15a At least one of ⁇ R 15g is a group represented by the above formula (W).
  • X 16a to X 16d each independently represents an S atom, an O atom, a Se atom or NR 16g
  • R 16a to R 16g each independently represents a hydrogen atom or a substituent
  • R 16a At least one of ⁇ R 16g is a group represented by the above formula (W).
  • a 1a and A 1b each independently represent an S atom (sulfur atom), an O atom (oxygen atom), or an Se atom (selenium atom).
  • a 1a and A 1b are preferably S atoms or O atoms.
  • a 1a and A 1b may be the same or different from each other, but are preferably the same.
  • R 1a to R 1f each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1f is a group represented by the following formula (W).
  • the compound represented by Formula (1) may have other substituents other than the group represented by Formula (W) described later.
  • the type of substituent that can be taken by R 1a to R 1f in formula (1) is not particularly limited, and examples thereof include substituent X described below.
  • substituent X a group represented by the formula (W) described later, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group), an alkenyl group (a cycloalkenyl group, Or a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (also referred to as a heterocyclic group), a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an aryloxy group, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group
  • examples of the “substituent” preferably include the above-described substituent X.
  • substituent X as a group other than the group represented by the formula (W) described later, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, or an aryl group is preferable, and a fluorine atom, carbon A substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted carbon group having 1 to 2 carbon atoms A substituted alkoxy group, a substituted or unsubstituted methylthio group, or a phenyl group is more preferable, and
  • a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted group
  • Particularly preferred methylthio group is.
  • R 1a to R 1f the number of other substituents other than the group represented by the formula (W) is preferably 0 to 4, and 0 to 2 Is more preferable, and 0 is particularly preferable. These substituents may further have the above substituent X.
  • R 1c to R 1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or 2 to 3 carbon atoms.
  • 3 is preferably a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group.
  • L represents a divalent linking group represented by any of the following formulas (L-1) to (L-25), or two or more of the following formulas (L-1) to (L And a divalent linking group to which the divalent linking group represented by any one of -25) is bonded.
  • Formula (L-13) ⁇ formula (L-24) binding to the binding position and R W of R 'at the position * may take any position on the aromatic ring or a heteroaromatic ring.
  • R ′ each independently represents a hydrogen atom or a substituent.
  • RN represents a hydrogen atom or a substituent.
  • R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
  • Formula (L-1) and formula (L-2) R 'in may form a condensed ring by combining with R W adjacent L W respectively.
  • the divalent linking group represented by any of the formulas (L-17) to (L-21), (L-23), and (L-24) is represented by the following formula (L- 17A) to the formula (L-21A), the formula (L-23A), and the divalent linking group represented by the formula (L-24A) are more preferable.
  • a substituted or unsubstituted alkyl group an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group.
  • a substituted trialkylsilyl group is present at the terminal of the substituent, it can be interpreted as -R W alone in the formula (W), or can be interpreted as -L W -R W in the formula (W). .
  • formula (W) when a substituted or unsubstituted alkyl group having N carbon atoms in the main chain is present at the terminal of the substituent, formula (W) after including all possible linking groups from the terminal of the substituent.
  • -L W -R W in the formula specifically, “one group represented by the formula (L-1) corresponding to L W in the formula (W)” and “R in the formula (W)” This is interpreted as a substituent in which the main chain corresponding to W is bonded to a substituted or unsubstituted alkyl group having N-1 carbon atoms.
  • an n-octyl group which is an alkyl group having 8 carbon atoms
  • one group represented by the formula (L-1) in which two R ′ are hydrogen atoms This is interpreted as a substituent bonded to the n-heptyl group of Formula 7.
  • a group is present at the end of the substituents on including a linking group as possible from the end of the substituent, it is interpreted as R W alone in the formula (W).
  • R W alone in the formula (W).
  • a — (OCH 2 CH 2 ) — (OCH 2 CH 2 ) — (OCH 2 CH 2 ) —OCH 3 group is present at the end of the substituent, an oligooxyethylene having a repeating number v of oxyethylene units of 3 Interpreted as a single group substituent.
  • formula (L-1) to formula (L-25) ) Is preferably 2 to 4, more preferably 2 or 3.
  • the substituent R ′ in the formula (L-1), the formula (L-2), the formula (L-6), and the formula (L-13) to the formula (L-24) is represented by the above formula (1).
  • the substituent R ′ in the formula (L-6) is preferably an alkyl group.
  • the alkyl group has 1 to It is preferably 9, more preferably 4 to 9 from the viewpoint of chemical stability and carrier transport properties, and further preferably 5 to 9.
  • the alkyl group is preferably a linear alkyl group from the viewpoint of improving carrier mobility.
  • R N represents a hydrogen atom or a substituent
  • examples of R N may be mentioned those exemplified as R 1a ⁇ substituent R 1f may take the above formula (1).
  • R N a hydrogen atom or a methyl group is preferable.
  • R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and is preferably an alkyl group.
  • the alkyl group that R si can take is not particularly limited, but the preferred range of the alkyl group that R si can take is the preferred range of the alkyl group that the trialkylsilyl group can take when R is a trialkylsilyl group. It is the same.
  • the alkenyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group has 2 to 3 carbon atoms.
  • the alkynyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a branched alkynyl group, and the alkynyl group has 2 to 3 carbon atoms. preferable.
  • L W represents a divalent linking group represented by any of formulas (L-1) to (L-5), formula (L-13), formula (L-17), or formula (L-18). Or a divalent linking group represented by any of formulas (L-1) to (L-5), formula (L-13), formula (L-17) or formula (L-18) It is preferably a divalent linking group in which two or more are bonded, and represented by any one of the formulas (L-1), (L-3), (L-13), and (L-18) A divalent linking group or two or more divalent linking groups represented by any of formula (L-1), formula (L-3), formula (L-13) or formula (L-18) are bonded.
  • There divalent linking group bonded is preferably a divalent linking group represented by the formula (L-1) binds to R W side.
  • L W the chemical stability, particularly preferable from the viewpoint of carrier transportability is a divalent linking group containing a divalent linking group represented by the formula (L-1), formula (L- more particularly preferably a divalent linking group represented by 1), L W is a divalent linking group represented by the formula (L-1), R W is a substituted or unsubstituted alkyl group Most preferably.
  • R W represents a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, a siloxane group, It represents an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group.
  • R W when L W adjacent to R W is a divalent linking group represented by the formula (L-1), R W is a substituted or unsubstituted alkyl group, oxyethylene group, It is preferably an oligooxyethylene group having 2 or more repeating oxyethylene units, a siloxane group, or an oligosiloxane group having 2 or more silicon atoms, and more preferably a substituted or unsubstituted alkyl group.
  • L W adjacent to R W is a divalent linking group represented by any of formulas (L-2) or formula (L-4) ⁇ formula (L-25) is , R W is more preferably a substituted or unsubstituted alkyl group.
  • R W when L W adjacent to R W is a divalent linking group represented by Formula (L-3), R W is a substituted or unsubstituted alkyl group, or substituted or unsubstituted. It is preferably a substituted trialkylsilyl group.
  • R W is a substituted or unsubstituted alkyl group, it preferably has a carbon number of 4-17, it is chemically stable is 6 to 14, more preferably from the viewpoint of carrier transportability, 6-12 More preferably it is.
  • R is preferably a long-chain alkyl group in the above-mentioned range, particularly a long-chain straight-chain alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility. If R W represents an alkyl group, a straight-chain alkyl group, even branched alkyl group, it may be a cyclic alkyl group, a straight-chain alkyl groups, increases the linearity of the molecules, to increase the carrier mobility It is preferable from the viewpoint that can be achieved.
  • R W and L W in formula (W), wherein (1) is a divalent linking group L W is represented by formula (L-1), and, R W Is a linear alkyl group having 7 to 17 carbon atoms, or L W is represented by any one of formula (L-3), formula (L-13), or formula (L-18).
  • R W is a straight chain alkyl group
  • L W is a divalent linking group represented by the formula (L-1)
  • R W is an alkyl group having 7-17 carbon atoms of straight-chain
  • the number of carbon atoms of R W is a linear 7
  • a linear alkyl group having 7 to 12 carbon atoms is particularly preferable.
  • L W is a divalent linking group represented by any one of formula (L-3), formula (L-13) or formula (L-18) and a divalent represented by formula (L-1) is a divalent linking group linking group is attached the, and, if R W is a straight chain alkyl group, more preferably R W is an alkyl group having a carbon number of 4 to 17 linear, straight
  • the chain is preferably an alkyl group having 6 to 14 carbon atoms from the viewpoint of chemical stability and carrier transportability, and the straight chain alkyl group having 6 to 12 carbon atoms is from the viewpoint of increasing carrier mobility. Particularly preferred.
  • R W is a branched alkyl group.
  • R W is an alkyl group having a substituent
  • a halogen atom a fluorine atom is preferable. It is also possible if R W is an alkyl group having a fluorine atom is substituted for all the hydrogen atoms of the alkyl group fluorine atom to form a perfluoroalkyl group. However, it is preferred that R W is an unsubstituted alkyl group.
  • R W is a number of repetitions is more than one oligo oxyethylene group of oxyethylene groups, herein and R represents "oligooxyethylene group", - represented by (OCH 2 CH 2) v -OY It refers to a group (the repeating number v of oxyethylene units represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group.
  • the number of repeating oxyethylene units v is preferably 2 to 4, and more preferably 2 to 3.
  • the terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent.
  • the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. More preferred is a methyl group.
  • R W is a siloxane group, or, when the number of silicon atoms is two or more oligosiloxane groups, the number of repetitions of the siloxane units is preferably from 2 to 4, more preferably 2-3.
  • a hydrogen atom or an alkyl group is preferably bonded to the silicon atom (Si atom).
  • the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded.
  • the same alkyl group may be bonded to the silicon atom, or a different alkyl group or a hydrogen atom may be bonded thereto.
  • all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.
  • R W adjacent to R W is a divalent linking group represented by the formula (L-3), it is also preferred R W is a substituted or unsubstituted trialkylsilyl group. It Among them if R W is a substituted or unsubstituted trialkylsilyl group, examples of the substituent of the silyl group is not particularly limited as long as it is a substituted or unsubstituted alkyl group, a branched alkyl group Is more preferable.
  • the alkyl group bonded to the silicon atom preferably has 1 to 3 carbon atoms. For example, a methyl group, an ethyl group, or an isopropyl group is preferably bonded. The same alkyl group may be bonded to the silicon atom, or different alkyl groups may be bonded to it.
  • the substituent when R W is a trialkylsilyl group having a substituent on the alkyl group is not particularly limited.
  • the total number of carbon atoms contained in L W and R W is preferably 5 to 18.
  • the carrier mobility is increased and the driving voltage is decreased.
  • the total number of carbon atoms contained in L W and R W is not more than the upper limit of the above range, solubility in an organic solvent is increased.
  • the total number of carbon atoms contained in L W and R W is preferably 5 to 14, more preferably 6 to 14, still more preferably 6 to 12, and preferably 8 to 12. Particularly preferred.
  • the number of groups represented by the formula (W) is preferably 1 to 4, and preferably 1 to 2. More preferably, it is particularly preferably 2.
  • R 1a and R 1b are preferably a group represented by formula (W). These positions are preferred as the substitution positions in the formula (1) because of the excellent chemical stability of the compound, the highest occupied orbital (HOMO) level, and also from the viewpoint of packing of molecules in the film. This is probably because of this.
  • a high carrier concentration can be obtained by using two positions of R 1a and R 1b as substituents.
  • R 1c to R 1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms. And a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group.
  • X 2a and X 2b each independently represent NR 2i (> N—R 2i ), an O atom or an S atom.
  • X 2a and X 2b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis.
  • X 2a and X 2b are preferably the same linking group. It is more preferable that both X 2a and X 2b are S atoms.
  • R 2i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and a carbon number of 1 Particularly preferred is an alkyl group of ⁇ 4.
  • R 2i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
  • a 2a represents CR 2g or an N atom
  • a 2b represents CR 2h or an N atom
  • R 2g and R 2h each independently represent a hydrogen atom or a substituent.
  • a 2a is CR 2 g, preferably A 2b is CR 2h
  • a 2a is CR 2 g, and more preferably A 2b is CR 2h.
  • a 2a and A 2b may be the same or different from each other, but are preferably the same.
  • R 2e and R 2g may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring. .
  • R 2f and R 2h may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring. .
  • R 2a to R 2h each independently represent a hydrogen atom or a substituent, and at least one represents a substituent represented by formula (W).
  • substituents that R 2a to R 2h can independently take include the substituent X described above.
  • the definition of the substituent represented by the formula (W) is as described above.
  • R 2a to R 2h each independently represents a substituent represented by an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula (W)
  • a heterocyclic group having 5 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable, a group having a linking group chain length of 3.7 ⁇ or less, or a group represented by the formula ( The group represented by W) is particularly preferred, and the group represented by formula (W) is more particularly preferred.
  • R 2a to R 2h 1 to 4 groups represented by the formula (W) increase carrier mobility and solubility in an organic solvent. From the viewpoint of increasing the number, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but R 2e or R 2f increases carrier mobility and increases solubility in an organic solvent. It is preferable from the viewpoint.
  • the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
  • a group having a linking group chain length of 1.0 to 3.7 mm is more preferable, and a group having a linking group chain length of 1.0 to 2.1 mm is more preferable.
  • the linking group chain length refers to the length from the C atom to the terminal of the substituent R in the C (carbon atom) -R bond.
  • the structure optimization calculation can be performed using a density functional method (Gaussian 03 (Gaussian, USA) / basis function: 6-31G * , exchange correlation functional: B3LYP / LANL2DZ).
  • the propyl group is 4.6 ⁇
  • the pyrrole group is 4.6 ⁇
  • the propynyl group is 4.5 ⁇
  • the propenyl group is 4.6 ⁇
  • the ethoxy group is 4.5 ⁇
  • the methylthio group Is 3.7 ⁇
  • the ethenyl group is 3.4 ⁇
  • the ethyl group is 3.5 ⁇
  • the ethynyl group is 3.6 ⁇
  • the methoxy group is 3.3 ⁇
  • the methyl group is 2.1 ⁇
  • the hydrogen atom is 1.0 ⁇ .
  • R 2a to R 2h are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms.
  • R 2a to R 2h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group
  • methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
  • R 2a to R 2h are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms
  • the substituents that the alkynyl group can take are as follows: And deuterium atoms.
  • Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
  • R 2a to R 2h are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, And deuterium atoms.
  • Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
  • R 2a to R 2h are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms
  • the substituents that the acyl group can take are as follows: And a fluorine atom.
  • the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
  • R 3a to R 3f and R 3g and R 3h described later each independently represent a hydrogen atom or a substituent.
  • at least one of R 3a to R 3h represents a group represented by the formula (W).
  • the substituent represented by R 3a to R 3h include the above-described substituent X.
  • the definition of the group represented by the formula (W) is as described above.
  • R 3a to R 3f can independently take, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula (W) is preferable.
  • a heterocyclic group having 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable.
  • X 3a and X 3b each independently represent an S atom, an O atom or NR 3g (> N—R 3g ), and R 3g represents a hydrogen atom or a substituent.
  • X is preferably an S atom or an O atom.
  • X 3a and X 3b are preferably the same.
  • R 3g is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 4 to 12 carbon atoms.
  • R 3g is a long-chain alkyl group within the above range, particularly a long-chain linear alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
  • R 3g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
  • a 3a and A 3b each independently represent CR 3h or an N atom, and preferably represents CR 3h .
  • a 3a and A 3b may be the same or different from each other, but are preferably the same.
  • R 3h is preferably a group having a linking group chain length of 3.7 mm or less, more preferably a group having a linking group chain length of 1.0 to 3.7 mm, and a linking group chain length of 1.0 to 3.7 mm. More preferably, it is a 2.1 ⁇ group.
  • the definition of the linking group chain length is as described above.
  • R 3h is a hydrogen atom, a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted alkynyl group having 2 or less carbon atoms, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a carbon number It is preferably a substituted or unsubstituted acyl group having 2 or less, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 2 or less carbon atoms, and particularly preferably a hydrogen atom.
  • R 3h represents a substituted alkyl group having 2 or less carbon atoms
  • substituent that the alkyl group can take include a cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by R 3h is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group, more preferably a methyl group or a cyano group-substituted methyl group, A group-substituted methyl group is particularly preferred.
  • R 3h represents a substituted alkynyl group having 2 or less carbon atoms
  • examples of the substituent that the alkynyl group can take include a deuterium atom.
  • examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by R 3h include an ethynyl group or a deuterium atom-substituted acetylene group, and an ethynyl group is preferable.
  • R 3h represents a substituted alkenyl group having 2 or less carbon atoms
  • examples of the substituent that the alkenyl group can take include a deuterium atom.
  • Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by R 3h include an ethenyl group or a deuterium atom-substituted ethenyl group, and an ethenyl group is preferable.
  • R 3h represents a substituted acyl group having 2 or less carbon atoms
  • examples of the substituent that the acyl group can take include a fluorine atom.
  • Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by R 3h include a formyl group, an acetyl group, and a fluorine-substituted acetyl group, and a formyl group is preferable.
  • X 4a and X 4b each independently represent an O atom, an S atom, or a Se atom.
  • X 4a and X 4b are each independently preferably an O atom or an S atom, and at least one of X 4a and X 4b is preferably an S atom, more preferably from the viewpoint of increasing carrier mobility.
  • X 4a and X 4b are preferably the same linking group. It is particularly preferred that both X 4a and X 4b are S atoms.
  • 4p and 4q each independently represents an integer of 0 to 2.
  • R 4a to R 4k and R 4m each independently represent a hydrogen atom, a halogen atom, or a group represented by the formula (W), and R 4a to R 4k and R 4m At least one of them is a group represented by the formula (W), provided that when at least one of R 4e and R 4f is a group represented by the formula (W), R 4e and R 4f are In the formula (W), L W is a divalent linking group represented by the above formula (L-2) or formula (L-3).
  • the definition of group represented by Formula (W) is as above-mentioned.
  • R 4e and R 4f are a group represented by the formula (W) corresponds to the case where either one of R 4e and R 4f is neither a hydrogen atom nor a halogen atom.
  • L W is represented by the above formula (L-3).
  • a divalent linking group is preferred. If at least one of R 4e and R 4f are groups represented by the formula (W), R 4e and R 4f are preferably both a group represented by the formula (W).
  • R 4e and R 4f are both hydrogen atoms or halogen atoms
  • R 4a to R 4d , R 4g to R 4k and R 4m are each independently represented by a hydrogen atom, a halogen atom or formula (W).
  • at least one of R 4a to R 4d , R 4g to R 4k and R 4m is a group represented by the formula (W).
  • examples of the halogen atom represented by R 4a to R 4k and R 4m include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and may be a fluorine atom, a chlorine atom or a bromine atom. Preferably, it is a fluorine atom or a chlorine atom, more preferably a fluorine atom.
  • the halogen atom is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 More preferably, it is particularly preferably 0.
  • the number of the group represented by the formula (W) is 1 to 4, which increases the carrier mobility and increases the organic solvent. From the viewpoint of increasing the solubility in water, 1 or 2 is more preferable, and 2 is particularly preferable.
  • the position of the group represented by the formula (W) is not particularly limited.
  • R 4a , R 4d to R 4g , R 4j , R 4k and R 4m are each independently a hydrogen atom or a halogen atom
  • R 4b , R 4c , R 4 4h and R 4i are each independently a hydrogen atom, a halogen atom or a group represented by formula (W)
  • at least one of R 4b , R 4c , R 4h and R 4i is represented by formula (W) Is preferable from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent.
  • R 4a , R 4c to R 4h and R 4j each independently represent a hydrogen atom or a halogen atom
  • R 4b and R 4i each independently represent a hydrogen atom, a halogen atom or a formula (W). More preferably, at least one of the groups is a group represented by the formula (W).
  • both R 4b and R 4i are groups represented by the formula (W)
  • R 4c and R 4h are both hydrogen atoms or halogen atoms
  • R 4c and R 4h are both represented by the formula (W More preferably, R 4b and R 4i are both a hydrogen atom or a halogen atom.
  • both R 4b and R 4i are groups represented by the formula (W), and R 4c and R 4h are both hydrogen atoms or halogen atoms, or R 4c and R 4h are both represented by the formula (W It is particularly preferred that R 4b and R 4i are both hydrogen atoms or halogen atoms.
  • R 4a to R 4k and R 4m may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but may be bonded to each other to form a ring. It is preferable not to form them.
  • X 5a and X 5b each independently represent NR 5i , an O atom, or an S atom.
  • X 5a and X 5b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis.
  • at least one of X 5a and X 5b is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 5a and X 5b are preferably the same linking group. It is more preferable that both X 5a and X 5b are S atoms.
  • R 5i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, Or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
  • R 5i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
  • a 5a represents CR 5g or an N atom
  • a 5b represents CR 5h or an N atom
  • R 5g and R 5h each independently represent a hydrogen atom or a substituent.
  • a 5a is CR 5 g, preferably A 5b is CR 5h, A 5a it is more preferably CR 5 g and A 5b is CR 5h.
  • a 5a and A 5b may be the same or different from each other, but are preferably the same.
  • R 5e and R 5g may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • R 5e and R 5i may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • R 5f and R 5h may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • R 5f and R 5i may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • R 5a to R 5h each independently represents a hydrogen atom or a substituent, and at least one of R 5a to R 5h is a group represented by formula (W).
  • R 5a to R 5h examples include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • R 5a to R 5h 1 to 4 groups represented by the formula (W) increase carrier mobility and dissolve in an organic solvent. From the viewpoint of enhancing the properties, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but R 5e or R 5f increases carrier mobility and solubility in an organic solvent. It is preferable from the viewpoint.
  • the number of substituents other than the group represented by formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
  • R 5a to R 5h are substituents other than the group represented by the formula (W)
  • the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1
  • the group is more preferably a group having a length of 0.0 to 3.7 mm, and further preferably a group having a linking group chain length of 1.0 to 2.1 mm.
  • the definition of the linking group chain length is as described above.
  • the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted group having 2 or less carbon atoms.
  • It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms.
  • R 5a to R 5h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group
  • methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
  • R 5a to R 5h are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms
  • the substituents that the alkynyl group can take are as follows: And deuterium atoms.
  • the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent is an ethynyl group or a deuterium atom-substituted acetylene group. And an ethynyl group is preferred.
  • R 5a to R 5h are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, And deuterium atoms.
  • Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
  • R 5a to R 5h are substituents other than the group represented by formula (W)
  • each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms
  • the substituents that the acyl group can take are as follows: And a fluorine atom.
  • the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
  • X 6a to X 6d each independently represents NR 6g , O atom or S atom
  • R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl.
  • X 6a to X 6d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis.
  • X 6a to X 6d are preferably the same linking group.
  • X 6a to X 6d are more preferably S atoms.
  • R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, and is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, An alkyl group is more preferable, an alkyl group having 1 to 14 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
  • R 6g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
  • R 6a to R 6f each independently represents a hydrogen atom or a substituent, and at least one represents a group represented by formula (W).
  • substituent represented by R 6a to R 6f include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • R 6a to R 6f each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a formula (W).
  • a heterocyclic group having 5 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable, a group having a linking group chain length of 3.7 ⁇ ⁇ or less, A group represented by (W) is more preferred, and a group represented by formula (W) is particularly preferred.
  • the number of groups represented by formula (W) is 1 to 4, which increases carrier mobility and dissolves in an organic solvent. From the viewpoint of enhancing the properties, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but is preferably R 6c to R 6f , and is preferably R 6e or R 6f. Is more preferable from the viewpoint of increasing the solubility in organic solvents.
  • the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
  • the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and further preferably a group having a linking group chain length of 1.0 to 2.1 mm.
  • the definition of the linking group chain length is as described above.
  • R 6a to R 6f are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having a prime number of 2 or less, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms.
  • R 6a to R 6f are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group
  • methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
  • R 6a to R 6f are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms
  • the substituents that the alkynyl group can take are as follows: And deuterium atoms.
  • Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
  • R 6a to R 6f are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms. And deuterium atoms.
  • Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
  • R 6a to R 6f are substituents other than the group represented by formula (W)
  • each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms
  • the substituents that the acyl group can take are as follows: And a fluorine atom.
  • the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
  • X 7a and X 7c each independently represents an S atom, an O atom, a Se atom or NR 7i (> N—R 7i ), and X 7b and X 7d each independently represent an S atom, O atom or Se atom is represented.
  • X 7a to X 7d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis.
  • at least one of X 7a to X 7d is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 7a to X 7d are preferably the same linking group.
  • X 7a to X 7d are more preferably S atoms.
  • R 7a to R 7i each independently represents a hydrogen atom or a substituent, and at least one of R 7a to R 7i is a group represented by formula (W).
  • substituent represented by R 7a to R 7i include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • R 7i is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
  • R 7i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred from the viewpoint of overlapping HOMO orbitals.
  • R 7a to R 7i 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but R 7d or R 7h increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 7d and R 7h are more preferable.
  • the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, Or it is more preferable that it is 1 piece, and it is especially preferable that it is 0 piece.
  • the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and even more preferably a group having a linking group chain length of 1.0 to 2.1 mm.
  • the definition of the linking group chain length is as described above.
  • R 7a to R 7i are substituents other than the group represented by formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted carbon group having 2 or less carbon atoms, It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms. More preferably, it is a group.
  • R 7a to R 7i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group
  • methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
  • R 7a to R 7i are substituents other than the group represented by formula (W)
  • each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms
  • the substituents that the alkynyl group can take are as follows: And deuterium atoms.
  • the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent is an ethynyl group or a deuterium atom-substituted acetylene group. And an ethynyl group is preferred.
  • R 7a to R 7i are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms. And deuterium atoms.
  • the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent includes an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
  • R 7a to R 7i are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms. And a fluorine atom.
  • the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by the formula (W) is a formyl group, an acetyl group, or a fluorine-substituted acetyl group And a formyl group is preferred.
  • X 8a and X 8c each independently represent an S atom, O atom, Se atom or NR 8i
  • X 8b and X 8d each independently represent an S atom, O atom or Se atom.
  • X 8a to X 8d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis.
  • at least one of X 8a to X 8d is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 8a to X 8d are preferably the same linking group. It is more preferable that all of X 8a to X 8d are S atoms.
  • R 8a to R 8i each independently represents a hydrogen atom or a substituent, and at least one of R 8a to R 8i is a group represented by formula (W).
  • substituent represented by R 8a to R 8i include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • R 8i is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
  • R 8i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferable from the viewpoint of overlapping HOMO orbitals.
  • R 8a to R 8i 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but R 8c or R 8g increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 8c and R 8g are more preferable.
  • the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is more preferable, and 0 is particularly preferable.
  • R 8a to R 8i are substituents other than the group represented by the formula (W)
  • the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and even more preferably a group having a linking group chain length of 1.0 to 2.1 mm.
  • the definition of the linking group chain length is as described above.
  • R 8a to R 8i are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted carbon group having 2 or less carbon atoms, It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms. More preferably, it is a group.
  • R 8a to R 8i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable.
  • the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group
  • methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
  • R 8a to R 8i are substituents other than the group represented by formula (W)
  • each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms
  • the substituents that the alkynyl group can take are as follows: And deuterium atoms.
  • Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
  • R 8a to R 8i are substituents other than the group represented by the formula (W)
  • each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms
  • the substituents that the alkenyl group can take are as follows: And deuterium atoms.
  • Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
  • R 8a to R 8i are substituents other than the group represented by formula (W)
  • each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms
  • the substituents that the acyl group can take are as follows: And a fluorine atom.
  • the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
  • X 9a and X 9b each independently represent an O atom, an S atom, or an Se atom. Among these, S atom is preferable.
  • R 9c , R 9d and R 9g to R 9j each independently represents a hydrogen atom, a halogen atom or a substituent represented by the formula (W).
  • the definition of the group represented by the formula (W) is as described above.
  • R 9a , R 9b , R 9e and R 9f each independently represent a hydrogen atom or a substituent.
  • the substituent X mentioned above is mentioned as a substituent represented by R ⁇ 9a > , R ⁇ 9b> , R ⁇ 9e> and R ⁇ 9f> .
  • R 9c , R 9d and R 9g to R 9j are each independently a hydrogen atom, a halogen atom or a group represented by the formula (W) (where L W is the formula (L-3), the formula (L— 5), a group represented by any one of formulas (L-7) to (L-9) and (L-12) to (L-24).
  • R 9c , R 9d and R 9g to R 9j are more preferably hydrogen atoms.
  • L W is a group represented by any one of formula (L-3), formula (L-5), formula (L-13), formula (L-17), or formula (L-18).
  • At least one of R 9a to R 9i preferably represents a group represented by the formula (W).
  • R 9a to R 9i 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
  • the position of the group represented by the formula (W) is not particularly limited, but R 9b or R 9f increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 9b and R 9f are more preferable.
  • the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is particularly preferable, and 0 is particularly preferable.
  • R 10a to R 10h each independently represents a hydrogen atom or a substituent, and at least one of R 10a to R 10h represents a group represented by formula (W).
  • R 10a to R 10h examples include the substituent X described above.
  • the definition of the substituent represented by Formula (W) is as above-mentioned.
  • R 10a to R 10h each independently represents a hydrogen atom, a halogen atom or a substituent, and at least one of R 10a to R 10h is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroary It is preferably a ruthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group.
  • R 10a to R 10h in the formula (10) are such that at least one of R 10b and R 10f is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group A substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, preferably a substituted or unsubstituted arylthio group or a substituted or unsubstituted heteroarylthio group.
  • each of R 10b and R 10f is more preferably a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroarylthio group, and a substituted or unsubstituted phenylthio group or the following group
  • a Particularly preferred is a heteroarylthio group selected from Most preferably, it is a substituted or unsubstituted phenylthio group or a heteroarylthio group represented by the following formula (A-17), formula (A-18), or formula (A-20).
  • the arylthio group is preferably a group having a sulfur atom linked to an aryl group having 6 to 20 carbon atoms, more preferably a naphthylthio group or a phenylthio group, and particularly preferably a phenylthio group.
  • the heteroarylthio group is preferably a group in which a sulfur atom is linked to a 3- to 10-membered heteroaryl group, more preferably a group in which a sulfur atom is linked to a 5- or 6-membered heteroaryl group.
  • a group represented by any one of formulas (A-14) to (A-27)) is particularly preferable.
  • R ′′ and R ′′ N each independently represent a hydrogen atom or a substituent.
  • each R ′ preferably independently represents a hydrogen atom or a group represented by the formula (W).
  • R ′′ N preferably represents a substituent, more preferably an alkyl group, an aryl group, or a heteroaryl group, and is substituted with an alkyl group, an aryl group substituted with an alkyl group, or an alkyl group.
  • the heteroaryl group is more preferably a 5-membered alkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
  • a heteroaryl group is particularly preferred.
  • the alkyloxycarbonyl group is preferably a group in which a carbonyl group is linked to an alkyl group having 1 to 20 carbon atoms.
  • the number of carbon atoms of the alkyl group is more preferably 2-15, and particularly preferably 5-10.
  • the aryloxycarbonyl group is preferably a group in which a carbonyl group is linked to an aryl group having 6 to 20 carbon atoms.
  • the number of carbon atoms of the aryl group is more preferably 6-15, and particularly preferably 8-12.
  • the alkylamino group is preferably a group in which an amino group is linked to an alkyl group having 1 to 20 carbon atoms.
  • the number of carbon atoms of the alkyl group is more preferably 2-15, and particularly preferably 5-10.
  • R 10a to R 10h a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted
  • the number of substituents other than the unsubstituted alkylamino group (hereinafter also referred to as other substituents) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
  • X 10a and X 10b each independently represent an S atom, an O atom, a Se atom, or NR x (> N—R x ). It is preferable from the viewpoint of increasing carrier mobility that at least one of X 10a and X 10b is an S atom. X 10a and X 10b are preferably the same linking group. As for X10a and X10b , it is more preferable that all are S atoms. R x each independently represents a hydrogen atom or a group represented by the formula (W). The definition of the group represented by the formula (W) is as described above.
  • X 11a and X 11b each independently represent an S atom, O atom, Se atom or NR 11n
  • R 11a to R 11k , R 11m and R 11n each independently represent a hydrogen atom or a substituent
  • at least one of R 11a to R 11k , R 11m and R 11n represents a group represented by the formula (W).
  • substituent include the substituent X described above.
  • the definition of the substituent represented by the formula (W) is as described above.
  • At least one of X 11a and X 11b is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 11a and X 11b are preferably the same linking group. It is more preferable that both X 11a and X 11b are S atoms.
  • R 11a to R 11k and R 11m in the formula (11) are such that at least one of R 11c and R 11i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group.
  • both R 11c and R 11i are more preferably substituted or unsubstituted alkyl groups.
  • X 12a and X 12b each independently represent an S atom, an O atom, a Se atom or NR 12n
  • R 12a to R 12k , R 12m and R 12n each independently represent a hydrogen atom or a substituent
  • at least one of R 12a to R 12k , R 12m and R 12n represents a group represented by the formula (W).
  • substituent include the substituent X described above.
  • the definition of the substituent represented by the formula (W) is as described above.
  • X 12a and X 12b are preferably the same linking group. It is more preferable that both X 12a and X 12b are S atoms.
  • R 12a to R 12k and R 12m in the formula (12) are such that at least one of R 12c and R 12i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group.
  • both R 12c and R 12i are more preferably substituted or unsubstituted alkyl groups.
  • X 13a and X 13b each independently represent an S atom, an O atom, a Se atom or NR 13n
  • R 13a to R 13k , R 13m and R 13n each independently represent a hydrogen atom or a substituent
  • at least one of R 13a to R 13k , R 13m and R 13n represents a group represented by the formula (W).
  • substituent include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • At least one of X 13a and X 13b is preferably an S atom, from the viewpoint of increasing carrier mobility.
  • X 13a and X 13b are preferably the same linking group. It is more preferable that both X 13a and X 13b are S atoms.
  • R 13a to R 13k and R 13m in the formula (13) are such that at least one of R 13c and R 13i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group.
  • both R 13c and R 13i are more preferably substituted or unsubstituted alkyl groups.
  • X 14a to X 14c each independently represents an S atom, O atom, Se atom or NR 14i
  • R 14a to R 14i each independently represents a hydrogen atom or a substituent
  • R 14a At least one of ⁇ R 14i represents a group represented by the formula (W).
  • substituent include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • L W is a formula (L-2) to a formula (L-25) It is preferable that it is group represented by either.
  • At least one of X 14a to X 14c is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 14a to X 14c are preferably the same linking group. It is more preferable that all of X 14a to X 14c are S atoms.
  • L W in the case where R W is an alkyl group is represented by Formula (L-2) to Formula (L-5), Formula (L-13), Formula (L-17), or Formula (L-18).
  • a group represented by any one of formula (L-3), formula (L-13), or formula (L-18) is more preferred.
  • R 14a ⁇ R 14h of formula (14), at least one of R 14b and R 14 g, is preferably a group represented by the formula (W), any of R 14b and R 14 g is represented by the formula ( More preferred is a group represented by W).
  • X 15a ⁇ X 15d each independently S atom, O atom, a Se atom or a NR 15g
  • R 15a ⁇ R 15g each independently represent a hydrogen atom or a substituent
  • R 15a ⁇ At least one of R 15g represents a group represented by the formula (W).
  • substituent include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • At least one of X 15a to X 15d is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 15a to X 15d are preferably the same linking group. It is more preferable that all of X 15a to X 15d are S atoms.
  • R 15a ⁇ R 15f of formula (15) at least one of R 15b and R 15e, is preferably a group represented by the formula (W), any of R 15b and R 15e is the formula ( More preferred is a group represented by W).
  • X 16a to X 16d each independently represents an S atom, an O atom, a Se atom, or NR 16g .
  • R 16a to R 16g each independently represents a hydrogen atom or a substituent, and at least one of R 16a to R 16g represents a group represented by the formula (W). Examples of the substituent include the substituent X described above.
  • the definition of the group represented by the formula (W) is as described above.
  • R 16c and R 16f are a hydrogen atom, a halogen atom or a group represented by the formula (W) (where L W is a formula (L-3), a formula (L-5), a formula (L-7 To a group represented by any one of formulas (L-9) and (L-12) to (L-24)).
  • R 16a , R 16b , R 16d , R 16e and R 16g each independently preferably represent a hydrogen atom or a substituent.
  • L W is expressed by Formula (L-3), Formula (L-5), Formula (L-7) to Formula (L-9), Formula (L-12) to Formula (L -24), and when R 16c and R 16f are groups represented by formula (W), formula (L-3), formula (L-5), formula (L- 13), a group represented by any of formulas (L-17) and (L-18) is preferable.
  • At least one of X 16a to X 16d is preferably an S atom from the viewpoint of increasing carrier mobility.
  • X 16a to X 16d are preferably the same linking group. It is more preferable that all of X 16a to X 16d are S atoms.
  • R 16a ⁇ R 16f of formula (16) at least one of R 16a and R 16d, is preferably a group represented by the formula (W), none of R 16a and R 16d is the formula ( More preferred is a group represented by W).
  • R 16c and R 16f are preferably hydrogen atoms.
  • Component A preferably has an alkyl group on the condensed polycyclic aromatic ring in the condensed polycyclic aromatic group, more preferably an alkyl group having 6 to 20 carbon atoms, and an alkyl group having 7 to 14 carbon atoms. More preferably, it has a group. It is excellent in the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.
  • Component A preferably has one or more alkyl groups on the condensed polycyclic aromatic ring in the above condensed polycyclic aromatic group, more preferably has 2 to 4 alkyl groups, and more preferably 2 alkyl groups. More preferably, it has a group. It is excellent in the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.
  • the molecular weight of component A is not particularly limited, but the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and 850 or less. Is particularly preferred. By making molecular weight below the said upper limit, the solubility to a solvent can be improved. On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.
  • the method for synthesizing component A is not particularly limited, and can be synthesized with reference to known methods.
  • Examples of the method for synthesizing the compounds represented by the above formulas (1) to (16) include, for example, Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), Org. Lett. , 2001, 3, 3471, Macromolecules, 2010, 43, 6264, Tetrahedron, 2002, 58, 10197, Japanese translations of PCT publication No. 2012-513659, JP 2011-46687A, Journal of Chemical Research. miniprint, 3, 601-635 (1991), Bull. Chem. Soc.
  • the component A contains at least one compound represented by any one of formulas (1) to (9), formula (14), or formula (15).
  • at least one compound represented by any one of formulas (1) to (9) or (15) is included.
  • the concentration of the organic semiconductor material in the composition for forming an organic semiconductor layer is not particularly limited, but is preferably 0.01 to 20% by weight, and preferably 0.1 to 10% by weight with respect to the total weight of the composition for forming an organic semiconductor layer. % Is more preferable, and 0.2 to 5% by mass is particularly preferable.
  • the solvent is not particularly limited as long as it dissolves or disperses the organic semiconductor material and / or the photoacid generating resin.
  • an organic solvent, water, and these mixed solvents are mentioned.
  • the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, tetralin, decalin, or 1-methylnaphthalene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone.
  • Ketone solvent halogenated hydrocarbon solvent such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, or chlorotoluene, ester solvent such as ethyl acetate, butyl acetate, or amyl acetate, Methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, or ethylene glycol Alcohol solvent such as dibutyl ether, ether solvent such as dibutyl ether, tetrahydrofuran, dioxane, or anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, or 1-methyl-2 -Amide / imide solvents
  • Organic solvents may be used alone or in combination of two or more.
  • organic solvent toluene, xylene, mesitylene, tetralin, methyl ethyl ketone, cyclopentanone, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, anisole, benzonitrile and the like are particularly preferable.
  • Organic semiconductor layer precursor layer forming method The method for applying these organic semiconductor layer forming compositions is not particularly limited, and a printing method such as inkjet printing, flexographic printing, gravure printing, or screen printing, or a spin coating method is preferable, and a spin coating method is more preferable.
  • the application conditions are not particularly limited. You may apply
  • the coating temperature is preferably 15 to 150 ° C., more preferably 15 to 100 ° C., further preferably 15 to 50 ° C., and particularly preferably around room temperature (20 to 30 ° C.).
  • the rotational speed is preferably set to 100 to 3000 rpm.
  • the applied organic semiconductor layer forming composition is preferably dried.
  • the drying conditions may be any conditions that can remove the solvent by volatilization, and examples include methods such as standing at room temperature, drying by heating, drying by blowing, or drying under reduced pressure.
  • the photoacid generating resin in the organic semiconductor layer precursor layer is cleaved, and the main chain portion having an acid anion in the side chain as a dopant And decomposition with a cation site.
  • the light (actinic ray or radiation) irradiation treatment examples include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • radiation examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • suitable forms include scanning irradiation with an infrared laser, irradiation with a high illuminance flash such as a xenon discharge lamp, or irradiation with an infrared lamp.
  • the irradiation time varies depending on the reactivity of the photoacid generating resin and the light source, but is usually between 10 seconds and 5 hours.
  • the irradiation energy may be about 10 to 8000 mJ, and is preferably in the range of 50 to 3000 mJ.
  • the organic semiconductor layer further forms an organic semiconductor layer precursor layer as at least two layers of an organic semiconductor material layer containing an organic semiconductor material and a photoacid generating resin layer containing a photoacid generating resin. It may be formed by irradiating the body layer with actinic rays or radiation.
  • the formation method of an organic-semiconductor material layer and a photo-acid generating resin layer is not specifically limited, Like the 1st aspect, by the formation solution containing an organic-semiconductor material, photo-acid generating resin, and the solvent which melt
  • the forming solution may contain other additives such as a solvent, a surfactant, or a binder resin.
  • concentration of the organic semiconductor material in the composition for forming an organic semiconductor material layer is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total mass of the composition for forming an organic semiconductor material layer, preferably 0.1 to 10% by mass is more preferable, and 0.2 to 5% by mass is particularly preferable.
  • concentration of the photoacid generating resin in the photoacid generating resin layer forming composition is not particularly limited. The amount is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 3% by mass based on the total mass of the product.
  • the method for applying these forming solutions is not particularly limited, and a printing method such as inkjet printing, flexographic printing, gravure printing, or screen printing or a spin coating method is preferable, and a spin coating method is more preferable.
  • the second embodiment can be carried out in the same manner as the first embodiment except as described above.
  • the substrate may be any substrate as long as it can support the OTFT and the display panel produced thereon.
  • the substrate is not particularly limited as long as the surface is insulative, has a sheet shape, and has a flat surface.
  • the substrate may be integrated with a gate electrode described later. That is, the substrate may also function as a gate electrode.
  • An inorganic material may be used as the material for the substrate.
  • a substrate made of an inorganic material for example, various glass substrates such as soda lime glass or quartz glass, various glass substrates having an insulating film formed on the surface, quartz substrates having an insulating film formed on the surface, Examples thereof include a silicon substrate on which an insulating film is formed, a sapphire substrate, stainless steel, aluminum, various alloys such as nickel, metal substrates made of these various metals, metal foil, or paper.
  • a conductive or semiconducting material such as stainless steel sheet, aluminum foil, copper foil or silicon wafer, an insulating polymer material or metal oxide is usually applied or laminated on the surface. Used.
  • the material of the substrate may be either an organic material or an inorganic material.
  • the organic material include polymethyl methacrylate (also referred to as polymethyl methacrylate or PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyether sulfone (PES), polyimide, polyamide, polyacetal, and polycarbonate (PC ), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethyl ether ketone, polyolefin, polycycloolefin, or a flexible plastic substrate composed of an organic polymer exemplified by an epoxy resin (plastic film or Also referred to as a plastic sheet). If such a flexible substrate or the like is used, for example, the OTFT can be incorporated or integrated into a display device or electronic device having a curved shape.
  • the glass transition point is preferably high, and the glass transition point is preferably 40 ° C. or higher.
  • the coefficient of linear expansion is small from the viewpoint that the dimensional change is hardly caused by the heat treatment at the time of manufacture and the transistor performance is stable.
  • a material having a linear expansion coefficient of 25 ⁇ 10 ⁇ 5 cm / cm ⁇ ° C. or less is preferable, and a material having a coefficient of 10 ⁇ 10 ⁇ 5 cm / cm ⁇ ° C. or less is more preferable.
  • the organic material constituting the substrate is preferably a material having resistance to a solvent used at the time of manufacturing the OTFT, and a material having excellent adhesion to the gate insulating layer and the electrode is preferable.
  • a plastic substrate made of an organic polymer having a high gas barrier property. It is also preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate, or to deposit or laminate an inorganic material.
  • a conductive substrate (a substrate made of metal such as gold or aluminum, a substrate made of highly oriented graphite, a stainless steel substrate, or the like) can also be cited.
  • a glass epoxy resin etc. can be mentioned as an organic inorganic composite.
  • an inorganic material what was formed with mica etc. can be used, for example.
  • a functional film such as a buffer layer for improving adhesion or flatness or a barrier film for improving gas barrier properties may be formed on the substrate.
  • a surface treatment layer such as an easy adhesion layer may be formed on the surface of the substrate, or a surface treatment such as corona treatment, plasma treatment or UV / ozone treatment may be performed.
  • the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. On the other hand, it is preferably 0.01 mm or more, and more preferably 0.05 mm or more. In particular, in the case of a plastic substrate, the thickness is preferably about 0.05 to 0.1 mm. In the case of a substrate made of an inorganic material, the thickness is preferably about 0.1 to 10 mm.
  • a conductive material (also referred to as an electrode material) constituting the gate electrode is not particularly limited.
  • metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, molybdenum, titanium, magnesium, calcium, barium, sodium, palladium, iron, or manganese; InO 2 , SnO 2 , indium / tin oxide
  • Conductive metal oxides such as (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), or gallium-doped zinc oxide (GZO); polyaniline, polypyrrole, polythiophene, polyacetylene, or poly (3 , 4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS), etc .; acid such as hydrochloric acid, sulfuric acid or sulf
  • the method of forming the gate electrode there is no limitation on the method of forming the gate electrode.
  • a film formed by physical vapor deposition (PVD) such as vacuum vapor deposition, chemical vapor deposition (CVD), sputtering, printing (coating), transfer, sol-gel, or plating,
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • sputtering sputtering
  • printing coating
  • transfer sol-gel
  • sol-gel sol-gel
  • plating A method of patterning to a desired shape as needed is mentioned.
  • a solution, paste or dispersion of the above materials is prepared to form a composition, and the resulting composition is coated and dried, and then a film is formed by treatment such as baking, photocuring or aging.
  • the electrodes can be formed directly.
  • ink-jet printing screen printing, (reversal) offset printing, letterpress printing, intaglio printing, planographic printing, thermal transfer printing, or microcontact printing can be performed with desired patterning, simplifying processes and reducing costs. Or, it is preferable in terms of speeding up.
  • a spin coating method, a die coating method, a micro gravure coating method, or a dip coating method is adopted, patterning can be performed in combination with the following photolithography method or the like.
  • Examples of the photolithography method include a method of combining a patterning of a photoresist and an etching such as a wet etching with an etching solution, a dry etching with a reactive plasma, a lift-off method, or the like.
  • a method of irradiating the material with an energy beam such as a laser or an electron beam to polish the material or changing the conductivity of the material may be used.
  • substrate is also mentioned.
  • the thickness of the gate electrode is arbitrary, but is preferably 1 nm or more, particularly preferably 10 nm or more. Moreover, 500 nm or less is preferable and 200 nm or less is especially preferable.
  • the gate insulating layer is not particularly limited as long as it is an insulating layer, and may be a single layer or a multilayer.
  • the gate insulating layer is preferably formed of an insulating material, and examples of the insulating material include organic polymers and inorganic oxides.
  • the organic polymer and the inorganic oxide may be used alone or in combination of two or more, or may be an organic-inorganic hybrid.
  • the organic polymer and the inorganic oxide are not particularly limited as long as they have insulating properties, but are preferably formed of an organic polymer or an organic-inorganic hybrid that can be applied.
  • the thickness of the gate insulating layer is arbitrary, but is preferably 10 nm to 10 ⁇ m, more preferably 50 nm to 5 ⁇ m, and particularly preferably 100 nm to 1 ⁇ m.
  • poly (meth) acrylate represented by polyvinylphenol (PVP), polystyrene (PS), polymethylmethacrylate, polyvinyl alcohol, polyvinyl chloride (PVC) , Cyclic fluoroalkyl polymers represented by polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), CYTOP (registered trademark, manufactured by Asahi Glass Co., Ltd.), polycycloolefin, polyester resin, polyethersulfone, polyetherketone, polyimide , Epoxy resins (including glass epoxy resins), polyorganosiloxanes typified by polydimethylsiloxane (PDMS), polysilsesquioxane, butadiene rubber, and the like.
  • PVP polyvinylphenol
  • PS polystyrene
  • PVC polyvinyl chloride
  • Cyclic fluoroalkyl polymers represented by polyvinylidene fluoride (PV
  • High-density polyethylene ethylene-vinyl acetate copolymer (EVA), polypropylene, acrylonitrile-butadiene-styrene resin (ABS resin), methacrylic resin, polyacetal, diallyl phthalate, ionomer, polyamide, polycarbonate, polyphenylene oxide, polysulfone, urea
  • the resin include melamine resin, cellulose acetate, silicon resin, urethane resin, and polybenzoxazole.
  • thermosetting resins such as phenol resin, novolac resin, cinnamate resin, acrylic resin, or polyparaxylylene resin are also included.
  • polyimide, polycycloolefin, polyacrylic acid, polyvinylphenol, polybenzoxazole, or the like can be preferably used.
  • a low dielectric constant fluorine-based material can also be preferably used as the organic polymer.
  • the organic polymer can be used in combination with a compound having a reactive substituent such as an alkoxysilyl group, a vinyl group, an acryloyloxy group, an epoxy group, or a methylol group.
  • the organic polymer is preferably crosslinked and cured for the purpose of increasing the solvent resistance or the insulation resistance of the gate insulating layer.
  • Crosslinking is preferably carried out by generating acid or radical using light, heat or both.
  • radical generator that generates radicals by light or heat
  • thermal polymerization initiators (H1) described in [0182] to [0186] of JP2013-214649A and photopolymerization initiation Agent (H2) photo radical generators described in JP-A-2011-186069, [0046] to [0051], or photo-radicals described in JP-A 2010-285518, [0042] to [0056]
  • Polymerization initiators and the like can be suitably used, and preferably the contents thereof are incorporated herein.
  • “Number average molecular weight (Mn) is 140 to 5,000, described in JP2013-214649A [0167] to [0177], has a crosslinkable functional group, and does not have a fluorine atom. It is also preferred to use "compound (G)", the contents of which are preferably incorporated herein.
  • a photoacid generator that generates an acid by light
  • a photocationic polymerization initiator described in [0033] to [0034] of JP2010-285518A or JP2012-2012A.
  • the acid generators described in [0120] to [0136] of JP-A-163946 can be used, and the contents thereof are preferably incorporated herein.
  • a sulfonium salt or an iodonium salt can be preferably used.
  • thermal acid generator that generates an acid by heat
  • a thermal cationic polymerization initiator particularly an onium salt
  • the catalysts especially sulfonic acids and sulfonic acid amine salts described in [0034] to [0035] of JP-A-2005-354012 can be preferably used, and the contents thereof are preferably incorporated herein.
  • a crosslinking agent (particularly a bifunctional or higher functional epoxy compound or oxetane compound) described in JP-A-2005-354012 [0032] to [0033], [0046]-[0062] in JP-A-2006-303465.
  • a compound having two or more crosslinking groups, and at least one of the crosslinking groups is a methylol group or an NH group
  • JP 2012-163946 A It is also preferable to use compounds having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule described in [0137] to [0145], the contents of which are preferably incorporated herein.
  • a method for forming the gate insulating layer with an organic polymer for example, there is a method in which an organic polymer is applied (coated) and then cured.
  • the coating method is not particularly limited, and examples thereof include the above printing methods. Of these, a wet coating method such as a micro gravure coating method, a dip coating method, a screen coating printing, a die coating method or a spin coating method is preferable.
  • the inorganic oxide is not particularly limited.
  • silicon oxide in addition to silicon oxide (SiO X ), BPSG (Boron Phosphorus Silicon Glass), PSG (Phosphorus Silicon Glass), BSG (Boron Silicon Glass), AsSG (As-doped silica glass) Silicon oxynitride (SiON) and SOG (spin on glass) are included.
  • a vacuum film formation method such as a vacuum evaporation method, a sputtering method, an ion plating method, a CVD method, or the like can be used.
  • Assist may be performed with the plasma, ion gun or radical gun used.
  • a precursor corresponding to each metal oxide specifically, a metal halide such as chloride or bromide, a metal alkoxide, or a metal hydroxide, such as hydrochloric acid, sulfuric acid or nitric acid in alcohol or water. You may form by reacting with an acid or bases, such as sodium hydroxide or potassium hydroxide, and hydrolyzing. When such a solution process is used, the above wet coating method can be used.
  • the gate insulating layer can also be provided by a method that combines any one of the lift-off method, the sol-gel method, the electrodeposition method, and the shadow mask method, and, if necessary, the patterning method.
  • the above-described organic polymers and organically modified inorganic fine particles may be used in combination.
  • the source electrode is an electrode through which current flows from the outside through the wiring.
  • the drain electrode is an electrode that sends current to the outside through wiring, and is usually provided in contact with the organic semiconductor layer.
  • a conductive material used in a conventional organic thin film transistor can be used, and examples thereof include the conductive material described for the gate electrode.
  • the source electrode and the drain electrode can be formed by a method similar to the method for forming the gate electrode, respectively.
  • a lift-off method or an etching method can be employed.
  • the source electrode and the drain electrode can be preferably formed by an etching method.
  • the etching method is a method of removing unnecessary portions by etching after forming a conductive material.
  • the conductive material remaining on the base when the resist is removed can be prevented, and the resist residue or the removed conductive material can be prevented from reattaching to the base, so that the shape of the electrode edge portion is excellent. This is preferable to the lift-off method.
  • a resist is applied to a part of the base, a conductive material is formed thereon, and the resist is removed together with the solvent by elution or peeling with a solvent.
  • This is a method of forming a film of a conductive material only on a portion where no is applied.
  • a source electrode and a drain electrode is arbitrary, 1 nm or more is preferable respectively and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
  • the interval (channel length) between the source electrode and the drain electrode is arbitrary, but is preferably 500 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
  • the channel width is preferably 5000 ⁇ m or less, and particularly preferably 1000 ⁇ m or less.
  • the OTFT of the present invention may have an overcoat layer.
  • the overcoat layer is usually a layer formed as a protective layer on the surface of the OTFT.
  • a single layer structure or a multilayer structure may be used.
  • the overcoat layer may be an organic overcoat layer or an inorganic overcoat layer.
  • the material for forming the organic overcoat layer is not particularly limited, but for example, an organic polymer such as polystyrene, acrylic resin, polyvinyl alcohol, polyolefin, polyimide, polyurethane, polyacetylene, or epoxy resin, or an organic polymer thereof. Examples thereof include a derivative in which a crosslinkable group or a water repellent group is introduced into the polymer.
  • organic polymers or derivatives thereof can be used in combination with a crosslinking component, a fluorine compound, a silicon compound, or the like.
  • the material for forming the inorganic overcoat layer is not particularly limited, and examples thereof include metal oxides such as silicon oxide and aluminum oxide, and metal nitrides such as silicon nitride. These materials may be used alone or in combination of two or more in any combination and ratio.
  • the organic overcoat layer is formed by, for example, applying a solution containing a material to be an overcoat layer to the underlying layer and then drying the solution containing the material to be an overcoat layer. It can be formed by a method such as patterning by exposure and development. Note that the patterning of the overcoat layer can also be directly formed by a printing method, an inkjet method, or the like. Further, the overcoat layer may be crosslinked by exposure or heating after the patterning of the overcoat layer.
  • the inorganic overcoat layer can be formed by a dry method such as a sputtering method or an evaporation method, or a wet method such as a sol-gel method.
  • the OTFT of the present invention may be provided with layers or members other than those described above.
  • Examples of other layers or members include banks.
  • the bank is used for the purpose of blocking the discharge liquid at a predetermined position when a semiconductor layer or an overcoat layer is formed by an inkjet method or the like. For this reason, the bank usually has liquid repellency.
  • Examples of the bank forming method include a method of performing liquid repellency treatment such as a fluorine plasma method after patterning by a photolithography method or the like, a method of curing a photosensitive composition containing a liquid repellent component such as a fluorine compound, and the like.
  • the method of curing the photosensitive composition containing the latter liquid repellent component may cause the gate insulating layer to be affected by the liquid repellent treatment.
  • a technique may be used in which a liquid repellent contrast is given to the base without using the bank so as to have the same role as the bank.
  • the OTFT of the present invention has a bottom gate / bottom contact structure shown in FIG. 1A, FIG. 1B shows a bottom gate / top contact structure, FIG. 1C shows a top gate / bottom contact structure, and FIG. 1D shows a top gate / top contact structure. It can also be applied to.
  • the OTFT of the present invention is preferably used by being mounted on a display panel.
  • the display panel include a liquid crystal panel, an organic EL panel, and an electronic paper panel.
  • composition for forming organic semiconductor layer The organic semiconductor material and the resin (hereinafter referred to as “photoacid generator resin”) having a repeating unit containing a structure that generates an acid anion by irradiation with actinic rays or radiation in the side chain (hereinafter referred to as “photoacid generating resin”) have a blending ratio shown in Table 1 below.
  • the organic semiconductor layer forming compositions of Examples and Comparative Examples were prepared by mixing and stirring.
  • any organic semiconductor layer forming composition it is prepared as a solution having a solid content concentration of 0.5% by mass using toluene as a solvent, and is necessary when the organic semiconductor material or the photoacid generator resin is difficult to dissolve. Accordingly, stirring was performed while heating at about 50 ° C. to dissolve each component.
  • a doped silicon substrate (also serving as the gate electrode 5) having a thickness of 1 mm was used as the substrate 6, and the gate insulating layer 2 was formed thereon.
  • the said composition for organic-semiconductor layer formation was apply
  • the organic semiconductor layer precursor layer obtained was irradiated with light having a wavelength of 254 to 365 nm (irradiation amount 30 mW / cm 2 ) for 10 seconds using a high pressure UV lamp (manufactured by USHIO INC.) To generate photoacid
  • the organic semiconductor layer was formed by decomposing the resin to produce a main chain component having an acid anion in the side chain in the system.
  • an organic semiconductor layer 1 having a thickness of 150 nm was formed, and organic thin film transistors (bottom gate / bottom contact type) of Examples 1 to 20 and Comparative Examples 1 to 3 were obtained.
  • an organic thin film transistor II was prepared with the formulation shown in Table 1. Details are as follows. First, a composition for forming an organic semiconductor material layer (organic semiconductor) obtained by dissolving an organic semiconductor material represented by Compound No. N7 in Table 1 below in 1 mL of toluene so as to cover the gate insulating layer 2, the source electrode 3, and the drain electrode 4.
  • the organic semiconductor material concentration in the composition for forming a material layer 0.5 mass%) was applied by spin coating (rotation speed: 1000 rpm) at 25 ° C. Thereafter, an organic semiconductor material layer having a thickness of 150 nm was formed by heating on a hot plate at 150 ° C. for 30 minutes.
  • each photoacid-generating resin layer forming composition each light having a photoacid-generating resin (A-1 to 8) shown in Table 1 below dissolved in 1 mL of toluene)
  • the photoacid generating resin concentration in the acid generating resin layer forming composition: 0.1% by mass was applied at 25 ° C. by spin coating (rotation speed: 1000 rpm).
  • an organic semiconductor layer precursor layer having a thickness of 150 nm was formed to produce an OTFT.
  • the organic semiconductor layer precursor layer obtained was irradiated with light having a wavelength of 254 to 365 nm (irradiation amount 30 mW / cm 2 ) for 10 seconds using a high pressure UV lamp (manufactured by USHIO INC.) To generate photoacid
  • the organic semiconductor layer 1 was formed by decomposing the resin to produce a main chain component having an acid anion in the side chain in the system.
  • an organic semiconductor layer 1 having a thickness of 150 nm was formed, and organic thin film transistors (bottom gate / bottom contact type) of Examples 21 to 28 were obtained.
  • the performance was investigated by evaluating carrier mobility (micro
  • the results are shown in Table 1.
  • the pKa of the photoacid generator resin is “a unit having a structural site that generates an acid anion of the photoacid generator resin (a monomer of a repeating unit represented by formulas (III) to (V)”). ) PKa ".
  • 10 ⁇ 6 is intended to be “10 to the sixth power” (10 6 ).
  • the organic thin film transistors of Examples 1 to 28 are all produced using a composition for forming an organic semiconductor layer using a photoacid generating resin, the main chain acid dissociated by light irradiation of the photoacid generating resin is used. The component did not diffuse into the insulating layer, which resulted in an excellent on / off ratio.
  • the organic semiconductor layer formed by the composition for forming an organic semiconductor layer has a structure in which the photoacid-generating resin is decomposed in the system by light irradiation after the crystal structure is formed by the organic semiconductor material.
  • the main chain portion having an acid anion in the generated side chain exists in the system in phase separation from the crystal structure of the organic semiconductor material, that is, it does not disturb the crystallinity and is uniformly doped.
  • the degree ⁇ was also excellent.
  • the carrier mobility ⁇ is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight.
  • Comparative Example 1 in which no photoacid-generating resin was added did not have sufficient carrier mobility ⁇ .

Abstract

The present invention addresses the problem of providing an organic thin film transistor of superior carrier mobility and insulation reliability, and an organic semiconductor layer-forming composition with which said organic thin film transistor can be produced.　This organic thin film transistor has a gate electrode, an organic semiconductor layer, a gate insulation layer provided between the gate electrode and the organic semiconductor layer, and a source electrode and drain electrode that are provided in contact with the organic semiconductor layer and are linked via the organic semiconductor layer, wherein the organic semiconductor layer is obtained by irradiating, with active light rays or radiation, an organic semiconductor layer precursor layer comprising an organic semiconductor material and a resin that has repeating units including, in a side chain, a structural site that produces acid anions when irradiated with active light rays or radiation.

Description

有機薄膜トランジスタ、有機半導体層形成用組成物Organic thin film transistor, composition for forming organic semiconductor layer
　本発明は、有機薄膜トランジスタ及び有機半導体層形成用組成物に関する。 The present invention relates to an organic thin film transistor and a composition for forming an organic semiconductor layer.
　軽量化、低コスト化及び柔軟化が可能であることから、液晶ディスプレイ又は有機エレクトロルミネッセンス（有機ＥＬ）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）又はメモリなどの論理回路を用いる装置等に、有機半導体層（有機半導体膜）を有する有機薄膜トランジスタ（有機ＴＦＴ（thin film transistor））が利用されている。 Because it is possible to reduce weight, cost and flexibility, such as FET (Field Effect Transistor), RFID (Radio Frequency Identifier, RF tag) or memory used for liquid crystal display or organic electroluminescence (organic EL) display An organic thin film transistor (organic TFT (thin film transistor)) having an organic semiconductor layer (organic semiconductor film) is used in a device using a logic circuit.
　昨今、有機薄膜トランジスタへの期待が高まるなか、有機薄膜トランジスタには、移動度（特にキャリア移動度）の向上及び安定性（絶縁信頼性の向上）などが求められている。
　このようななか、特許文献１には、「トランジスタにおいて、半導体層、上記半導体層の上又は内に配置されたチャネル、上記半導体層の上又は内に配置されたソース、上記半導体層の上又は内に配置されたドレイン、上記半導体層と電気的に結合されたゲート、及び光活性材料であって、(ａ)上記半導体層に隣接し、上記半導体層と接触して、(ｂ)上記半導体層内に、又は(ｃ)上記ソース、上記ドレイン及び上記ゲートの１つないしさらに多くの内に、配された光活性材料、を有し、分子、陽子及び／又はイオンが上記光活性材料から上記半導体材料内に拡散する、ことを特徴とするトランジスタ。」が開示されている。 In recent years, as expectations for organic thin film transistors have increased, organic thin film transistors are required to have improved mobility (particularly carrier mobility) and stability (improved insulation reliability).
Among them, Patent Document 1 states that “in a transistor, a semiconductor layer, a channel disposed on or in the semiconductor layer, a source disposed on or in the semiconductor layer, on or in the semiconductor layer. A drain disposed on the semiconductor layer, a gate electrically coupled to the semiconductor layer, and a photoactive material comprising: (a) adjacent to the semiconductor layer and in contact with the semiconductor layer; and (b) the semiconductor layer Or (c) a photoactive material disposed within one or more of the source, the drain and the gate, wherein molecules, protons and / or ions are from the photoactive material. A transistor characterized in that it diffuses into the semiconductor material.
特開２０１３－５３１８８４号公報JP 2013-531884 A
　本発明者は、特許文献１に記載の方法を参照して、有機薄膜トランジスタの製造を行ったところ、製造された有機薄膜トランジスタは、有機半導体層を構成する有機半導体材料が結晶化された後に、有機半導体層中あるいはその近傍に配された光酸発生剤を光照射によって分解し、分解フラグメントを有機半導体層へ拡散させる構成をとるため、比較的結晶性を乱さずにドーピングすることが可能であることが確認された。
　しかしながら、引用文献１に記載された光酸発生剤はいずれも低分子型光酸発生剤であるため、拡散性には優れるものの、場合によっては、拡散によって有機薄膜トランジスタの絶縁性能が低下し、すなわち、ＯＮ／ＯＦＦ比が低下する傾向があることを知見した。
　また、昨今の有機薄膜トランジスタに対する移動度（特にキャリア移動度）向上の要求を鑑みると、さらに高いキャリア移動度を有する有機薄膜トランジスタが望まれるところである。 The present inventor made an organic thin film transistor by referring to the method described in Patent Document 1, and the manufactured organic thin film transistor was organic after the organic semiconductor material constituting the organic semiconductor layer was crystallized. Since the photoacid generator disposed in or near the semiconductor layer is decomposed by light irradiation and the decomposed fragments are diffused into the organic semiconductor layer, it is possible to dope without disturbing the crystallinity relatively. It was confirmed.
However, since all of the photoacid generators described in the cited document 1 are low molecular photoacid generators, the diffusibility is excellent, but in some cases, the insulation performance of the organic thin film transistor is reduced due to diffusion, that is, It was found that the ON / OFF ratio tends to decrease.
In view of recent demands for improving mobility (particularly carrier mobility) with respect to organic thin film transistors, organic thin film transistors having higher carrier mobility are desired.
　本発明は、上記実情に鑑みて、キャリア移動度及び絶縁信頼性に優れた有機薄膜トランジスタ、並びにそれを作製することができる有機半導体層形成用組成物を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide an organic thin film transistor excellent in carrier mobility and insulation reliability, and an organic semiconductor layer forming composition capable of producing the same.
　本発明者は、上記課題について鋭意検討した結果、有機薄膜トランジスタにおいて、まず、有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位を有する樹脂と、を含む有機半導体層前駆体層を構成し、この有機半導体層前駆体層に対して活性光線又は放射線を照射し、上記樹脂を分解してドーパント（好ましくは、酸アニオンポリマー）を系内に形成することで、上記課題を解決できることを見出し、本発明に至った。
　すなわち、本発明者は、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 earnestly examining the above problems, the present inventor, in an organic thin film transistor, first, an organic semiconductor material and a resin having a repeating unit containing a structural site that generates an acid anion by irradiation with actinic rays or radiation in the side chain, An organic semiconductor layer precursor layer is formed, and the organic semiconductor layer precursor layer is irradiated with actinic rays or radiation, and the resin is decomposed to form a dopant (preferably an acid anion polymer) in the system. Thus, the inventors have found that the above problems can be solved, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.
（１）　ゲート電極と、有機半導体層と、上記ゲート電極及び上記有機半導体層の間に設けられたゲート絶縁層と、上記有機半導体層に接して設けられ、上記有機半導体層を介して連結されたソース電極及びドレイン電極と、を有する有機薄膜トランジスタであって、
　上記有機半導体層が、有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位を有する樹脂と、を含む有機半導体層前駆体層に対して活性光線又は放射線を照射することにより得られる層である、有機薄膜トランジスタ。
（２）　上記繰り返し単位が、後述する式（ＩＩＩ）～（Ｖ）から選択される少なくとも１種類である、（１）に記載の有機薄膜トランジスタ。
（３）　上記繰り返し単位中の酸アニオンを生じる構造部位が、スルホニウム塩構造又はヨードニウム塩構造を有する、（１）又は（２）に記載の有機薄膜トランジスタ。
（４）　上記有機半導体材料が、縮合多環芳香族基を有し、上記縮合多環芳香族基中の環数が４つ以上であり、上記縮合多環芳香族基中の少なくとも２つの環が、硫黄原子、窒素原子、セレン原子及び酸素原子よりなる群から選択される少なくとも１つの原子を含み、上記縮合多環芳香族基中の部分構造として、ベンゼン環、ナフタレン環、及び、フェナントレン環よりなる群から選択される少なくともいずれか１つの構造を含む、（１）～（３）のいずれかに記載の有機薄膜トランジスタ。
（５）　上記有機半導体材料における上記縮合多環芳香族基中の環数が、４～６である、（４）に記載の有機薄膜トランジスタ。
（６）　上記有機半導体材料の上記縮合多環芳香族基中に少なくとも２つの複素環が含まれ、上記複素環がそれぞれ、ヘテロ原子を１つのみ有する複素環である、（４）又は（５）に記載の有機薄膜トランジスタ。
（７）　上記有機半導体層において、上記樹脂の含有量が、有機半導体材料１００質量部に対して０．００１～３０質量部である、（１）～（６）のいずれかに記載の有機薄膜トランジスタ。
（８）　上記ゲート絶縁層が有機高分子を少なくとも含む、（１）～（７）のいずれかに記載の有機薄膜トランジスタ。
（９）　有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造を側鎖に含む繰り返し単位を有する樹脂と、を含む、有機半導体層形成用組成物。 (1) A gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and provided in contact with the organic semiconductor layer and connected via the organic semiconductor layer. An organic thin film transistor having a source electrode and a drain electrode,
The organic semiconductor layer comprises an organic semiconductor material and an organic semiconductor layer precursor containing an organic semiconductor material and a resin having a repeating unit containing a structural site that generates acid anions upon irradiation with active light or radiation. An organic thin film transistor which is a layer obtained by irradiation with radiation.
(2) The organic thin film transistor according to (1), wherein the repeating unit is at least one selected from formulas (III) to (V) described later.
(3) The organic thin film transistor according to (1) or (2), wherein the structural site that generates an acid anion in the repeating unit has a sulfonium salt structure or an iodonium salt structure.
(4) The organic semiconductor material has a condensed polycyclic aromatic group, the number of rings in the condensed polycyclic aromatic group is 4 or more, and at least two rings in the condensed polycyclic aromatic group Includes at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and as a partial structure in the condensed polycyclic aromatic group, a benzene ring, a naphthalene ring, and a phenanthrene ring The organic thin film transistor according to any one of (1) to (3), comprising at least one structure selected from the group consisting of:
(5) The organic thin film transistor according to (4), wherein the condensed polycyclic aromatic group in the organic semiconductor material has 4 to 6 rings.
(6) The condensed polycyclic aromatic group of the organic semiconductor material contains at least two heterocycles, and each of the heterocycles is a heterocycle having only one heteroatom, (4) or (5 ) Organic thin film transistor.
(7) The organic thin film transistor according to any one of (1) to (6), wherein the content of the resin in the organic semiconductor layer is 0.001 to 30 parts by mass with respect to 100 parts by mass of the organic semiconductor material. .
(8) The organic thin film transistor according to any one of (1) to (7), wherein the gate insulating layer includes at least an organic polymer.
(9) A composition for forming an organic semiconductor layer, comprising: an organic semiconductor material; and a resin having a repeating unit containing a structure that generates acid anions upon irradiation with actinic rays or radiation in the side chain.
　本明細書において、化合物の表示については、その化合物そのものの他、その塩、そのイオンを含む意味に用いる。 In this specification, the term “compound” is used to mean not only the compound itself but also its salt and its ion.
　本明細書において、特定の符号で表示された置換基若しくは連結基等（以下、置換基等という）が複数あるとき、又は複数の置換基等を同時に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよいことを意味する。このことは、置換基等の数の規定についても同様である。
　また、特に断らない限り、複数の置換基等が近接（特に隣接）するときには、それらが互いに連結したり縮環したりして環を形成していてもよい意味である。
　さらに、本明細書において置換・無置換を明記していない置換基等については、目的とする効果を損なわない範囲で、その基にさらに置換基を有していてもよい意味である。これは置換・無置換を明記していない化合物についても同義である。 In this specification, when there are a plurality of substituents or linking groups or the like (hereinafter referred to as substituents or the like) indicated by a specific symbol, or when a plurality of substituents or the like are defined simultaneously, Means the same or different. The same applies to the definition of the number of substituents and the like.
In addition, unless otherwise specified, when a plurality of substituents and the like are close (particularly adjacent), it means that they may be connected to each other or condensed to form a ring.
Furthermore, in the present specification, a substituent or the like that does not clearly indicate substitution / unsubstitution means that the group may further have a substituent as long as the intended effect is not impaired. This is also synonymous for compounds that do not specify substitution / non-substitution.
　本明細書において「～」を用いて表される数値範囲は、「～」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。 In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
　本発明によれば、キャリア移動度及び絶縁信頼性に優れた有機薄膜トランジスタ、及びそれを作製することができる有機半導体層形成用組成物を提供することができる。 According to the present invention, it is possible to provide an organic thin film transistor excellent in carrier mobility and insulation reliability, and an organic semiconductor layer forming composition capable of producing the same.
本発明の有機薄膜トランジスタの好ましい構造の一例を模式的に示す図である。It is a figure which shows typically an example of the preferable structure of the organic thin-film transistor of this invention. 本発明の有機薄膜トランジスタの好ましい構造の他の一例を模式的に示す図である。It is a figure which shows typically another example of the preferable structure of the organic thin-film transistor of this invention. 本発明の有機薄膜トランジスタの好ましい構造の他の一例を模式的に示す図である。It is a figure which shows typically another example of the preferable structure of the organic thin-film transistor of this invention. 本発明の有機薄膜トランジスタの好ましい構造の他の一例を模式的に示す図である。It is a figure which shows typically another example of the preferable structure of the organic thin-film transistor of this 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（以下、単に「本発明のＯＴＦＴ」という。）の構造を以下に説明する。 [Organic thin film transistor]
The structure of the organic thin film transistor of the present invention (hereinafter simply referred to as “OTFT of the present invention”) will be described below.
　本発明のＯＴＦＴは、基板上に、ゲート電極と、有機半導体層と、ゲート電極と有機半導体層との間に設けられたゲート絶縁層と、有機半導体層に接して設けられ、有機半導体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。ゲート電極に電圧が印加されると、ソース電極－ドレイン電極間の有機半導体層とこれに隣接する層との界面に電流の流路（チャネル）が形成される。すなわち、ゲート電極に印加される入力電圧に応じて、ソース電極とドレイン電極との間を流れる電流が制御される。 The OTFT of the present invention is provided on a substrate in contact with an organic semiconductor layer, a gate electrode, an organic semiconductor layer, a gate insulating layer provided between the gate electrode and the organic semiconductor layer, and the organic semiconductor layer. And a source electrode and a drain electrode connected to each other. When a voltage is applied to the gate electrode, a current flow channel (channel) is formed at the interface between the organic semiconductor layer between the source electrode and the drain electrode and the adjacent layer. That is, the current flowing between the source electrode and the drain electrode is controlled according to the input voltage applied to the gate electrode.
　本発明のＯＴＦＴの好ましい構造を図面に基づいて説明する。各図面に示されるＯＴＦＴは、本発明の理解を容易にするための模式図であり、各部材のサイズないし相対的な大小関係等は説明の便宜上大小を変えている場合があり、実際の関係をそのまま示すものではない。また、本発明で規定する事項以外はこれらの図面に示された外形又は形状に限定されるものでもない。例えば、図１Ａ及び図１Ｂにおいて、ゲート電極５は必ずしも基板６のすべてを覆っている必要はなく、基板６の中央部分に設けられた形態も、本発明のＯＴＦＴの形態として好ましい。
　図１Ａ～図１Ｄは、各々、本発明のＯＴＦＴの代表的な好ましい構造を模式的に表す縦断面図である。図１Ａ～図１Ｄはいずれも、有機半導体層１と、ゲート絶縁層２と、ソース電極３と、ドレイン電極４と、ゲート電極５と、基板６とを備えて構成される。
　また、図１Ａは、ボトムゲート・ボトムコンタクト構造、図１Ｂは、ボトムゲート・トップコンタクト構造、図１Ｃはトップゲート・ボトムコンタクト構造、図１Ｄはトップゲート・トップコンタクト構造のＯＴＦＴを示している。
　本発明のＯＴＦＴには上記４つの形態のすべてが包含される。図示を省略するが、各ＯＴＦＴの図面最上部（基板６に対して反対側）には、オーバーコート層が形成されている場合もある。 A preferred structure of the OTFT of the present invention will be described with reference to the drawings. The OTFT shown in each drawing is a schematic diagram for facilitating the understanding of the present invention, and the size or relative size relationship of each member may be changed for convenience of explanation. Is not shown as it is. Moreover, it is not limited to the external shape or shape shown by these drawings except the matter prescribed | regulated by this invention. For example, in FIGS. 1A and 1B, the gate electrode 5 does not necessarily cover the entire substrate 6, and a form provided in the central portion of the substrate 6 is also preferable as a form of the OTFT of the present invention.
1A to 1D are longitudinal sectional views each schematically showing a typical preferable structure of an OTFT of the present invention. 1A to 1D each include an organic semiconductor layer 1, a gate insulating layer 2, a source electrode 3, a drain electrode 4, a gate electrode 5, and a substrate 6.
1A shows a bottom gate / bottom contact structure, FIG. 1B shows a bottom gate / top contact structure, FIG. 1C shows a top gate / bottom contact structure, and FIG. 1D shows a top gate / top contact structure OTFT.
The OTFT of the present invention includes all of the above four forms. Although not shown, an overcoat layer may be formed on the top of each OTFT in the drawing (the side opposite to the substrate 6).
　本発明のＯＴＦＴの特徴は、有機半導体層１が、有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位を有する樹脂（以下、単に「光酸発生樹脂」とも称する。）と、を含む有機半導体層前駆体層に対し、活性光線又は放射線を照射することにより形成される点にある。
　この有機半導体層１の具体的な形成方法としては、有機半導体材料と、光酸発生樹脂とを含む有機半導体層形成組成物により形成する方法が一例として挙げられる。この形成方法を用いて、例えば、図１Ａに示すボトムゲート・ボトムコンタクト構造のＯＴＦＴを作製する場合には、まず上記の有機半導体層形成組成物を調製し、これを下層となるゲート絶縁層２、ソース電極３及びドレイン電極４上に塗設して有機半導体層前駆体層を形成する。その後、上記有機半導体層前駆体層に対して活性光線又は放射線を照射することにより、所定の有機半導体層を形成することができる。
　有機半導体層前駆体層において、結晶性の高い有機半導体材料と、光酸発生樹脂とは、互いに相分離して存在しているものと推測される。この有機半導体層前駆体層に対し活性光線又は放射線を照射すると、光酸発生樹脂がエネルギーを吸収して開裂し、主に、側鎖に酸アニオンを有する主鎖部分と、カチオン部分とに分解する。このとき、ドーパントである側鎖に酸アニオンを有する主鎖部分は、特許文献１に挙げるような低分子型光酸発生剤により形成される低分子型の酸アニオンと比較して分子量が大きく拡散性に乏しいため、有機半導体層内に有機半導体材料と相分離した状態で留まるものと考えられる。
　この構成により、本発明の有機薄膜トランジスタは、ドーパントのゲート絶縁層への拡散によって生じる絶縁性能の低下が抑制されているため、ＯＮ／ＯＦＦ比に優れたものとなる。また、ドーパントである側鎖に酸アニオンを有する主鎖部分と有機半導体材料の結晶とが相分離して存在するため、拡散性に富む低分子型光酸発生剤を用いた場合と比較して有機半導体材料の結晶性を損傷することが少なく、キャリア移動度にも優れたものとなる。 The feature of the OTFT of the present invention is that the organic semiconductor layer 1 is a resin (hereinafter simply referred to as “photoacid generation”) having an organic semiconductor material and a repeating unit containing a structural site that generates an acid anion upon irradiation with actinic rays or radiation. It is also formed by irradiating an actinic ray or radiation to an organic semiconductor layer precursor layer containing a resin.
As a specific method for forming the organic semiconductor layer 1, a method of forming the organic semiconductor layer 1 using an organic semiconductor layer-forming composition containing an organic semiconductor material and a photoacid generating resin can be cited as an example. For example, when the OTFT having the bottom gate / bottom contact structure shown in FIG. 1A is manufactured by using this forming method, the above-mentioned organic semiconductor layer forming composition is first prepared, and this is used as the lower gate insulating layer 2. The organic semiconductor layer precursor layer is formed by coating on the source electrode 3 and the drain electrode 4. Then, a predetermined organic semiconductor layer can be formed by irradiating the organic semiconductor layer precursor layer with actinic rays or radiation.
In the organic semiconductor layer precursor layer, it is presumed that the organic semiconductor material having high crystallinity and the photoacid-generating resin are present in phase separation from each other. When this organic semiconductor layer precursor layer is irradiated with actinic rays or radiation, the photoacid-generating resin absorbs energy and cleaves, and mainly decomposes into a main chain portion having an acid anion in the side chain and a cation portion. To do. At this time, the main chain portion having an acid anion in the side chain as a dopant has a large molecular weight compared with a low molecular acid anion formed by a low molecular photoacid generator as described in Patent Document 1. It is considered that it remains in a state separated from the organic semiconductor material in the organic semiconductor layer because of its poor property.
With this configuration, the organic thin film transistor of the present invention has an excellent ON / OFF ratio because a decrease in insulating performance caused by diffusion of the dopant into the gate insulating layer is suppressed. In addition, since the main chain portion having an acid anion in the side chain which is a dopant and the crystal of the organic semiconductor material are phase-separated, compared with the case of using a low molecular photoacid generator rich in diffusibility There is little damage to the crystallinity of the organic semiconductor material, and the carrier mobility is excellent.
　一方、本発明の有機薄膜トランジスタにおいて、有機半導体層１は、上述のような有機半導体材料と光酸発生樹脂とを含む有機半導体層形成用組成物を用いる方法の他に、有機半導体材料を含む有機半導体材料層と光酸発生樹脂を含む光酸発生樹脂層との少なくとも２層構成として有機半導体層前駆体層を形成し、この有機半導体層前駆体層に対し活性光線又は放射線を照射することにより形成されてもよい。なお、２層構成にする場合、有機半導体材料層と光酸発生樹脂層との積層順は特に制限されないが、本発明の効果がより優れる点で、有機半導体材料層がゲート絶縁層側に配置され、光発生樹脂層がゲート絶縁層から離れた位置にあることが好ましい。
　具体的には、図１Ａに示すボトムゲート・ボトムコンタクト構造を参照して説明すると、下層となるゲート絶縁層２、ソース電極３及びドレイン電極４上に、有機半導体材料層を形成した後、有機半導体材料層の表面の全部又はその一部に光酸発生樹脂層を積層して有機半導体層前駆体層を形成し、この有機半導体層前駆体層に対して活性光線又は放射線を照射する。 On the other hand, in the organic thin film transistor of the present invention, the organic semiconductor layer 1 includes an organic semiconductor material containing an organic semiconductor material in addition to the method using the organic semiconductor layer forming composition containing the organic semiconductor material and the photoacid generating resin as described above. By forming an organic semiconductor layer precursor layer as at least two layers of a semiconductor material layer and a photoacid generating resin layer containing a photoacid generating resin, and irradiating the organic semiconductor layer precursor layer with actinic rays or radiation It may be formed. In the case of a two-layer structure, the stacking order of the organic semiconductor material layer and the photoacid generating resin layer is not particularly limited, but the organic semiconductor material layer is disposed on the gate insulating layer side in that the effect of the present invention is more excellent. In addition, it is preferable that the photogenerating resin layer is located away from the gate insulating layer.
Specifically, referring to the bottom gate / bottom contact structure shown in FIG. 1A, an organic semiconductor material layer is formed on the lower gate insulating layer 2, the source electrode 3, and the drain electrode 4, and then the organic semiconductor material layer is formed. An organic semiconductor layer precursor layer is formed by laminating a photoacid-generating resin layer on all or part of the surface of the semiconductor material layer, and the organic semiconductor layer precursor layer is irradiated with actinic rays or radiation.
　上述したいずれの態様においても、光（活性光線又は放射線）照射後の有機半導体層中では、有機半導体材料と、光酸発生樹脂が開裂することで発生したドーパントとが相分離して存在し、これにより有機薄膜トランジスタは、キャリア移動度及び絶縁信頼性に優れたものとなる。 In any of the above-described aspects, in the organic semiconductor layer after irradiation with light (active light or radiation), the organic semiconductor material and the dopant generated by the cleavage of the photoacid-generating resin are present in phase separation, As a result, the organic thin film transistor is excellent in carrier mobility and insulation reliability.
　以下、本発明のＯＴＦＴ及びこれに用いられる各種材料について、詳細に説明する。 Hereinafter, the OTFT of the present invention and various materials used in the OTFT will be described in detail.
[有機半導体層]
　有機半導体層は、半導体性を示し、キャリアを蓄積可能な層である。
　上述した通り、本発明における有機半導体層は、有機半導体材料と、光酸発生樹脂とを含む有機半導体層前駆体層に対し、活性光線又は放射線を照射することにより形成される。 [Organic semiconductor layer]
The organic semiconductor layer is a layer that exhibits semiconductor properties and can accumulate carriers.
As described above, the organic semiconductor layer in the present invention is formed by irradiating the organic semiconductor layer precursor containing the organic semiconductor material and the photoacid generating resin with actinic rays or radiation.
　有機半導体層の膜厚（全体）は、特に限定されないが、１ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。また、１０μｍ以下が好ましく、１μｍ以下がより好ましく、５００ｎｍ以下が特に好ましい。
　有機半導体材料と光酸発生樹脂とをそれぞれ別層として有機半導体層前駆体層を形成する場合には、形成される有機半導体層における有機半導体材料層の膜厚又は光酸発生樹脂層の膜厚は、有機半導体層全体の膜厚が上記範囲内であれば、それぞれ特に限定されない。 Although the film thickness (whole) of an organic-semiconductor layer is not specifically limited, 1 nm or more is preferable and 10 nm or more is more preferable. Moreover, 10 micrometers or less are preferable, 1 micrometer or less is more preferable, and 500 nm or less is especially preferable.
When forming the organic semiconductor layer precursor layer with the organic semiconductor material and the photoacid generating resin as separate layers, the film thickness of the organic semiconductor material layer or the film thickness of the photoacid generating resin layer in the formed organic semiconductor layer Are not particularly limited as long as the thickness of the entire organic semiconductor layer is within the above range.
　有機半導体層において、光酸発生樹脂の含有量は、有機半導体材料１００質量部に対して、０．００１～３０質量部であるのが好ましく、０．０１～２０質量部であるのがより好ましく、０．１～５質量部であるのがさらに好ましい。上記の範囲とすることで、よりキャリア移動度及び絶縁信頼性に優れた有機薄膜トランジスタとすることができる。
　また、有機半導体層において、光酸発生樹脂の含有量は、有機半導体層の全固形分に対して、有機半導体層の全固形分：光酸発生樹脂の質量比で１０００００：１～１０：１であることが好ましく、１００００：１～１００：５であることがより好ましく、１０００：１～１００：１であることが特に好ましい。 In the organic semiconductor layer, the content of the photoacid-generating resin is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the organic semiconductor material. More preferably, the content is 0.1 to 5 parts by mass. By setting it as said range, it can be set as the organic thin-film transistor more excellent in carrier mobility and insulation reliability.
In the organic semiconductor layer, the content of the photoacid generating resin is 100000: 1 to 10: 1 in a mass ratio of the total solid content of the organic semiconductor layer to the photoacid generating resin with respect to the total solid content of the organic semiconductor layer. It is preferably 10000: 1 to 100: 5, more preferably 1000: 1 to 100: 1.
≪有機半導体層の形成方法≫
＜第１の実施態様＞
　以下、まず、第１の実施態様として、有機半導体材料と光酸発生樹脂とを含む有機半導体層形成組成物を用いて有機半導体層を形成する方法について詳細に説明する。
　有機半導体層形成用組成物は、有機半導体材料及び光酸発生樹脂を含むが、その他に溶媒、界面活性剤又はバインダー樹脂等の他の添加剤等を含んでもよい。 ≪Method of forming organic semiconductor layer≫
<First Embodiment>
Hereinafter, first, as a first embodiment, a method for forming an organic semiconductor layer using an organic semiconductor layer forming composition containing an organic semiconductor material and a photoacid generating resin will be described in detail.
The composition for forming an organic semiconductor layer includes an organic semiconductor material and a photoacid generating resin, but may further include other additives such as a solvent, a surfactant, or a binder resin.
（光酸発生樹脂）
　光酸発生樹脂は、活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位を有する樹脂であれば特に限定されるものではなく、単独、もしくは２種以上を併用してもよい。
　本発明において「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、Ｘ線、又は、電子線等を意味する。また、本発明において光とは、活性光線又は放射線を意味する。 (Photoacid generator resin)
The photoacid-generating resin is not particularly limited as long as it is a resin having a repeating unit containing a structural site that generates an acid anion in the side chain upon irradiation with actinic rays or radiation, either alone or in combination of two or more. Also good.
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, or electron beams. In the present invention, light means actinic rays or radiation.
　活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位としては、例えば、下記一般式（ＩＩＩ）～（Ｖ）のいずれかで表される繰り返し単位が好ましい。 As the repeating unit containing in its side chain a structural moiety that generates an acid anion upon irradiation with actinic rays or radiation, for example, a repeating unit represented by any one of the following general formulas (III) to (V) is preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（ＩＩＩ）～（Ｖ）中、
　Ａは、活性光線又は放射線の照射により分解して酸アニオンを生じる構造部位を表す。
　Ｒ04、Ｒ05及びＲ07～Ｒ09は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
　Ｒ06は、シアノ基、カルボキシル基、－ＣＯ－ＯＲ25又は－ＣＯ－Ｎ（Ｒ26）（Ｒ27）を表す。Ｒ26とＲ27が結合して窒素原子とともに環を形成してもよい。
　Ｘ1～Ｘ3は、各々独立に、単結合、アリーレン基、アルキレン基、シクロアルキレン基、－Ｏ－、－ＳＯ2－、－ＣＯ－、－Ｎ（Ｒ33）－又はこれらの複数を組み合わせた２価の連結基を表す。
　Ｒ25は、アルキル基、シクロアルキル基、アルケニル基、アリール基又はアラルキル基を表す。
　Ｒ26、Ｒ27及びＲ33は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、アリール基又はアラルキル基を表す。 In general formulas (III) to (V),
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R 04 , R 05 and R 07 to R 09 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R 06 represents a cyano group, a carboxyl group, —CO—OR 25 or —CO—N (R 26 ) (R 27 ). R 26 and R 27 may combine to form a ring with the nitrogen atom.
X 1 to X 3 each independently represents a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R 33 ) —, or a combination thereof. Represents a divalent linking group.
R 25 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
R 26 , R 27 and R 33 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
　上記Ｒ04～Ｒ05、Ｒ07～Ｒ09、Ｒ25～Ｒ27及びＲ33において、アルキル基は、直鎖型でも分岐型でもよく、好ましくは置換基を有していてもよいメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、ドデシル基など炭素数２０以下のアルキル基が挙げられ、より好ましくは炭素数８以下のアルキル基が挙げられる。
　また、シクロアルキル基は、単環型でも、多環型でもよく、更に置換基を有していてもよい。好ましくはシクロプロピル基、シクロペンチル基、シクロヘキシル基のような炭素数３～８個の単環型のシクロアルキル基が挙げられる。
　また、上記Ｒ04、Ｒ05及びＲ07～Ｒ09において、ハロゲン原子としては、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、フッ素原子がより好ましい。
　また、上記Ｒ04、Ｒ05及びＲ07～Ｒ099において、アルコキシカルボニル基に含まれるアルキル基としては、上記Ｒ04～Ｒ05、Ｒ07～Ｒ09におけるアルキル基と同様のものが好ましい。 In the above R 04 to R 05 , R 07 to R 09 , R 25 to R 27 and R 33 , the alkyl group may be linear or branched, preferably a methyl group which may have a substituent, Examples include an alkyl group having 20 or less carbon atoms, such as an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and more preferably a carbon number of 8 The following alkyl groups are mentioned.
The cycloalkyl group may be monocyclic or polycyclic, and may further have a substituent. Preferred are monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group.
In the above R 04 , R 05 and R 07 to R 09 , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is more preferable.
Further, in R 04 , R 05 and R 07 to R 099 , the alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R 04 to R 05 and R 07 to R 09 .
　また、上記Ｒ25～Ｒ27及びＲ33において、アルケニル基としては、好ましくは置換基を有していてもよいビニル基、プロペニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、シクロヘキセニル基の様な炭素数２～６個のものが挙げられる。
　アリール基としては、置換基を有していてもよい炭素数６～１４個の単環、多環の芳香族基が好ましく、具体的にはフェニル基、トリル基、クロロフェニル基、メトキシフェニル基、ナフチル基等が挙げられる。またアリール基同士が結合して、複環を形成していてもよい。
　アラルキル基としては、ベンジル基、フェネチル基、クミル基等の置換基を有していてもよい炭素数７～１５個のものが挙げられる。
　Ｒ26とＲ27が結合して窒素原子とともに形成しうる環としては、５～８員環を形成するものが好ましいが、具体的にはピロリジン、ピペリジン、ピペラジン等が挙げられる。 In the above R 25 to R 27 and R 33 , the alkenyl group is preferably a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group which may have a substituent. And those having 2 to 6 carbon atoms.
The aryl group is preferably a monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms which may have a substituent. Specifically, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, A naphthyl group etc. are mentioned. Aryl groups may be bonded to each other to form a double ring.
Examples of the aralkyl group include those having 7 to 15 carbon atoms which may have a substituent such as a benzyl group, a phenethyl group or a cumyl group.
The ring that can be formed by combining R 26 and R 27 together with the nitrogen atom is preferably a ring that forms a 5- to 8-membered ring. Specific examples include pyrrolidine, piperidine, and piperazine.
　また、上記Ｘ1～Ｘ3のアリーレン基は、置換基を有していてもよい炭素数６～１４個のものが好ましく、具体的にはフェニレン基、トリレン基、ナフチレン基等が挙げられる。
　アルキレン基としては、好ましくはメチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、オクチレン基等の炭素数１～８個のものが挙げられる。
　シクロアルキレン基としては、好ましくは置換基を有していてもよいシクロペンチレン基、シクロヘキシレン基等の炭素数５～８個のものが挙げられる。
　なお、後述するように、各基は置換基を有していてもよく、例えば、本発明の効果がより優れる点で、アルキレン基にはハロゲン原子が置換していることが好ましい。なかでも、アルキレン基の水素原子が全てハロゲン原子で置換されていることが好ましく、水素原子の全てがフッ素原子で置換されたアルキレン基（パーフルオロアルキレン基）が好ましい。 The arylene group of X 1 to X 3 is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group.
The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.
Examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
As will be described later, each group may have a substituent. For example, the alkylene group is preferably substituted with a halogen atom from the viewpoint of more excellent effects of the present invention. Especially, it is preferable that all the hydrogen atoms of an alkylene group are substituted by the halogen atom, and the alkylene group (perfluoroalkylene group) by which all the hydrogen atoms were substituted by the fluorine atom is preferable.
　これら各基が更に有していてもよい置換基の好ましい例としては、水酸基、ハロゲン原子（フッ素、塩素、臭素、ヨウ素）、ニトロ基、シアノ基、アミド基、スルホンアミド基、Ｒ04～Ｒ05、Ｒ07～Ｒ09、Ｒ25～Ｒ27及びＲ33で挙げたアルキル基、メトキシ基、エトキシ基、ヒドロキシエトキシ基、プロポキシ基、ヒドロキシプロポキシ基若しくはブトキシ基等のアルコキシ基、メトキシカルボニル基若しくはエトキシカルボニル基等のアルコキシカルボニル基、ホルミル基、アセチル基若しくはベンゾイル基等のアシル基、アセトキシ基若しくはブチリルオキシ基等のアシロキシ基、又は、カルボキシ基が挙げられ、更に有していてもよい置換基の炭素数は８以下が好ましい。 Preferred examples of the substituent that each of these groups may further have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R 04 to R 05 , R 07 -R 09 , R 25 -R 27 and R 33 , an alkyl group, an methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an alkoxy group such as a butoxy group, a methoxycarbonyl group or Examples include an alkoxycarbonyl group such as ethoxycarbonyl group, an acyl group such as formyl group, acetyl group or benzoyl group, an acyloxy group such as acetoxy group or butyryloxy group, or a carboxy group. The number of carbon atoms is preferably 8 or less.
　Ａは、活性光線又は放射線の照射により分解して酸アニオンを生じる構造部位を表し、具体的には光カチオン重合の光開始剤、光ラジカル重合の光開始剤、色素類の光消色剤、光変色剤、又は、マイクロレジスト等に使用されている公知の光により酸アニオンを発生する化合物が有する構造部位が挙げられる。
　活性光線又は放射線の照射により酸アニオンを発生する構造部位の一例として、例えば、ジアゾニウム塩構造、アンモニウム塩構造、ホスホニウム塩構造、ヨードニウム塩構造、スルホニウム塩構造、セレノニウム塩構造、又は、アルソニウム塩構造等のオニウム塩構造部位を挙げることができる。 A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion, specifically, photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecolorant for dyes, Examples thereof include a structural portion possessed by a compound that generates an acid anion by known light used in a photochromic agent or a microresist.
Examples of structural sites that generate acid anions upon irradiation with actinic rays or radiation include, for example, diazonium salt structures, ammonium salt structures, phosphonium salt structures, iodonium salt structures, sulfonium salt structures, selenonium salt structures, or arsonium salt structures. The onium salt structure site | part can be mentioned.
　Ａとしては、分解性及び保存安定性の観点から、スルホニウム塩構造又はヨードニウム塩構造を含むイオン性構造部位がより好ましい。より具体的には、Ａとして、下記一般式（ＺＩ）又は（ＺＩＩ）で表される基が好ましい。 A is more preferably an ionic structure site containing a sulfonium salt structure or an iodonium salt structure from the viewpoint of degradability and storage stability. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記一般式（ＺＩ）において、
　Ｒ201、Ｒ202及びＲ203は、各々独立に、有機基を表す。
　Ｒ201、Ｒ202及びＲ203としての有機基の炭素数は、一般的に１～３０、好ましくは１～２０である。
　また、Ｒ201～Ｒ203のうち２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合又はカルボニル基を含んでいてもよい。Ｒ201～Ｒ203の内の２つが結合して形成する環構造としては、例えば、シクロブタン、又は、シクロペンタン等のシクロアルカンを挙げることができる。
　Ｚ－は、活性光線又は放射線の照射により分解して発生する酸アニオンを示し、非求核性アニオンが好ましい。非求核性アニオンとしては、例えば、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ビス（アルキルスルホニル）イミドアニオン、又は、トリス（アルキルスルホニル）メチルアニオン等を挙げることができる。
　非求核性アニオンとは、求核反応を起こす能力が著しく低いアニオンであり、分子内求核反応による経時分解を抑制することができるアニオンである。これにより樹脂の経時安定性が向上する。 In the general formula (ZI),
R 201 , R 202 and R 203 each independently represents an organic group.
The organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the ring structure formed by combining two of R 201 to R 203 include cycloalkanes such as cyclobutane and cyclopentane.
Z − represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the stability of the resin over time.
　Ｒ201、Ｒ202及びＲ203で表される有機基としては、アリール基、アルキル基、又は、シクロアルキル基などが挙げられる。
　Ｒ201、Ｒ202及びＲ203で表されるアリール基、アルキル基、又は、シクロアルキル基は、上述したＲ04～Ｒ05、Ｒ07～Ｒ09、Ｒ25～Ｒ27及びＲ33で表されるアリール基、アルキル基、又は、シクロアルキル基と同様のものが挙げられる。
　なかでも、Ｒ201、Ｒ202及びＲ203のうち、少なくとも1つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基又はピロール残基などのヘテロアリール基も可能である。これらアリール基は更に置換基を有していてもよい。その置換基としては、ニトロ基若しくはフッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（好ましくは炭素数１～１５）、シクロアルキル基（好ましくは炭素数３～１５）、アリール基（好ましくは炭素数６～１４）、アルコキシカルボニル基（好ましくは炭素数２～７）、アシル基（好ましくは炭素数２～１２）、又は、アルコキシカルボニルオキシ基（好ましくは炭素数２～７）等が挙げられるが、これらに限定されるものではない。 Examples of the organic group represented by R 201 , R 202 and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
The aryl group, alkyl group or cycloalkyl group represented by R 201 , R 202 and R 203 is represented by the above-mentioned R 04 to R 05 , R 07 to R 09 , R 25 to R 27 and R 33. And the same aryl group, alkyl group, and cycloalkyl group as above.
Among these, at least one of R 201 , R 202 and R 203 is preferably an aryl group, and more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue or a pyrrole residue is also possible. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro group or fluorine atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), or an alkoxycarbonyloxy group (preferably having a carbon number) 2-7) and the like, but are not limited thereto.
　Ｒ201、Ｒ202及びＲ203のうち、少なくとも１つがアリール基でない場合の好ましい構造としては、特開２００４－２３３６６１号公報の段落００４７～００４８、特開２００３－３５９４８号公報の段落００４０～００４６、米国特許出願公開第２００３／０２２４２８８号明細書に式（Ｉ－１）～（Ｉ－７０）として例示されている化合物、又は、米国特許出願公開第２００３／００７７５４０号明細書に式（ＩＡ－１）～（ＩＡ－５４）、式（ＩＢ－１）～（ＩＢ－２４）として例示されている化合物等のカチオン構造を挙げることができる。 Preferred structures when at least one of R 201 , R 202 and R 203 is not an aryl group include paragraphs 0047 to 0048 of JP-A No. 2004-233661, paragraphs 0040 to 0046 of JP-A No. 2003-35948, Compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003/0224288 or Formula (IA-1) in U.S. Patent Application Publication No. 2003/0077540. ) To (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).
　上記一般式（ＺＩＩ）中、Ｒ204～Ｒ205は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。これらアリール基、アルキル基、シクロアルキル基としては、前述の化合物（ＺＩ）におけるＲ201～Ｒ203のアリール基、アルキル基、シクロアルキル基と同様である。
　また、Ｒ204～Ｒ205のアリール基、アルキル基、シクロアルキル基は、置換基を有していてもよい。この置換基としては、前述の化合物（ＺＩ）におけるＲ201～Ｒ203のアリール基、アルキル基又はシクロアルキル基が有していてもよい置換基と同様のものが挙げられる。 In the general formula (ZII), R 204 to R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group are the same as the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
In addition, the aryl group, alkyl group, and cycloalkyl group of R 204 to R 205 may have a substituent. Examples of the substituent include the same substituents that the aryl group, alkyl group, or cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
　Ｚ－は、活性光線又は放射線の照射により分解して発生する酸アニオンを示し、非求核性アニオンが好ましく、一般式（ＺＩ）に於けるＺ－と同様のものを挙げることができる。 Z − represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z − in formula (ZI).
　また、活性光線又は放射線の照射により酸アニオンを発生する構造部位としては、例えば、下記光酸発生剤が有しているスルホン酸前駆体となる構造部位も挙げることができる。
　Ｍ．ＴＵＮＯＯＫＡ　ｅｔａｌ，Ｐｏｌｙｍｅｒ  Ｐｒｅｐｒｉｎｔｓ　Ｊａｐａｎ，３５（８）、Ｇ．Ｂｅｒｎｅｒ　ｅｔａｌ，Ｊ．Ｒａｄ．Ｃｕｒｉｎｇ，１３（４）、Ｗ．Ｊ．Ｍｉｊｓ　ｅｔａｌ，Ｃｏａｔｉｎｇ　Ｔｅｃｈｎｏｌ．，５５（６９７），４５（１９８３），Ａｋｚｏ、Ｈ．Ａｄａｃｈｉｅｔａｌ，Ｐｏｌｙｍｅｒ　Ｐｒｅｐｒｉｎｔｓ，Ｊａｐａｎ，３７（３）、欧州特許第０１９９，６７２号、同８４５１５号、同１９９，６７２号、同０４４，１１５号、同０１０１，１２２号、米国特許第６１８，５６４号、同４，３７１，６０５号、同４，４３１，７７４号、特開昭６４－１８１４３号、特開平２－２４５７５６号、特願平３－１４０１０９号等に記載のイミノスルフォネ－ト等に代表される光分解してスルホン酸を発生する化合物、特開昭６１－１６６５４４号等に記載のジスルホン化合物、Ｖ．Ｎ．Ｒ．Ｐｉｌｌａｉ，Ｓｙｎｔｈｅｓｉｓ，（１），１（１９８０）、Ａ．Ａｂａｄ　ｅｔａｌ，Ｔｅｔｒａｈｅｄｒｏｎ　Ｌｅｔｔ．，（４７）４５５５（１９７１）、Ｄ．Ｈ．Ｒ．Ｂａｒｔｏｎ　ｅｔａｌ，Ｊ．Ｃｈｅｍ．Ｓｏｃ．，（Ｃ），３２９（１９７０）、米国特許第３，７７９，７７８号、又は、欧州特許第１２６，７１２号等に記載の光により酸を発生する化合物。 Moreover, as a structural site | part which generate | occur | produces an acid anion by irradiation of actinic light or a radiation, the structural site | part used as the sulfonic acid precursor which the following photoacid generator has can also be mentioned, for example.
M.M. TUNOOKA et al, Polymer Preprints Japan, 35 (8), G.M. Berner et al. Rad. Curing, 13 (4), W.M. J. et al. Mijs et al, Coating Technol. , 55 (697), 45 (1983), Akzo, H .; Adachietal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, US Pat. No. 618,564, Represented by the iminosulfonates described in JP-A-4,371,605, JP-A-4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application 3-140109, etc. Compounds that generate sulfonic acid by photolysis, disulfone compounds described in JP-A No. 61-166544, and the like; N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al., Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al. Chem. Soc. , (C), 329 (1970), US Pat. No. 3,779,778, European Patent 126,712, etc.
　Ａで表される部分構造の好ましい具体例を以下に挙げるが、特にこれらに限定されない。 Preferred specific examples of the partial structure represented by A are listed below, but are not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記一般式（ＩＩＩ）～（Ｖ）のいずれかで表される繰り返し単位としては、より好ましくは、各々下記一般式（ＩＩＩ－１）～（ＩＩＩ－６）、一般式（ＩＶ－１）～（ＩＶ－４）、又は、一般式（Ｖ－１）～（Ｖ－２）のいずれかで表されるものを挙げることができる。 As the repeating unit represented by any one of the above general formulas (III) to (V), more preferably, the following general formulas (III-1) to (III-6), general formulas (IV-1) to Examples thereof include (IV-4) and those represented by general formulas (V-1) to (V-2).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記一般式中、Ａｒ1aは、置換基を有していてもよいアリーレン基を表す。置換基を有していてもよいアリーレン基としては、上記のＸ1～Ｘ3で示したアリーレン基及び上記アリーレン基に置換していてもよい置換基と同様のものが挙げられる。
　Ａｒ2a～Ａｒ4aは、置換基を有していてもよいアリール基を表す。置換基を有していてもよいアリール基としては、上記の一般式（ＺＩ）及び（ＺＩＩ）におけるＲ201～Ｒ203、Ｒ204～Ｒ205で示したアリール基及び上記アリール基に置換していてもよい置換基と同様のものが挙げられる。
　Ｒ01は、水素原子、メチル基、クロロメチル基、トリフルオロメチル基、又はシアノ基を表す。
　Ｒ02及びＲ021は、単結合、アリーレン基、アルキレン基、シクロアルキレン基、－Ｏ－、－ＳＯ2－、ＣＯ－、－Ｎ（Ｒ33）－又はこれらの複数を組み合わせた２価の連結基を表す。これらは、Ｘ1～Ｘ3で示したものと同様のものが挙げられる。 In the above general formula, Ar 1a represents an arylene group which may have a substituent. Examples of the arylene group which may have a substituent include the arylene groups represented by the above X 1 to X 3 and the same substituents as the substituent which may be substituted on the arylene group.
Ar 2a to Ar 4a represent an aryl group which may have a substituent. As the aryl group which may have a substituent, the aryl group represented by R 201 to R 203 and R 204 to R 205 in the above general formulas (ZI) and (ZII) and the above aryl group are substituted. The thing similar to the substituent which may be mentioned is mentioned.
R 01 represents a hydrogen atom, a methyl group, a chloromethyl group, a trifluoromethyl group, or a cyano group.
R 02 and R 021 are a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, CO—, —N (R 33 ) —, or a divalent linkage in which a plurality of these are combined. Represents a group. These are the same as those shown for X 1 to X 3 .
　Ｒ03及びＲ019は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又は、アラルキル基を表す。アルキル基及びシクロアルキル基としては、それぞれ上記したＲ04で示したアルキル基及びシクロアルキル基と同様のものを挙げることができる。アリール基としては、例えば炭素数６～１５個のアリール基であって、具体的には、フェニル基、トリル基、ナフチル基又はアントリル基等を好ましく挙げることができる。アラルキル基としては、例えば、炭素数６～２０であって、ベンジル基又はフェネチル基などが挙げられる。 R 03 and R 019 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group and cycloalkyl group include those similar to the alkyl group and cycloalkyl group represented by R 04 described above. As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group and the like can be preferably exemplified. Examples of the aralkyl group include 6 to 20 carbon atoms and a benzyl group or phenethyl group.
　上記一般式（ＩＩＩ－１）～（ＩＩＩ－６）、一般式（ＩＶ－１）～（ＩＶ－４）、又は、一般式（Ｖ－１）～（Ｖ－２）では、酸アニオンを生じる構造部位がスルホニウム塩構造又はヨードニウム塩構造を含むイオン性構造部位である例を説明したが、酸アニオンを生じる構造部位は塩構造を含まない非イオン性構造部位であってもよい。
　酸アニオンを生じる構造部位が塩構造ではない場合、一般式（ＩＩＩ）～一般式（Ｖ）のいずれかで表される繰り返し単位としては、好ましくは下記一般式で表されるものを挙げることができる。 In the above general formulas (III-1) to (III-6), general formulas (IV-1) to (IV-4), or general formulas (V-1) to (V-2), an acid anion is generated. Although an example in which the structural site is an ionic structural site including a sulfonium salt structure or an iodonium salt structure has been described, the structural site that generates an acid anion may be a nonionic structural site that does not include a salt structure.
In the case where the structural site that generates the acid anion is not a salt structure, the repeating unit represented by any one of the general formulas (III) to (V) preferably includes those represented by the following general formula. it can.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-I000013
　上記一般式中、Ａｒ1は、置換基を有していてもよいアリーレン基を表す。置換基を有していてもよいアリーレン基としては、上記のＸ1～Ｘ3で示したアリーレン基及び上記アリーレン基に置換していてもよい置換基と同様のものが挙げられる。
　Ａｒ6及びＡｒ7は、置換基を有していてもよいアリール基を表す。置換基を有していてもよいアリール基としては、上記のＲ25～Ｒ27で示したアリール基及び上記アリール基に置換していてもよい置換基と同様のものが挙げられる。
　Ｒ01は、水素原子、メチル基、クロロメチル基又はシアノ基を表す。 In the above general formula, Ar 1 represents an arylene group which may have a substituent. Examples of the arylene group which may have a substituent include the arylene groups represented by the above X 1 to X 3 and the same substituents as the substituent which may be substituted on the arylene group.
Ar 6 and Ar 7 represent an aryl group which may have a substituent. Examples of the aryl group which may have a substituent include the aryl groups represented by R 25 to R 27 described above and the same substituents that may be substituted on the aryl group.
R 01 represents a hydrogen atom, a methyl group, a chloromethyl group or a cyano group.
　Ｒ02及びＲ021は、アリーレン基、アルキレン基又はシクロアルキレン基を表す。アリーレン基、アルキレン基又はシクロアルキレン基としては、Ｘ1～Ｘ3で示したものと同様のものが挙げられる。
　Ｒ03、Ｒ05～Ｒ010、Ｒ013、Ｒ015及びＲ022は、アルキル基、ハロアルキル基、シクロアルキル基、アリール基、又は、アラルキル基を表し、これらは上記Ｒ25～Ｒ27で示したものと同義である（ハロアルキル基については、ハロアルキル基中のアルキル基がＲ25～Ｒ27で示したアルキル基と同義である）。
　Ｒ04は、アリーレン基、アルキレン基、又は、置換基を有していてもよい炭素数２～６個のアルケニレン基を表す。アリーレン基又はアルキレン基としては、Ｘ1～Ｘ3で示したものと同様のものが挙げられる。また、上記アルケニレン基としては、置換基を有していてもよい、エチニレン基、プロペニレン基、又は、ブテニレン基等の炭素数２～６個のアルケニレン基が好ましい。置換基としては、上記の更に有していてもよい置換基が挙げられる。 R 02 and R 021 each represents an arylene group, an alkylene group or a cycloalkylene group. Examples of the arylene group, alkylene group, or cycloalkylene group include the same groups as those represented by X 1 to X 3 .
R 03 , R 05 to R 010 , R 013 , R 015 and R 022 each represents an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and these are represented by R 25 to R 27 above. (For the haloalkyl group, the alkyl group in the haloalkyl group has the same meaning as the alkyl group represented by R 25 to R 27 ).
R 04 represents an arylene group, an alkylene group, or an alkenylene group having 2 to 6 carbon atoms which may have a substituent. Examples of the arylene group or alkylene group include the same groups as those represented by X 1 to X 3 . The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms, such as an ethynylene group, a propenylene group, or a butenylene group, which may have a substituent. Examples of the substituent include the substituents that may be further included.
　Ｒ011及びＲ014は、水素原子、水酸基、ハロゲン原子（フッ素原子、塩素原子、臭素原子又はヨウ素原子）、又は、上記で好ましい更なる置換基として示したアルキル基、アルコキシ基、アルコキシカルボニル基若しくはアシロキシ基を表す。
　Ｒ012はニトロ基、シアノ基、又はトリフルオロメチル基、又は、ペンタフルオロエチル基等の過フルオロアルキル基を表す。 R 011 and R 014 are a hydrogen atom, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), or an alkyl group, an alkoxy group, an alkoxycarbonyl group, or Represents an acyloxy group.
R 012 represents a nitro group, a cyano group, a trifluoromethyl group, or a perfluoroalkyl group such as a pentafluoroethyl group.
　本発明において、光酸発生樹脂は酸解離指数ｐＫａが低いことが好ましく、光酸発生樹脂の酸アニオンを生じる構造部位を有するユニット（一般式（ＩＩＩ）～（Ｖ）で表される繰り返し単位の単量体）のｐＫａが６以下であることが好ましく、－４以下であることがより好ましく、－１０以下であることが最も好ましい。
　尚、ｐＫａ値は、弱電解質の水溶液中での解離定数Ｋａの常用対数に負号を付けたもの、即ち、ｐＫａ＝－ｌｏｇ10Ｋａと定義され、例えば、エタノール／水（７／３）中、ＨＣｌ及びＮａＯＨ標準液による滴定により算出されるが、本発明におけるｐＫａ値は、市販ソフトウェアであるＡＣＤ／ＣｈｅｍＳｋｅｔｃｈ（ＡＣＤ／Ｌａｂｓ　８．００　Ｒｅｌｅａｓｅ　Ｐｒｏｄｕｃｔ　Ｖｅｒｓｉｏｎ：８．０８）で計算した値を表す。 In the present invention, the photoacid generator resin preferably has a low acid dissociation index pKa, and is a unit having a structural site that generates an acid anion of the photoacid generator resin (a repeating unit represented by formulas (III) to (V)). Monomer) preferably has a pKa of 6 or less, more preferably −4 or less, and most preferably −10 or less.
The pKa value is defined as a value obtained by adding a negative sign to the common logarithm of the dissociation constant Ka in an aqueous solution of a weak electrolyte, that is, pKa = −log 10 Ka, for example, in ethanol / water (7/3) The pKa value in the present invention is a value calculated by commercially available software ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
　以下に一般式（ＩＩＩ）～一般式（Ｖ）のいずれかで表される繰り返し単位の具体例を示すが、本発明がこれに限定されるものではない。 Specific examples of the repeating unit represented by any one of the general formulas (III) to (V) are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　また、一般式（ＩＩＩ）～一般式(Ｖ)のいずれかで表される繰り返し単位の具体例として、特開平１０－２２１８５２号公報中の例示(ａ１）～（ａ１９６）のうち、樹脂側鎖に酸アニオンを発生する構造のものも挙げられる。 Further, as specific examples of the repeating unit represented by any one of the general formulas (III) to (V), the resin side chain in the examples (a1) to (a196) in JP-A No. 10-221852 is disclosed. In addition, those having a structure generating an acid anion are also included.
　光酸発生樹脂中における繰り返し単位（ＩＩＩ）～（Ｖ）の含有量は、全繰り返し単位に対して、１０～１００モル％の範囲で含有することが好ましく、３０～１００モル％の範囲で含有することがより好ましく、４０～１００モル％の範囲で含有することが特に好ましい。溶解性、塗布性、ガラス転移温度又は分子量制御などを目的として、共重合成分として公知の重合性モノマーを共重合することもできる。共重合されるモノマーはラジカル重合性化合物であることが好ましく、好ましくは（メタ）アクリル酸エステル類、スチレン誘導体、酢酸ビニル、クロトン酸又は無水マレイン酸などが挙げられる。
　繰り返し単位（ＩＩＩ）～（Ｖ）に相当するモノマーの合成方法としては、特に限定されないが、例えば、上記繰り返し単位に対応する重合性不飽和結合を有する酸アニオンと既知のオニウム塩のハライドを交換して合成する方法が挙げられる。
　より具体的には、上記繰り返し単位に対応する重合性不飽和結合を有する酸の金属イオン塩（例えば、ナトリウムイオン又はカリウムイオン等）あるいはアンモニウム塩（アンモニウム又はトリエチルアンモニウム塩等）と、ハロゲンイオン（塩化物イオン、臭化物イオン又はヨウ化物イオン等）を有するオニウム塩を、水又はメタノールの存在下で攪拌してアニオン交換反応を行い、ジクロロメタン、クロロホルム、酢酸エチル、メチルイソブチルケトン又はテトラヒドロキシフラン等の有機溶媒と水で分液・洗浄操作をすることにより、目的とする繰り返し単位に相当するモノマーを合成することができる。
　また、ジクロロメタン、クロロホルム、酢酸エチル、メチルイソブチルケトン又はテトラヒドロキシフラン等の水との分離が可能な有機溶媒と水との存在下で攪拌してアニオン交換反応を行った後に、水で分液・洗浄操作をすることにより合成することもできる。 The content of repeating units (III) to (V) in the photoacid-generating resin is preferably in the range of 10 to 100 mol%, preferably in the range of 30 to 100 mol%, based on all repeating units. More preferably, it is particularly preferably contained in the range of 40 to 100 mol%. For the purpose of solubility, coatability, glass transition temperature or molecular weight control, a known polymerizable monomer can be copolymerized as a copolymerization component. The monomer to be copolymerized is preferably a radical polymerizable compound, preferably (meth) acrylic acid esters, styrene derivatives, vinyl acetate, crotonic acid or maleic anhydride.
The method for synthesizing the monomers corresponding to the repeating units (III) to (V) is not particularly limited. For example, an acid anion having a polymerizable unsaturated bond corresponding to the above repeating unit is exchanged with a known onium salt halide. And a synthesis method.
More specifically, a metal ion salt of an acid having a polymerizable unsaturated bond corresponding to the above repeating unit (for example, sodium ion or potassium ion) or ammonium salt (ammonium or triethylammonium salt etc.) and a halogen ion ( Onium salt having chloride ion, bromide ion or iodide ion) is stirred in the presence of water or methanol to carry out anion exchange reaction, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone or tetrahydroxyfuran. By performing a liquid separation / washing operation with an organic solvent and water, a monomer corresponding to the target repeating unit can be synthesized.
In addition, after an anion exchange reaction by stirring in the presence of an organic solvent that can be separated from water, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, or tetrahydroxyfuran, and water, the solution is separated with water. It can also be synthesized by a washing operation.
　光酸発生樹脂の分子量は、特に制限されないが、重量平均分子量が１０００～１０００００の範囲であることが好ましく、１５００～７００００の範囲であることがより好ましく、３０００～５００００の範囲であることが特に好ましい。ここで、光酸発生樹脂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／キャリア：テトラヒドロフラン（ＴＨＦ）あるいはＮ－メチル－２－ピロリドン（ＮＭＰ））によって測定したポリスチレン換算分子量を示す。
　また分散度（Ｍｗ／Ｍｎ）は、好ましくは１．００～５．００、より好ましくは１．０３～３．５０であり、更に好ましくは、１．０５～２．５０である。 The molecular weight of the photoacid generator resin is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 70000, and particularly preferably in the range of 3000 to 50000. preferable. Here, the weight average molecular weight of the photoacid-generating resin indicates a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC / carrier: tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP)).
The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.
　有機半導体層形成用組成物中の光酸発生樹脂の濃度は、特に限定されないが、有機半導体層形成用組成物全質量に対して、０．０００１～５質量％が好ましく、０．００１～３質量％がより好ましく、０．０１～１質量％が特に好ましい。 The concentration of the photoacid generating resin in the composition for forming an organic semiconductor layer is not particularly limited, but is preferably 0.0001 to 5% by weight, preferably 0.001 to 3% with respect to the total weight of the composition for forming an organic semiconductor layer. % By mass is more preferable, and 0.01 to 1% by mass is particularly preferable.
（有機半導体材料）
　本発明の有機半導体層は、有機半導体材料を含有する。有機半導体材料は、半導体としての性質を示す材料である。本発明において、有機半導体材料はＰ型であることが好ましい。 (Organic semiconductor materials)
The organic semiconductor layer of the present invention contains an organic semiconductor material. An organic semiconductor material is a material exhibiting properties as a semiconductor. In the present invention, the organic semiconductor material is preferably P-type.
　有機半導体材料としては、例えば、６，１３－ビス（トリイソプロピルシリルエチニル）ペンタセン（ＴＩＰＳペンタセン）、テトラメチルペンタセン、若しくは、パーフルオロペンタセン等のペンタセン類、５，１１－ビス(トリエチルシリルエチニル)アントラジチオフェン（ＴＥＳ－ＡＤＴ）、若しくは、２，８－ジフルオロ－５，１１－ビス（トリエチルシリルエチニル）アントラジチオフェン（ｄｉＦ－ＴＥＳ－ＡＤＴ）等のアントラジチオフェン類、ジフェニルベンゾチエノベンゾチオフェン（ＤＰｈ－ＢＴＢＴ）、若しくは、アルキルベンゾチエノベンゾチオフェン（Ｃｎ－ＢＴＢＴ）等のベンゾチエノベンゾチオフェン類、アルキルジナフトチエノチオフェン（Ｃｎ－ＤＮＴＴ）等のジナフトチエノチオフェン類、ペリキサンテノキサンテン等のジオキサアンタントレン類、ルブレン類、Ｃ６０、若しくは、フェニルＣ６１酪酸メチルエステル（ＰＣＢＭ）等のフラーレン類、銅フタロシアニン、若しくは、フッ素化銅フタロシアニン等のフタロシアニン類、ポリ（３－ヘキシルチオフェン）（Ｐ３ＲＴ）、ポリクアテルチオフェン（ＰＱＴ）、若しくは、ポリ（３－ヘキシルチオフェン）（Ｐ３ＨＴ）等のポリチオフェン類、ポリ［２，５－ビス（３－ドデシルチオフェン－２－イル）チエノ［３，２－ｂ］チオフェン］（ＰＢＴＴＴ）等のポリチエノチオフェン類、又は、後述する特定有機半導体材料などが挙げられる。
　これらの中でも、作製される有機半導体層のキャリア移動度などの性能がより向上する等の観点から、以下の特定有機半導体材料（以下、「成分Ａ」ともいう。）を用いることが好ましい。
　本発明において、特定有機半導体材料（成分Ａ）とは、縮合多環芳香族基を有し、上記縮合多環芳香族基中の環数が４つ以上であり、上記縮合多環芳香族基中の少なくとも２つの環が、硫黄原子、窒素原子、セレン原子及び酸素原子よりなる群から選択される少なくとも１つの原子を含み、上記縮合多環芳香族基中の部分構造として、ベンゼン環、ナフタレン環、及び、フェナントレン環よりなる群から選択される少なくともいずれか１つの構造を含む有機半導体材料のことをいう。
　ただし、特定有機半導体材料における縮合多環芳香族基中の部分構造には、アントラセン環は含まれないことが好ましい。
　なお、縮合多環芳香族基とは、芳香族環が複数縮合して得られる基である。
　芳香族環としては、芳香族炭化水素環（例えば、ベンゼン環）及び芳香族複素環（例えば、チオフェン環、フラン環、ピロール環、セレノフェン環、又は、イミダゾール環）が挙げられる。 Examples of the organic semiconductor material include pentacenes such as 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS pentacene), tetramethylpentacene, or perfluoropentacene, and 5,11-bis (triethylsilylethynyl) an Anthradithiophenes such as tradithiophene (TES-ADT) or 2,8-difluoro-5,11-bis (triethylsilylethynyl) anthradithiophene (diF-TES-ADT), diphenylbenzothienobenzothiophene (DPh) -BTBT), or benzothienobenzothiophenes such as alkylbenzothienobenzothiophene (Cn-BTBT), dinaphthothienothiophenes such as alkyldinaphthothienothiophene (Cn-DNTT), perixan Di oxa-en tanto Len such as Nokisanten, rubrene compounds, C60, or fullerenes such as phenyl C 61 butyric acid methyl ester (PCBM), copper phthalocyanine, or, phthalocyanines such as fluorinated copper phthalocyanine, poly (3-hexylthiophene ) (P3RT), polyquaterthiophene (PQT), or polythiophene such as poly (3-hexylthiophene) (P3HT), poly [2,5-bis (3-dodecylthiophen-2-yl) thieno [3 , 2-b] thiophene] (PBTTT), or specific organic semiconductor materials described later.
Among these, it is preferable to use the following specific organic semiconductor material (hereinafter also referred to as “component A”) from the viewpoint of further improving performance such as carrier mobility of the organic semiconductor layer to be produced.
In the present invention, the specific organic semiconductor material (component A) has a condensed polycyclic aromatic group, the number of rings in the condensed polycyclic aromatic group is 4 or more, and the condensed polycyclic aromatic group At least two of the rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and the partial structure in the condensed polycyclic aromatic group includes a benzene ring, naphthalene An organic semiconductor material containing at least one structure selected from the group consisting of a ring and a phenanthrene ring.
However, it is preferable that the anthracene ring is not included in the partial structure in the condensed polycyclic aromatic group in the specific organic semiconductor material.
The condensed polycyclic aromatic group is a group obtained by condensing a plurality of aromatic rings.
Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring) and an aromatic heterocyclic ring (for example, a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, or an imidazole ring).
　成分Ａ中には、縮合多環芳香族基（縮合多環芳香族構造）が含まれるが、この基が主成分として含まれることが好ましい。ここで主成分とは、縮合多環芳香族基の分子量の含有量が、成分Ａの全分子量に対して、３０％以上であることを意図し、４０％以上であることが好ましい。上限は特に制限されないが、溶解性の点から、８０％以下であることが好ましい。
　縮合多環芳香族基は、複数の環が縮合して形成される環構造であり、芳香族性を示す。
　成分Ａにおける縮合多環芳香族基中の環数は４以上であり、有機薄膜トランジスタのキャリア移動度の観点から、４～９が好ましく、４～７がより好ましく、４～６が更に好ましい。
　また、上記縮合多環芳香族基中、少なくとも２つの環が、硫黄原子、窒素原子、セレン原子及び酸素原子よりなる群から選択された少なくとも１種の原子を含み、有機薄膜トランジスタのキャリア移動度の観点から、２～６つの環が上記原子を含むことが好ましく、２～４つの環が上記原子を含むことがより好ましい。
　また、有機薄膜トランジスタのキャリア移動度の観点から、上記縮合多環芳香族基中に少なくとも２つの複素環が含まれ、上記複素環中にそれぞれ１個のヘテロ原子を有することが好ましい。ヘテロ原子の種類は特に制限されず、Ｏ原子（酸素原子）、Ｓ原子（硫黄原子）、Ｎ原子（窒素原子）、又は、Ｓｅ原子（セレン原子）などが挙げられる。
　成分Ａにおける縮合多環芳香族基中には、部分構造として、ベンゼン環、ナフタレン環及びフェナントレン環よりなる群から選択された少なくともいずれか１つの構造が含まれる。なお、上記部分構造としては、アントラセン環は含まれないことが好ましい。
　また、成分Ａは、有機薄膜トランジスタのキャリア移動度の観点から、チオフェン環構造及び／又はセレノフェン環構造を少なくとも有することが好ましく、チオフェン環構造を少なくとも有することがより好ましく、成分Ａが有する複素環構造が全てチオフェン環構造であることが更に好ましい。 Component A contains a condensed polycyclic aromatic group (condensed polycyclic aromatic structure), and this group is preferably contained as a main component. Here, the main component means that the molecular weight content of the condensed polycyclic aromatic group is 30% or more with respect to the total molecular weight of Component A, and is preferably 40% or more. The upper limit is not particularly limited, but is preferably 80% or less from the viewpoint of solubility.
The condensed polycyclic aromatic group is a ring structure formed by condensing a plurality of rings, and exhibits aromaticity.
The number of rings in the condensed polycyclic aromatic group in Component A is 4 or more, preferably 4 to 9, more preferably 4 to 7, and still more preferably 4 to 6 from the viewpoint of carrier mobility of the organic thin film transistor.
In the condensed polycyclic aromatic group, at least two rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and the carrier mobility of the organic thin film transistor From the viewpoint, it is preferable that 2 to 6 rings include the above atoms, and it is more preferable that 2 to 4 rings include the above atoms.
Further, from the viewpoint of carrier mobility of the organic thin film transistor, it is preferable that at least two heterocycles are contained in the condensed polycyclic aromatic group, and each heterocycle has one heteroatom. The kind of the hetero atom is not particularly limited, and examples thereof include an O atom (oxygen atom), an S atom (sulfur atom), an N atom (nitrogen atom), or an Se atom (selenium atom).
The condensed polycyclic aromatic group in Component A includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure. The partial structure preferably does not include an anthracene ring.
Component A preferably has at least a thiophene ring structure and / or a selenophene ring structure, more preferably at least a thiophene ring structure, from the viewpoint of carrier mobility of the organic thin film transistor, and a heterocyclic structure of component A It is more preferable that all have a thiophene ring structure.
　上記縮合多環芳香族基としては、有機薄膜トランジスタのキャリア移動度の観点から、部分構造として、ベンゼン環、ナフタレン環及びフェナントレン環よりなる群から選択されたいずれか少なくとも１つの構造を含み、２つ以上のチオフェン環を含み、環数が４つ以上の縮合多環芳香族基が好ましい。中でも、部分構造として、ベンゼン環を含み、２つ以上のチオフェン環とを含み、環数が４つ以上の縮合多環芳香族基がより好ましい。
　また、上記縮合多環芳香族基としては、有機薄膜トランジスタのキャリア移動度の観点から、上記縮合多環芳香族基中のチオフェン環の数は、３つ以上が好ましく、３～５つがより好ましく、３～４つが更に好ましく、３つが特に好ましい。
　また、有機薄膜トランジスタのキャリア移動度の観点から、上記縮合多環芳香族基中の環数は、４～６つが好ましく、５～６つがより好ましく、５つが更に好ましい。上記縮合多環芳香族基としては、２つのベンゼン環と、３つのチオフェン環とを含み、かつ、環数が５つである縮合多環芳香族基であることが特に好ましい。 The condensed polycyclic aromatic group includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure from the viewpoint of carrier mobility of an organic thin film transistor, A condensed polycyclic aromatic group containing the above thiophene ring and having 4 or more rings is preferable. Among these, a condensed polycyclic aromatic group containing a benzene ring, 2 or more thiophene rings, and 4 or more rings is more preferable as the partial structure.
Further, as the condensed polycyclic aromatic group, from the viewpoint of carrier mobility of the organic thin film transistor, the number of thiophene rings in the condensed polycyclic aromatic group is preferably 3 or more, more preferably 3 to 5, Three to four are more preferable, and three are particularly preferable.
Further, from the viewpoint of carrier mobility of the organic thin film transistor, the number of rings in the condensed polycyclic aromatic group is preferably 4 to 6, more preferably 5 to 6, and still more preferably 5. The condensed polycyclic aromatic group is particularly preferably a condensed polycyclic aromatic group containing two benzene rings and three thiophene rings and having 5 rings.
　更に、縮合多環芳香族基としては、硫黄原子、窒素原子、セレン原子及び酸素原子よりなる群から選択された少なくとも１種の原子を含む環（複素環。好ましくは、チオフェン環）と、ベンゼン環とが交互に縮合（縮環）した基（縮合してなる基）が好ましく挙げられる。 Further, the condensed polycyclic aromatic group includes a ring (heterocycle, preferably a thiophene ring) containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and benzene. A group in which a ring is alternately condensed (condensed) (a group formed by condensation) is preferable.
　成分Ａとしては、有機薄膜トランジスタのキャリア移動度の観点から、式（１）～式（１６）のいずれかで表される化合物を少なくとも１種含むことが好ましく、式（１）～式（１６）のいずれかで表される１種以上の化合物であることがより好ましい。
　有機半導体層中には、１種のみの成分Ａが含まれていても、２種以上の成分Ａが含まれていてもよい。 Component A preferably contains at least one compound represented by any one of formulas (1) to (16) from the viewpoint of carrier mobility of the organic thin film transistor, and includes formula (1) to formula (16). It is more preferable that it is 1 or more types of compounds represented by either.
The organic semiconductor layer may contain only one type of component A or two or more types of component A.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（１）中、Ａ１ａ及びＡ１ｂはそれぞれ独立に、Ｓ原子、Ｏ原子又はＳｅ原子を表し、Ｒ１ａ～Ｒ１ｆはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１ａ～Ｒ１ｆのうち少なくとも１つが下記式（Ｗ）で表される基である。
　　－ＬＷ－ＲＷ　　　（Ｗ）
　式（Ｗ）中、ＬＷは下記式（Ｌ－１）～式（Ｌ－２５）のいずれかで表される二価の連結基又は２以上の下記式（Ｌ－１）～（Ｌ－２５）のいずれかで表される二価の連結基が結合した二価の連結基を表し、ＲＷはアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、又は、トリアルキルシリル基を表す。 In formula (1), A 1a and A 1b each independently represents an S atom, an O atom or a Se atom, R 1a to R 1f each independently represents a hydrogen atom or a substituent, and R 1a to R 1f At least one of them is a group represented by the following formula (W).
-L W -R W (W)
In the formula (W), L W represents a divalent linking group represented by any of the following formulas (L-1) to (L-25), or two or more of the following formulas (L-1) to (L- represents a divalent linking group is a divalent linking group represented by any one bound of 25), R W is an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number of oxyethylene units v represents an oligooxyethylene group having 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｌ－１）～式（Ｌ－２５）中、＊はＲＷとの結合位置を表し、波線部分はもう一方の結合位置を表し、式（Ｌ－１）、式（Ｌ－２）、式（Ｌ－６）及び式（Ｌ－１３）～式（Ｌ－２４）におけるＲ’はそれぞれ独立に、水素原子又は置換基を表し、ＲＮは水素原子又は置換基を表し、Ｒｓｉはそれぞれ独立に、水素原子、アルキル基、アルケニル基又はアルキニル基を表す。
　式（２）中、Ｘ２ａ及びＸ２ｂはそれぞれ独立に、ＮＲ２ｉ、Ｏ原子又はＳ原子を表し、Ａ２ａはＣＲ２ｇ又はＮ原子を表し、Ａ２ｂはＣＲ２ｈ又はＮ原子を表し、Ｒ２ｉは水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基を表し、Ｒ２ａ～Ｒ２ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ２ａ～Ｒ２ｈのうち少なくとも１つが上記式（Ｗ）で表される基である。
　式（３）中、Ｘ３ａ及びＸ３ｂはそれぞれ独立に、Ｓ原子、Ｏ原子又はＮＲ３ｇを表し、Ａ３ａ及びＡ３ｂはそれぞれ独立に、ＣＲ３ｈ又はＮ原子を表す。Ｒ３ａ～Ｒ３ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ３ａ～Ｒ３ｈのうち少なくとも１つが上記式（Ｗ）で表される基である。
　式（４）中、Ｘ４ａ及びＸ４ｂはそれぞれ独立に、Ｏ原子、Ｓ原子又はＳｅ原子を表し、４ｐ及び４ｑはそれぞれ独立に、０～２の整数を表し、Ｒ４ａ～Ｒ４ｊ、Ｒ４ｋ及びＲ４ｍはそれぞれ独立に、水素原子、ハロゲン原子又は上記式（Ｗ）で表される基を表し、かつ、Ｒ４ａ～Ｒ４ｊ、Ｒ４ｋ及びＲ４ｍのうち少なくとも１つは上記式（Ｗ）で表される基であり、ただし、Ｒ４ｅ及びＲ４ｆのうち少なくとも一方が上記式（Ｗ）で表される基である場合はＲ４ｅ及びＲ４ｆが表す上記式（Ｗ）においてＬＷは上記式（Ｌ－２）又は式（Ｌ－３）で表される二価の連結基である。 Formula (L-1) ~ formula (L-25), * represents a bonding position to R W, wavy line portion represents the other coupling position of the formula (L-1), formula (L-2) , R 'are each independently of formula (L-6) and formula (L-13) ~ formula (L-24), represents a hydrogen atom or a substituent, R N represents a hydrogen atom or a substituent, R si Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
In formula (2), X 2a and X 2b each independently represent NR 2i , O atom or S atom, A 2a represents CR 2g or N atom, A 2b represents CR 2h or N atom, R 2 2i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, R 2a to R 2h each independently represents a hydrogen atom or a substituent, and at least one of R 2a to R 2h is represented by the above formula ( W).
In formula (3), X 3a and X 3b each independently represent an S atom, an O atom or NR 3g , and A 3a and A 3b each independently represent a CR 3h or an N atom. R 3a to R 3h each independently represents a hydrogen atom or a substituent, and at least one of R 3a to R 3h is a group represented by the above formula (W).
In the formula (4), X 4a and X 4b each independently represent an O atom, an S atom or a Se atom, 4p and 4q each independently represents an integer of 0 to 2, R 4a to R 4j , R 4k and R 4m each independently represent a hydrogen atom, a halogen atom or a group represented by the above formula (W), and at least one of R 4a to R 4j , R 4k and R 4m is represented by the above formula ( a group represented by W), however, the above formula when at least one of R 4e and R 4f is a group represented by the formula (W) represented by R 4e and R 4f in (W) L W is a divalent linking group represented by the above formula (L-2) or (L-3).
　式（５）中、Ｘ５ａ及びＸ５ｂはそれぞれ独立に、ＮＲ５ｉ、Ｏ原子又はＳ原子を表し、Ａ５ａはＣＲ５ｇ又はＮ原子を表し、Ａ５ｂはＣＲ５ｈ又はＮ原子を表し、Ｒ５ｉは水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、Ｒ５ａ～Ｒ５ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ５ａ～Ｒ５ｈのうち少なくとも１つが上記式（Ｗ）で表される基である。
　式（６）中、Ｘ６ａ～Ｘ６ｄはそれぞれ独立に、ＮＲ６ｇ、Ｏ原子又はＳ原子を表し、Ｒ６ｇは水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、Ｒ６ａ～Ｒ６ｆはそれぞれ独立に、水素原子又は置換基を表し、Ｒ６ａ～Ｒ６ｆのうち少なくとも１つが上記式（Ｗ）で表される基である。
　式（７）中、Ｘ７ａ及びＸ７ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ７ｉを表し、Ｘ７ｂ及びＸ７ｄはそれぞれ独立に、Ｓ原子、Ｏ原子又はＳｅ原子を表し、Ｒ７ａ～Ｒ７ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ７ａ～Ｒ７ｉのうち少なくとも１つが上記式（Ｗ）で表される基である。
　式（８）中、Ｘ８ａ及びＸ８ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ８ｉを表し、Ｘ８ｂ及びＸ８ｄはそれぞれ独立に、Ｓ原子、Ｏ原子又はＳｅ原子を表し、Ｒ８ａ～Ｒ８ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ８ａ～Ｒ８ｉのうち少なくとも１つが上記式（Ｗ）で表される基である。 In formula (5), X 5a and X 5b each independently represent NR 5i , O atom or S atom, A 5a represents CR 5g or N atom, A 5b represents CR 5h or N atom, R 5 5i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, R 5a to R 5h each independently represents a hydrogen atom or a substituent, and R 5a to R 5h At least one of them is a group represented by the above formula (W).
In the formula (6), X 6a to X 6d each independently represents NR 6g , O atom or S atom, and R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl. R 6a to R 6f each independently represents a hydrogen atom or a substituent, and at least one of R 6a to R 6f is a group represented by the above formula (W).
In formula (7), X 7a and X 7c each independently represents an S atom, O atom, Se atom or NR 7i , and X 7b and X 7d each independently represent an S atom, O atom or Se atom. R 7a to R 7i each independently represents a hydrogen atom or a substituent, and at least one of R 7a to R 7i is a group represented by the above formula (W).
In formula (8), X 8a and X 8c each independently represent an S atom, O atom, Se atom or NR 8i , and X 8b and X 8d each independently represent an S atom, O atom or Se atom. R 8a to R 8i each independently represents a hydrogen atom or a substituent, and at least one of R 8a to R 8i is a group represented by the above formula (W).
　式（９）中、Ｘ９ａ及びＸ９ｂはそれぞれ独立に、Ｏ原子、Ｓ原子又はＳｅ原子を表し、Ｒ９ｃ、Ｒ９ｄ及びＲ９ｇ～Ｒ９ｊはそれぞれ独立に、水素原子、ハロゲン原子又は上記式（Ｗ）で表される基を表し、Ｒ９ａ、Ｒ９ｂ、Ｒ９ｅ及びＲ９ｆはそれぞれ独立に、水素原子又は置換基を表す。
　式（１０）中、Ｒ１０ａ～Ｒ１０ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１０ａ～Ｒ１０ｈのうち少なくとも１つは上記式（Ｗ）で表される置換基を表し、Ｘ１０ａ及びＸ１０ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１０ｉを表し、Ｒ１０ｉはそれぞれ独立に、水素原子又は上記式（Ｗ）で表される基を表す。
　式（１１）中、Ｘ１１ａ及びＸ１１ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１１ｎを表し、Ｒ１１ａ～Ｒ１１ｋ、Ｒ１１ｍ及びＲ１１ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１１ａ～Ｒ１１ｋ、Ｒ１１ｍ及びＲ１１ｎのうち少なくとも１つは上記式（Ｗ）で表される基である。
　式（１２）中、Ｘ１２ａ及びＸ１２ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１２ｎを表し、Ｒ１２ａ～Ｒ１２ｋ、Ｒ１２ｍ及びＲ１２ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１２ａ～Ｒ１２ｋ、Ｒ１２ｍ及びＲ１２ｎのうち少なくとも１つは上記式（Ｗ）で表される基である。 In the formula (9), X 9a and X 9b each independently represent an O atom, an S atom or a Se atom, and R 9c , R 9d and R 9g to R 9j each independently represent a hydrogen atom, a halogen atom or the above The group represented by the formula (W) is represented, and R 9a , R 9b , R 9e and R 9f each independently represent a hydrogen atom or a substituent.
In formula (10), R 10a to R 10h each independently represents a hydrogen atom or a substituent, and at least one of R 10a to R 10h represents a substituent represented by the above formula (W), 10a and X 10b each independently represent an S atom, an O atom, a Se atom or NR 10i , and R 10i each independently represents a hydrogen atom or a group represented by the above formula (W).
In formula (11), X 11a and X 11b each independently represent an S atom, O atom, Se atom or NR 11n , and R 11a to R 11k , R 11m and R 11n each independently represent a hydrogen atom or a substituent And at least one of R 11a to R 11k , R 11m and R 11n is a group represented by the above formula (W).
In the formula (12), X 12a and X 12b each independently represent an S atom, an O atom, a Se atom or NR 12n , and R 12a to R 12k , R 12m and R 12n each independently represent a hydrogen atom or a substituent And at least one of R 12a to R 12k , R 12m and R 12n is a group represented by the above formula (W).
　式（１３）中、Ｘ１３ａ及びＸ１３ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１３ｎを表し、Ｒ１３ａ～Ｒ１３ｋ、Ｒ１３ｍ及びＲ１３ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１３ａ～Ｒ１３ｋ、Ｒ１３ｍ及びＲ１３ｎのうち少なくとも１つは上記式（Ｗ）で表される基である。
　式（１４）中、Ｘ１４ａ～Ｘ１４ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１４ｉを表し、Ｒ１４ａ～Ｒ１４ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１４ａ～Ｒ１４ｉのうち少なくとも１つは上記式（Ｗ）で表される基である。
　式（１５）中、Ｘ１５ａ～Ｘ１５ｄはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１５ｇを表し、Ｒ１５ａ～Ｒ１５ｇはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１５ａ～Ｒ１５ｇのうち少なくとも１つは上記式（Ｗ）で表される基である。
　式（１６）中、Ｘ１６ａ～Ｘ１６ｄはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１６ｇを表し、Ｒ１６ａ～Ｒ１６ｇはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１６ａ～Ｒ１６ｇのうち少なくとも１つは上記式（Ｗ）で表される基である。 In formula (13), X 13a and X 13b each independently represent an S atom, an O atom, a Se atom or NR 13n , and R 13a to R 13k , R 13m and R 13n each independently represent a hydrogen atom or a substituent And at least one of R 13a to R 13k , R 13m and R 13n is a group represented by the above formula (W).
In the formula (14), X 14a to X 14c each independently represents an S atom, O atom, Se atom or NR 14i , R 14a to R 14i each independently represents a hydrogen atom or a substituent, and R 14a At least one of ˜R 14i is a group represented by the above formula (W).
In the formula (15), X 15a to X 15d each independently represents an S atom, an O atom, a Se atom, or NR 15g , R 15a to R 15g each independently represents a hydrogen atom or a substituent, and R 15a At least one of ˜R 15g is a group represented by the above formula (W).
In the formula (16), X 16a to X 16d each independently represents an S atom, an O atom, a Se atom or NR 16g , R 16a to R 16g each independently represents a hydrogen atom or a substituent, and R 16a At least one of ˜R 16g is a group represented by the above formula (W).
－式（１）で表される化合物－ -Compound represented by Formula (1)-
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（１）において、Ａ１ａ及びＡ１ｂはそれぞれ独立に、Ｓ原子（硫黄原子）、Ｏ原子（酸素原子）又はＳｅ原子（セレン原子）を表す。Ａ１ａ及びＡ１ｂはＳ原子又はＯ原子が好ましい。また、Ａ１ａ及びＡ１ｂは互いに同一であっても異なっていてもよいが、互いに同一であることが好ましい。
　式（１）において、Ｒ１ａ～Ｒ１ｆはそれぞれ独立に、水素原子又は置換基を表す。ただし、Ｒ１ａ～Ｒ１ｆのうち少なくとも１つが後述する式（Ｗ）で表される基である。 In formula (1), A 1a and A 1b each independently represent an S atom (sulfur atom), an O atom (oxygen atom), or an Se atom (selenium atom). A 1a and A 1b are preferably S atoms or O atoms. A 1a and A 1b may be the same or different from each other, but are preferably the same.
In the formula (1), R 1a to R 1f each independently represents a hydrogen atom or a substituent. However, at least one of R 1a to R 1f is a group represented by the following formula (W).
　式（１）で表される化合物は、後述する式（Ｗ）で表される基以外のその他の置換基を有していてもよい。
　式（１）のＲ１ａ～Ｒ１ｆが採りうる置換基の種類は特に制限されないが、以下に説明する置換基Ｘが挙げられる。置換基Ｘとしては、後述する式（Ｗ）で表される基、ハロゲン原子、アルキル基（シクロアルキル基、ビシクロアルキル基、又は、トリシクロアルキル基を含む。）、アルケニル基（シクロアルケニル基、又は、ビシクロアルケニル基を含む。）、アルキニル基、アリール基、複素環基（ヘテロ環基といってもよい。）、シアノ基、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基（アニリノ基を含む。）、アンモニオ基、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、スルファモイルアミノ基、アルキル及びアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキル及びアリールスルフィニル基、アルキル及びアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール及びヘテロ環アゾ基、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、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、ボロン酸基（－Ｂ（ＯＨ）２）、ホスファト基（－ＯＰＯ（ＯＨ）２）、スルファト基（－ＯＳＯ３Ｈ）、又は、その他の公知の置換基が挙げられる。なお、本明細書の式（１）～式（１６）においては、「置換基」としては、上記置換基Ｘが好ましく挙げられる。
　これらの中でも、後述する式（Ｗ）で表される基以外の基としては、ハロゲン原子、アルキル基、アルキニル基、アルケニル基、アルコキシ基、アルキルチオ基、又は、アリール基が好ましく、フッ素原子、炭素数１～３の置換若しくは無置換のアルキル基、炭素数２～３の置換若しくは無置換のアルキニル基、炭素数２～３の置換若しくは無置換のアルケニル基、炭素数１～２の置換若しくは無置換のアルコキシ基、置換若しくは無置換のメチルチオ基、又は、フェニル基がより好ましく、フッ素原子、炭素数１～３の置換若しくは無置換のアルキル基、炭素数２～３の置換若しくは無置換のアルキニル基、炭素数２～３の置換若しくは無置換のアルケニル基、炭素数１～２の置換若しくは無置換のアルコキシ基、又は、置換若しくは無置換のメチルチオ基が特に好ましい。 The compound represented by Formula (1) may have other substituents other than the group represented by Formula (W) described later.
The type of substituent that can be taken by R 1a to R 1f in formula (1) is not particularly limited, and examples thereof include substituent X described below. As the substituent X, a group represented by the formula (W) described later, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group), an alkenyl group (a cycloalkenyl group, Or a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (also referred to as a heterocyclic group), a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an aryloxy group, Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino Group, aryloxycarbonylamino group, sulfamo Ruamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, Alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) 2 ), phosphato group (—OPO (OH) 2 ), sulfato group (—OSO 3 H), or other known substituents. In the formulas (1) to (16) of the present specification, examples of the “substituent” preferably include the above-described substituent X.
Among these, as a group other than the group represented by the formula (W) described later, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, or an aryl group is preferable, and a fluorine atom, carbon A substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted carbon group having 1 to 2 carbon atoms A substituted alkoxy group, a substituted or unsubstituted methylthio group, or a phenyl group is more preferable, and a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms. Group, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted group Particularly preferred methylthio group is.
　式（１）で表される化合物中において、Ｒ１ａ～Ｒ１ｆのうち、式（Ｗ）で表される基以外のその他の置換基の個数は０～４であることが好ましく、０～２であることがより好ましく、０であることが特に好ましい。
　また、これら置換基は、更に上記置換基Ｘを有していてもよい。
　中でも、Ｒ１ｃ～Ｒ１ｆはそれぞれ独立に、水素原子、フッ素原子、炭素数１～３の置換若しくは無置換のアルキル基、炭素数２～３の置換若しくは無置換のアルキニル基、炭素数２～３の置換若しくは無置換のアルケニル基、炭素数１～２の置換若しくは無置換のアルコキシ基、又は、置換若しくは無置換のメチルチオ基であることが好ましい。 In the compound represented by the formula (1), among R 1a to R 1f , the number of other substituents other than the group represented by the formula (W) is preferably 0 to 4, and 0 to 2 Is more preferable, and 0 is particularly preferable.
These substituents may further have the above substituent X.
Among them, R 1c to R 1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or 2 to 3 carbon atoms. 3 is preferably a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group.
　次に、式（Ｗ）で表される基について説明する。
　　－ＬＷ－ＲＷ　　　（Ｗ）
　式（Ｗ）中、Ｌは下記式（Ｌ－１）～式（Ｌ－２５）のいずれかで表される二価の連結基、又は、二以上の下記式（Ｌ－１）～（Ｌ－２５）のいずれかで表される二価の連結基が結合した二価の連結基を表す。 Next, the group represented by the formula (W) will be described.
-L W -R W (W)
In the formula (W), L represents a divalent linking group represented by any of the following formulas (L-1) to (L-25), or two or more of the following formulas (L-1) to (L And a divalent linking group to which the divalent linking group represented by any one of -25) is bonded.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（Ｌ－１）～式（Ｌ－２５）中、＊はＲＷとの結合位置を表し、波線部分はもう一方の結合位置を表す。より具体的には、例えば、式（１）で表される化合物においては、波線部分は式（１）で表される骨格を形成する環と結合する。なお、後述するように、式（Ｗ）が他の化合物に含まれる場合、波線部分は各化合物の骨格を形成する環と結合する。
　なお、ＬＷが式（Ｌ－１）～式（Ｌ－２５）のいずれかで表される二価の連結基が２つ以上結合した二価の連結基を表す場合、一方の連結基の＊が、他方の連結基の波線部分と結合する。
　式（Ｌ－１３）～式（Ｌ－２４）におけるＲ’の結合位置及びＲＷとの結合位置＊は、芳香環又は複素芳香環上の任意の位置をとることができる。
　式（Ｌ－１）、式（Ｌ－２）、式（Ｌ－６）及び式（Ｌ－１３）～式（Ｌ－２４）におけるＲ’はそれぞれ独立に、水素原子又は置換基を表す。ＲＮは水素原子又は置換基を表す。Ｒｓｉはそれぞれ独立に、水素原子、アルキル基、アルケニル基又はアルキニル基を表す。
　式（Ｌ－１）及び式（Ｌ－２）中のＲ’はそれぞれＬＷに隣接するＲＷと結合して縮合環を形成してもよい。 Wherein (L-1) ~ formula (L-25), * represents a bonding position to R W, wavy line portion represents the other coupling position. More specifically, for example, in the compound represented by the formula (1), the wavy line part is bonded to the ring forming the skeleton represented by the formula (1). As will be described later, when formula (W) is contained in another compound, the wavy line part is bonded to a ring forming the skeleton of each compound.
In addition, when L W represents a divalent linking group in which two or more divalent linking groups represented by any of formulas (L-1) to (L-25) are bonded, * Couple | bonds with the wavy line part of the other connection group.
Formula (L-13) ~ formula (L-24) binding to the binding position and R W of R 'at the position * may take any position on the aromatic ring or a heteroaromatic ring.
In formula (L-1), formula (L-2), formula (L-6) and formula (L-13) to formula (L-24), R ′ each independently represents a hydrogen atom or a substituent. RN represents a hydrogen atom or a substituent. R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
Formula (L-1) and formula (L-2) R 'in may form a condensed ring by combining with R W adjacent L W respectively.
　これらの中でも、式（Ｌ－１７）～式（Ｌ－２１）、式（Ｌ－２３）及び式（Ｌ－２４）のいずれかで表される二価の連結基は、下記式（Ｌ－１７Ａ）～式（Ｌ－２１Ａ）、式（Ｌ－２３Ａ）及び式（Ｌ－２４Ａ）で表される二価の連結基であることがより好ましい。 Among these, the divalent linking group represented by any of the formulas (L-17) to (L-21), (L-23), and (L-24) is represented by the following formula (L- 17A) to the formula (L-21A), the formula (L-23A), and the divalent linking group represented by the formula (L-24A) are more preferable.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　ここで、置換又は無置換のアルキル基、オキシエチレン基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、あるいは、置換又は無置換のトリアルキルシリル基が置換基の末端に存在する場合は、式（Ｗ）における－ＲＷ単独と解釈することもでき、式（Ｗ）における－ＬＷ－ＲＷと解釈することもできる。
　本発明では、主鎖が炭素数Ｎ個の置換又は無置換のアルキル基が置換基の末端に存在する場合は、置換基の末端から可能な限りの連結基を含めた上で式（Ｗ）における－ＬＷ－ＲＷと解釈することとし、具体的には「式（Ｗ）におけるＬＷに相当する式（Ｌ－１）で表される基１個」と「式（Ｗ）におけるＲＷに相当する主鎖が炭素数Ｎ－１個の置換又は無置換のアルキル基」とが結合した置換基として解釈する。例えば、炭素数８のアルキル基であるｎ－オクチル基が置換基の末端に存在する場合、２個のＲ’が水素原子である式（Ｌ－１）で表される基１個と、炭素数７のｎ－ヘプチル基とが結合した置換基として解釈する。
　一方、本発明では、オキシエチレン基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、あるいは、置換又は無置換のトリアルキルシリル基が置換基の末端に存在する場合は、置換基の末端から可能な限りの連結基を含めた上で、式（Ｗ）におけるＲＷ単独と解釈する。例えば、－（ＯＣＨ２ＣＨ２）－（ＯＣＨ２ＣＨ２）－（ＯＣＨ２ＣＨ２）－ＯＣＨ３基が置換基の末端に存在する場合、オキシエチレン単位の繰り返し数ｖが３のオリゴオキシエチレン基単独の置換基として解釈する。 Here, a substituted or unsubstituted alkyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group. When a substituted trialkylsilyl group is present at the terminal of the substituent, it can be interpreted as -R W alone in the formula (W), or can be interpreted as -L W -R W in the formula (W). .
In the present invention, when a substituted or unsubstituted alkyl group having N carbon atoms in the main chain is present at the terminal of the substituent, formula (W) after including all possible linking groups from the terminal of the substituent. -L W -R W in the formula, specifically, “one group represented by the formula (L-1) corresponding to L W in the formula (W)” and “R in the formula (W)” This is interpreted as a substituent in which the main chain corresponding to W is bonded to a substituted or unsubstituted alkyl group having N-1 carbon atoms. For example, when an n-octyl group, which is an alkyl group having 8 carbon atoms, is present at the end of the substituent, one group represented by the formula (L-1) in which two R ′ are hydrogen atoms, This is interpreted as a substituent bonded to the n-heptyl group of Formula 7.
On the other hand, in the present invention, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. If a group is present at the end of the substituents on including a linking group as possible from the end of the substituent, it is interpreted as R W alone in the formula (W). For example, when a — (OCH 2 CH 2 ) — (OCH 2 CH 2 ) — (OCH 2 CH 2 ) —OCH 3 group is present at the end of the substituent, an oligooxyethylene having a repeating number v of oxyethylene units of 3 Interpreted as a single group substituent.
　ＬＷが式（Ｌ－１）～式（Ｌ－２５）のいずれかで表される二価の連結基が結合した連結基を形成する場合、式（Ｌ－１）～式（Ｌ－２５）のいずれかで表される２価の連結基の結合数は、２～４であることが好ましく、２又は３であることがより好ましい。 When L W forms a linking group to which a divalent linking group represented by any of formulas (L-1) to (L-25) is bonded, formula (L-1) to formula (L-25) ) Is preferably 2 to 4, more preferably 2 or 3.
　式（Ｌ－１）、式（Ｌ－２）、式（Ｌ－６）及び式（Ｌ－１３）～式（Ｌ－２４）中の置換基Ｒ’としては、上記の式（１）のＲ１ａ～Ｒ１ｆが採りうる置換基として例示したものを挙げることができる。その中でも、式（Ｌ－６）中の置換基Ｒ’はアルキル基であることが好ましく、式（Ｌ－６）中のＲ’がアルキル基である場合は、アルキル基の炭素数は１～９であることが好ましく、４～９であることが化学的安定性、キャリア輸送性の観点からより好ましく、５～９であることがさらに好ましい。式（Ｌ－６）中のＲ’がアルキル基である場合は、アルキル基は直鎖アルキル基であることが、キャリア移動度を高めることができる観点から好ましい。
　ＲＮは水素原子又は置換基を表し、ＲＮとしては、上記の式（１）のＲ１ａ～Ｒ１ｆが採りうる置換基として例示したものを挙げることができる。その中でも、ＲＮとしては、水素原子又はメチル基が好ましい。
　Ｒｓｉはそれぞれ独立に、水素原子、アルキル基、アルケニル基又はアルキニル基を表し、アルキル基であることが好ましい。Ｒｓｉがとり得るアルキル基としては、特に制限はないが、Ｒｓｉがとり得るアルキル基の好ましい範囲は、Ｒがトリアルキルシリル基である場合にトリアルキルシリル基がとり得るアルキル基の好ましい範囲と同様である。Ｒｓｉがとり得るアルケニル基としては、特に制限はないが、置換又は無置換のアルケニル基が好ましく、分枝アルケニル基であることがより好ましく、アルケニル基の炭素数は２～３であることが好ましい。Ｒｓｉがとり得るアルキニル基としては、特に制限はないが、置換又は無置換のアルキニル基が好ましく、分枝アルキニル基であることがより好ましく、アルキニル基の炭素数は２～３であることが好ましい。 The substituent R ′ in the formula (L-1), the formula (L-2), the formula (L-6), and the formula (L-13) to the formula (L-24) is represented by the above formula (1). Examples of the substituent that can be taken by R 1a to R 1f can be given. Among them, the substituent R ′ in the formula (L-6) is preferably an alkyl group. When R ′ in the formula (L-6) is an alkyl group, the alkyl group has 1 to It is preferably 9, more preferably 4 to 9 from the viewpoint of chemical stability and carrier transport properties, and further preferably 5 to 9. When R ′ in the formula (L-6) is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of improving carrier mobility.
R N represents a hydrogen atom or a substituent, examples of R N, may be mentioned those exemplified as R 1a ~ substituent R 1f may take the above formula (1). Among them, as the R N, a hydrogen atom or a methyl group is preferable.
R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and is preferably an alkyl group. The alkyl group that R si can take is not particularly limited, but the preferred range of the alkyl group that R si can take is the preferred range of the alkyl group that the trialkylsilyl group can take when R is a trialkylsilyl group. It is the same. The alkenyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group has 2 to 3 carbon atoms. preferable. The alkynyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a branched alkynyl group, and the alkynyl group has 2 to 3 carbon atoms. preferable.
　ＬＷは、式（Ｌ－１）～式（Ｌ－５）、式（Ｌ－１３）、式（Ｌ－１７）若しくは式（Ｌ－１８）のいずれかで表される二価の連結基、又は、式（Ｌ－１）～式（Ｌ－５）、式（Ｌ－１３）、式（Ｌ－１７）若しくは式（Ｌ－１８）のいずれかで表される二価の連結基が２以上結合した二価の連結基であることが好ましく、式（Ｌ－１）、式（Ｌ－３）、式（Ｌ－１３）若しくは式（Ｌ－１８）のいずれかで表される二価の連結基、又は、式（Ｌ－１）、式（Ｌ－３）、式（Ｌ－１３）若しくは式（Ｌ－１８）のいずれかで表される二価の連結基が２以上結合した二価の連結基であることがより好ましく、式（Ｌ－１）、式（Ｌ－３）、式（Ｌ－１３）若しくは式（Ｌ－１８）のいずれかで表される二価の連結基、又は、式（Ｌ－３）、式（Ｌ－１３）若しくは式（Ｌ－１８）のいずれか１つで表される二価の連結基と式（Ｌ－１）で表される二価の連結基とを結合した二価の連結基であることが特に好ましい。
　式（Ｌ－３）、式（Ｌ－１３）又は式（Ｌ－１８）のいずれか１つで表される二価の連結基と式（Ｌ－１）で表される二価の連結基が結合した二価の連結基は、式（Ｌ－１）で表される二価の連結基がＲＷ側に結合することが好ましい。
　また、ＬＷは、化学的安定性、キャリア輸送性の観点から式（Ｌ－１）で表される二価の連結基を含む二価の連結基であることが特に好ましく、式（Ｌ－１）で表される二価の連結基であることがより特に好ましく、ＬＷが式（Ｌ－１）で表される二価の連結基であり、ＲＷが置換又は無置換のアルキル基であることが最も好ましい。 L W represents a divalent linking group represented by any of formulas (L-1) to (L-5), formula (L-13), formula (L-17), or formula (L-18). Or a divalent linking group represented by any of formulas (L-1) to (L-5), formula (L-13), formula (L-17) or formula (L-18) It is preferably a divalent linking group in which two or more are bonded, and represented by any one of the formulas (L-1), (L-3), (L-13), and (L-18) A divalent linking group or two or more divalent linking groups represented by any of formula (L-1), formula (L-3), formula (L-13) or formula (L-18) are bonded. And more preferably a divalent linking group represented by any one of formula (L-1), formula (L-3), formula (L-13) or formula (L-18). A linking group, or a formula (L-3), a formula ( L-13) or a divalent linking group represented by formula (L-18) and a divalent linking group represented by formula (L-1) bonded to each other. It is particularly preferred that
A divalent linking group represented by any one of formula (L-3), formula (L-13) or formula (L-18) and a divalent linking group represented by formula (L-1) There divalent linking group bonded is preferably a divalent linking group represented by the formula (L-1) binds to R W side.
Further, L W, the chemical stability, particularly preferable from the viewpoint of carrier transportability is a divalent linking group containing a divalent linking group represented by the formula (L-1), formula (L- more particularly preferably a divalent linking group represented by 1), L W is a divalent linking group represented by the formula (L-1), R W is a substituted or unsubstituted alkyl group Most preferably.
　式（Ｗ）において、ＲＷは、置換若しくは無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、オキシエチレン単位の繰り返し数ｖが２以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が２以上のオリゴシロキサン基、又は、置換若しくは無置換のトリアルキルシリル基を表す。
　式（Ｗ）において、ＲＷに隣接するＬＷが式（Ｌ－１）で表される二価の連結基である場合は、ＲＷは、置換若しくは無置換のアルキル基、オキシエチレン基、オキシエチレン単位の繰り返し数が２以上のオリゴオキシエチレン基、シロキサン基、又は、ケイ素原子数が２以上のオリゴシロキサン基であることが好ましく、置換又は無置換のアルキル基であることがより好ましい。
　式（Ｗ）において、ＲＷに隣接するＬＷが式（Ｌ－２）又は式（Ｌ－４）～式（Ｌ－２５）のいずれかで表される二価の連結基である場合は、ＲＷは置換又は無置換のアルキル基であることがより好ましい。
　式（Ｗ）において、ＲＷに隣接するＬＷが式（Ｌ－３）で表される二価の連結基である場合は、ＲＷは置換若しくは無置換のアルキル基、又は、置換若しくは無置換のトリアルキルシリル基であることが好ましい。 In formula (W), R W represents a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, a siloxane group, It represents an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group.
In the formula (W), when L W adjacent to R W is a divalent linking group represented by the formula (L-1), R W is a substituted or unsubstituted alkyl group, oxyethylene group, It is preferably an oligooxyethylene group having 2 or more repeating oxyethylene units, a siloxane group, or an oligosiloxane group having 2 or more silicon atoms, and more preferably a substituted or unsubstituted alkyl group.
In formula (W), when L W adjacent to R W is a divalent linking group represented by any of formulas (L-2) or formula (L-4) ~ formula (L-25) is , R W is more preferably a substituted or unsubstituted alkyl group.
In Formula (W), when L W adjacent to R W is a divalent linking group represented by Formula (L-3), R W is a substituted or unsubstituted alkyl group, or substituted or unsubstituted. It is preferably a substituted trialkylsilyl group.
　ＲＷが置換又は無置換のアルキル基の場合、炭素数は４～１７であることが好ましく、６～１４であることが化学的安定性、キャリア輸送性の観点からより好ましく、６～１２であることが更に好ましい。Ｒが上記の範囲の長鎖アルキル基であること、特に長鎖の直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。
　ＲＷがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。
　これらの中でも、式（Ｗ）におけるＲＷとＬＷの組み合わせとしては、式（１）中、ＬＷが式（Ｌ－１）で表される二価の連結基であり、かつ、ＲＷが直鎖の炭素数７～１７のアルキル基であるか、あるいは、ＬＷが式（Ｌ－３）、式（Ｌ－１３）又は式（Ｌ－１８）のいずれか１つで表される二価の連結基と式（Ｌ－１）で表される二価の連結基が結合した二価の連結基であり、かつ、ＲＷが直鎖のアルキル基であることが、キャリア移動度を高める観点から好ましい。
　ＬＷが式（Ｌ－１）で表される二価の連結基であり、かつ、ＲＷが直鎖の炭素数７～１７のアルキル基である場合、ＲＷが直鎖の炭素数７～１４のアルキル基であることがキャリア移動度を高める観点からより好ましく、直鎖の炭素数７～１２のアルキル基であることが特に好ましい。
　ＬＷが式（Ｌ－３）、式（Ｌ－１３）又は式（Ｌ－１８）のいずれか１つで表される二価の連結基と式（Ｌ－１）で表される二価の連結基が結合した二価の連結基であり、かつ、ＲＷが直鎖のアルキル基である場合、ＲＷが直鎖の炭素数４～１７のアルキル基であることがより好ましく、直鎖の炭素数６～１４のアルキル基であることが化学的安定性、キャリア輸送性の観点からより好ましく、直鎖の炭素数６～１２のアルキル基であることがキャリア移動度を高める観点から特に好ましい。
　一方、有機溶媒への溶解度を高める観点からは、ＲＷが分枝アルキル基であることが好ましい。
　ＲＷが置換基を有するアルキル基である場合の置換基としては、ハロゲン原子などを挙げることができ、フッ素原子が好ましい。なお、ＲＷがフッ素原子を有するアルキル基である場合はアルキル基の水素原子が全てフッ素原子で置換されてパーフルオロアルキル基を形成してもよい。ただし、ＲＷは無置換のアルキル基であることが好ましい。 For R W is a substituted or unsubstituted alkyl group, it preferably has a carbon number of 4-17, it is chemically stable is 6 to 14, more preferably from the viewpoint of carrier transportability, 6-12 More preferably it is. R is preferably a long-chain alkyl group in the above-mentioned range, particularly a long-chain straight-chain alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
If R W represents an alkyl group, a straight-chain alkyl group, even branched alkyl group, it may be a cyclic alkyl group, a straight-chain alkyl groups, increases the linearity of the molecules, to increase the carrier mobility It is preferable from the viewpoint that can be achieved.
Among these, the combination of R W and L W in formula (W), wherein (1) is a divalent linking group L W is represented by formula (L-1), and, R W Is a linear alkyl group having 7 to 17 carbon atoms, or L W is represented by any one of formula (L-3), formula (L-13), or formula (L-18). is a divalent linking group of the divalent linking group represented by a divalent linking group and the formula (L-1) is bonded, and it is the carrier mobility R W is a straight chain alkyl group From the viewpoint of increasing
L W is a divalent linking group represented by the formula (L-1), and, if R W is an alkyl group having 7-17 carbon atoms of straight-chain, the number of carbon atoms of R W is a linear 7 From the viewpoint of increasing carrier mobility, a linear alkyl group having 7 to 12 carbon atoms is particularly preferable.
L W is a divalent linking group represented by any one of formula (L-3), formula (L-13) or formula (L-18) and a divalent represented by formula (L-1) is a divalent linking group linking group is attached the, and, if R W is a straight chain alkyl group, more preferably R W is an alkyl group having a carbon number of 4 to 17 linear, straight The chain is preferably an alkyl group having 6 to 14 carbon atoms from the viewpoint of chemical stability and carrier transportability, and the straight chain alkyl group having 6 to 12 carbon atoms is from the viewpoint of increasing carrier mobility. Particularly preferred.
On the other hand, from the viewpoint of enhancing the solubility in organic solvents, it is preferred that R W is a branched alkyl group.
The substituent when R W is an alkyl group having a substituent, can be mentioned a halogen atom, a fluorine atom is preferable. It is also possible if R W is an alkyl group having a fluorine atom is substituted for all the hydrogen atoms of the alkyl group fluorine atom to form a perfluoroalkyl group. However, it is preferred that R W is an unsubstituted alkyl group.
　ＲＷがオキシエチレン基の繰り返し数が２以上のオリゴオキシエチレン基の場合、Ｒが表す「オリゴオキシエチレン基」とは本明細書中、－（ＯＣＨ２ＣＨ２）ｖ－ＯＹで表される基のことを言う（オキシエチレン単位の繰り返し数ｖは２以上の整数を表し、末端のＹは、水素原子又は置換基を表す。）。なお、オリゴオキシエチレン基の末端のＹが水素原子である場合はヒドロキシ基となる。オキシエチレン単位の繰り返し数ｖは、２～４であることが好ましく、２～３であることがより好ましい。
　オリゴオキシエチレン基の末端のヒドロキシ基は封止されていること、すなわちＹが置換基を表すことが好ましい。この場合、ヒドロキシ基は、炭素数が１～３のアルキル基で封止されること、すなわち、Ｙが炭素数１～３のアルキル基であることが好ましく、Ｙがメチル基又はエチル基であることがより好ましく、メチル基であることが特に好ましい。 If R W is a number of repetitions is more than one oligo oxyethylene group of oxyethylene groups, herein and R represents "oligooxyethylene group", - represented by (OCH 2 CH 2) v -OY It refers to a group (the repeating number v of oxyethylene units represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The number of repeating oxyethylene units v is preferably 2 to 4, and more preferably 2 to 3.
The terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. More preferred is a methyl group.
　ＲＷが、シロキサン基、又は、ケイ素原子数が２以上のオリゴシロキサン基の場合、シロキサン単位の繰り返し数は２～４であることが好ましく、２～３であることがさらに好ましい。また、ケイ素原子（Ｓｉ原子）には、水素原子又はアルキル基が結合することが好ましい。ケイ素原子にアルキル基が結合する場合、アルキル基の炭素数は１～３であることが好ましく、例えば、メチル基又はエチル基が結合することが好ましい。ケイ素原子には、同一のアルキル基が結合してもよく、異なるアルキル基又は水素原子が結合してもよい。また、オリゴシロキサン基を構成するシロキサン単位はすべて同一であっても異なっていてもよいが、すべて同一であることが好ましい。 R W is a siloxane group, or, when the number of silicon atoms is two or more oligosiloxane groups, the number of repetitions of the siloxane units is preferably from 2 to 4, more preferably 2-3. In addition, a hydrogen atom or an alkyl group is preferably bonded to the silicon atom (Si atom). When an alkyl group is bonded to a silicon atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the silicon atom, or a different alkyl group or a hydrogen atom may be bonded thereto. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.
　ＲＷに隣接するＬＷが式（Ｌ－３）で表される二価の連結基である場合、ＲＷが置換又は無置換のトリアルキルシリル基であることも好ましい。ＲＷが置換又は無置換のトリアルキルシリル基である場合はその中でも、シリル基の置換基としては、置換又は無置換のアルキル基であれば特に制限はないが、分枝アルキル基であることがより好ましい。ケイ素原子に結合するアルキル基の炭素数は１～３であることが好ましく、例えば、メチル基又はエチル基又はイソプロピル基が結合することが好ましい。ケイ素原子には、同一のアルキル基が結合してもよく、異なるアルキル基が結合してもよい。ＲＷがアルキル基上に更に置換基を有するトリアルキルシリル基である場合の置換基としては、特に制限はない。 If L W adjacent to R W is a divalent linking group represented by the formula (L-3), it is also preferred R W is a substituted or unsubstituted trialkylsilyl group. It Among them if R W is a substituted or unsubstituted trialkylsilyl group, examples of the substituent of the silyl group is not particularly limited as long as it is a substituted or unsubstituted alkyl group, a branched alkyl group Is more preferable. The alkyl group bonded to the silicon atom preferably has 1 to 3 carbon atoms. For example, a methyl group, an ethyl group, or an isopropyl group is preferably bonded. The same alkyl group may be bonded to the silicon atom, or different alkyl groups may be bonded to it. The substituent when R W is a trialkylsilyl group having a substituent on the alkyl group is not particularly limited.
　式（Ｗ）において、ＬＷ及びＲＷに含まれる炭素数の合計は５～１８であることが好ましい。ＬＷ及びＲＷに含まれる炭素数の合計が上記範囲の下限値以上であると、キャリア移動度が高くなり、駆動電圧が低くなる。ＬＷ及びＲＷに含まれる炭素数の合計が上記範囲の上限値以下であると、有機溶媒に対する溶解性が高くなる。
　ＬＷ及びＲＷに含まれる炭素数の合計は、５～１４であることが好ましく、６～１４であることがより好ましく、６～１２であることが更に好ましく、８～１２であることが特に好ましい。 In the formula (W), the total number of carbon atoms contained in L W and R W is preferably 5 to 18. When the total number of carbon atoms contained in L W and R W is not less than the lower limit of the above range, the carrier mobility is increased and the driving voltage is decreased. If the total number of carbon atoms contained in L W and R W is not more than the upper limit of the above range, solubility in an organic solvent is increased.
The total number of carbon atoms contained in L W and R W is preferably 5 to 14, more preferably 6 to 14, still more preferably 6 to 12, and preferably 8 to 12. Particularly preferred.
　式（１）で表される化合物中において、Ｒ１ａ～Ｒ１ｆのうち、式（Ｗ）で表される基の個数は１～４個であることが好ましく、１～２個であることがより好ましく、２個であることが特に好ましい。 In the compound represented by the formula (1), among R 1a to R 1f , the number of groups represented by the formula (W) is preferably 1 to 4, and preferably 1 to 2. More preferably, it is particularly preferably 2.
　本発明では、式（１）において、Ｒ１ａ及びＲ１ｂのうち少なくとも１つが式（Ｗ）で表される基であることが好ましい。式（１）における置換位置として、これらの位置が好ましいのは、化合物の化学的安定性に優れ、最高被占軌道（ＨＯＭＯ）準位、分子の膜中でのパッキングの観点からも好適であるためであると考えられる。特に、式（１）において、Ｒ１ａ及びＲ１ｂの２箇所を置換基とすることにより、高いキャリア濃度を得ることができる。
　また、式（１）において、Ｒ１ｃ～Ｒ１ｆがそれぞれ独立に、水素原子、フッ素原子、炭素数１～３の置換若しくは無置換のアルキル基、炭素数２～３の置換若しくは無置換のアルキニル基、炭素数２～３の置換若しくは無置換のアルケニル基、炭素数１～２の置換若しくは無置換のアルコキシ基、又は、置換若しくは無置換のメチルチオ基であることが好ましい。 In the present invention, in formula (1), at least one of R 1a and R 1b is preferably a group represented by formula (W). These positions are preferred as the substitution positions in the formula (1) because of the excellent chemical stability of the compound, the highest occupied orbital (HOMO) level, and also from the viewpoint of packing of molecules in the film. This is probably because of this. In particular, in Formula (1), a high carrier concentration can be obtained by using two positions of R 1a and R 1b as substituents.
In the formula (1), R 1c to R 1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms. And a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group.
－式（２）で表される化合物－ -Compound represented by Formula (2)-
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（２）中、Ｘ２ａ及びＸ２ｂはそれぞれ独立に、ＮＲ２ｉ（＞Ｎ－Ｒ２ｉ）、Ｏ原子又はＳ原子を表す。Ｘ２ａ及びＸ２ｂはそれぞれ独立に、Ｏ原子又はＳ原子であることが合成容易性の観点から好ましい。一方、Ｘ２ａ及びＸ２ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。
　Ｘ２ａ及びＸ２ｂは、同じ連結基であることが好ましい。Ｘ２ａ及びＸ２ｂはいずれもＳ原子であることがより好ましい。
　Ｒ２ｉは、水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基を表し、水素原子又はアルキル基であることが好ましく、炭素数１～１４のアルキル基であることがより好ましく、炭素数１～４のアルキル基であることが特に好ましい。
　Ｒ２ｉがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。 In formula (2), X 2a and X 2b each independently represent NR 2i (> N—R 2i ), an O atom or an S atom. X 2a and X 2b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing carrier mobility that at least one of X 2a and X 2b is an S atom.
X 2a and X 2b are preferably the same linking group. It is more preferable that both X 2a and X 2b are S atoms.
R 2i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and a carbon number of 1 Particularly preferred is an alkyl group of ˜4.
When R 2i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
　式（２）中、Ａ２ａは、ＣＲ２ｇ又はＮ原子を表し、Ａ２ｂは、ＣＲ２ｈ又はＮ原子を表し、Ｒ２ｇ及びＲ２ｈはそれぞれ独立に、水素原子又は置換基を表す。Ａ２ａがＣＲ２ｇであるか、Ａ２ｂがＣＲ２ｈであることが好ましく、Ａ２ａがＣＲ２ｇであり、かつＡ２ｂがＣＲ２ｈであることがより好ましい。Ａ２ａ及びＡ２ｂは、同じであっても互いに異なっていてもよいが、同じあることが好ましい。
　式（２）において、Ｒ２ｅとＲ２ｇとは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しない方が好ましい。
　式（２）において、Ｒ２ｆとＲ２ｈとは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しない方が好ましい。 In Formula (2), A 2a represents CR 2g or an N atom, A 2b represents CR 2h or an N atom, and R 2g and R 2h each independently represent a hydrogen atom or a substituent. Or A 2a is CR 2 g, preferably A 2b is CR 2h, A 2a is CR 2 g, and more preferably A 2b is CR 2h. A 2a and A 2b may be the same or different from each other, but are preferably the same.
In Formula (2), R 2e and R 2g may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring. .
In the formula (2), R 2f and R 2h may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring. .
　式（２）中、Ｒ２ａ～Ｒ２ｈはそれぞれ独立に、水素原子又は置換基を表し、少なくとも１つは式（Ｗ）で表される置換基を表す。
　Ｒ２ａ～Ｒ２ｈがそれぞれ独立に、とりうる置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される置換基の定義は、上述の通りである。
　Ｒ２ａ～Ｒ２ｈがそれぞれ独立に、とりうる置換基として、アルキル基、アリール基、アルケニル基、アルキニル基、複素環基、アルコキシ基、アルキルチオ基、又は、式（Ｗ）で表される置換基が好ましく、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１１のアルコキシ基、炭素数５～１２の複素環基、炭素数１～１２のアルキルチオ基、又は、式（Ｗ）で表される基がより好ましく、後述の連結基鎖長が３．７Å以下の基、又は、式（Ｗ）で表される基が特に好ましく、式（Ｗ）で表される基がより特に好ましい。 In formula (2), R 2a to R 2h each independently represent a hydrogen atom or a substituent, and at least one represents a substituent represented by formula (W).
Examples of the substituent that R 2a to R 2h can independently take include the substituent X described above. The definition of the substituent represented by the formula (W) is as described above.
R 2a to R 2h each independently represents a substituent represented by an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula (W) Preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, A heterocyclic group having 5 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable, a group having a linking group chain length of 3.7 Å or less, or a group represented by the formula ( The group represented by W) is particularly preferred, and the group represented by formula (W) is more particularly preferred.
　式（２）で表される化合物中、Ｒ２ａ～Ｒ２ｈのうち、式（Ｗ）で表される基は１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ２ａ～Ｒ２ｈのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ２ｅ又はＲ２ｆであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましい。 In the compound represented by the formula (2), among R 2a to R 2h , 1 to 4 groups represented by the formula (W) increase carrier mobility and solubility in an organic solvent. From the viewpoint of increasing the number, it is preferably 1 or 2, more preferably 2.
Among R 2a to R 2h , the position of the group represented by the formula (W) is not particularly limited, but R 2e or R 2f increases carrier mobility and increases solubility in an organic solvent. It is preferable from the viewpoint.
　Ｒ２ａ～Ｒ２ｈのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。 Of R 2a to R 2h, the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基は、連結基鎖長が３．７Å（＝０．３７ｎｍ）以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることが更に好ましい。
　ここで、連結基鎖長とはＣ（炭素原子）－Ｒ結合におけるＣ原子から置換基Ｒの末端までの長さのことを指す。構造最適化計算は、密度汎関数法（Ｇａｕｓｓｉａｎ０３（米ガウシアン社）／基底関数：６－３１Ｇ＊、交換相関汎関数：Ｂ３ＬＹＰ／ＬＡＮＬ２ＤＺ）を用いて行うことができる。なお、代表的な置換基の分子長としては、プロピル基は４．６Å、ピロール基は４．６Å、プロピニル基は４．５Å、プロペニル基は４．６Å、エトキシ基は４．５Å、メチルチオ基は３．７Å、エテニル基は３．４Å、エチル基は３．５Å、エチニル基は３．６Å、メトキシ基は３．３Å、メチル基は２．１Å、水素原子は１．０Åである。 The substituent in the case where R 2a to R 2h are substituents other than the group represented by the formula (W) is preferably a group having a linking group chain length of 3.7 mm (= 0.37 nm) or less. A group having a linking group chain length of 1.0 to 3.7 mm is more preferable, and a group having a linking group chain length of 1.0 to 2.1 mm is more preferable.
Here, the linking group chain length refers to the length from the C atom to the terminal of the substituent R in the C (carbon atom) -R bond. The structure optimization calculation can be performed using a density functional method (Gaussian 03 (Gaussian, USA) / basis function: 6-31G * , exchange correlation functional: B3LYP / LANL2DZ). In addition, as the molecular length of a typical substituent, the propyl group is 4.6Å, the pyrrole group is 4.6Å, the propynyl group is 4.5Å, the propenyl group is 4.6Å, the ethoxy group is 4.5Å, and the methylthio group Is 3.7Å, the ethenyl group is 3.4Å, the ethyl group is 3.5Å, the ethynyl group is 3.6Å, the methoxy group is 3.3Å, the methyl group is 2.1Å, and the hydrogen atom is 1.0Å.
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基はそれぞれ独立に炭素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、炭素数２以下の置換若しくは無置換のアルキル基であることがより好ましい。
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ２ａ～Ｒ２ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 When R 2a to R 2h are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable that
In the case where R 2a to R 2h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group Are preferred, methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
In the case where R 2a to R 2h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are as follows: And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
When R 2a to R 2h are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
In the case where R 2a to R 2h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituents that the acyl group can take are as follows: And a fluorine atom. In the case of a substituent other than the group represented by the formula (W), the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
－式（３）で表される化合物－ -Compound represented by Formula (3)-
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（３）において、Ｒ３ａ～Ｒ３ｆ並びに後述するＲ３ｇ及びＲ３ｈはそれぞれ独立に、水素原子又は置換基を表す。ただし、Ｒ３ａ～Ｒ３ｈのうち少なくとも１つは、式（Ｗ）で表される基を表す。
　Ｒ３ａ～Ｒ３ｈで表される置換基としては、上記置換基Ｘが挙げられる。式（Ｗ）で表される基の定義は、上述の通りである。
　Ｒ３ａ～Ｒ３ｆがそれぞれ独立にとりうる置換基として、アルキル基、アリール基、アルケニル基、アルキニル基、複素環基、アルコキシ基、アルキルチオ基、又は、式（Ｗ）で表される置換基が好ましく、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１１のアルコキシ基、炭素数５～１２の複素環基、炭素数１～１２のアルキルチオ基、又は、式（Ｗ）で表される基がより好ましい。 In the formula (3), R 3a to R 3f and R 3g and R 3h described later each independently represent a hydrogen atom or a substituent. However, at least one of R 3a to R 3h represents a group represented by the formula (W).
Examples of the substituent represented by R 3a to R 3h include the above-described substituent X. The definition of the group represented by the formula (W) is as described above.
As the substituent that R 3a to R 3f can independently take, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula (W) is preferable. An alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, and 5 to 5 carbon atoms A heterocyclic group having 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable.
　式（３）において、Ｘ３ａ及びＸ３ｂはそれぞれ独立に、Ｓ原子、Ｏ原子又はＮＲ３ｇ（＞Ｎ－Ｒ３ｇ）を表し、Ｒ３ｇは水素原子又は置換基を表す。Ｘは、Ｓ原子又はＯ原子が好ましい。式（３）において、Ｘ３ａ及びＸ３ｂは、同じであることが好ましい。
　Ｒ３ｇは、水素原子、アルキル基、又は、アリール基であることが好ましく、炭素数１～１４のアルキル基であることがより好ましく、炭素数４～１２のアルキル基であることが特に好ましい。Ｒ３ｇが上記の範囲の長鎖アルキル基であること、特に長鎖の直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。
　Ｒ３ｇがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。 In the formula (3), X 3a and X 3b each independently represent an S atom, an O atom or NR 3g (> N—R 3g ), and R 3g represents a hydrogen atom or a substituent. X is preferably an S atom or an O atom. In the formula (3), X 3a and X 3b are preferably the same.
R 3g is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 4 to 12 carbon atoms. It is preferable that R 3g is a long-chain alkyl group within the above range, particularly a long-chain linear alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
When R 3g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
　式（３）において、Ａ３ａ及びＡ３ｂはそれぞれ独立に、ＣＲ３ｈ又はＮ原子を表し、ＣＲ３ｈを表すことが好ましい。式（３）において、Ａ３ａ及びＡ３ｂは、同じであっても互いに異なっていてもよいが、同じあることが好ましい。
　Ｒ３ｈは連結基鎖長が３．７Å以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることが更に好ましい。連結基鎖長の定義は、上述の通りである。
　Ｒ３ｈは、水素原子、炭素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、水素原子、又は、炭素数２以下の置換若しくは無置換のアルキル基であることがより好ましく、水素原子であることが特に好ましい。
　Ｒ３ｈが炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。Ｒ３ｈが表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ３ｈが炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。Ｒ３ｈが表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ３ｈが炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。Ｒ３ｈが表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ３ｈが炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。Ｒ３ｈが表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 In Formula (3), A 3a and A 3b each independently represent CR 3h or an N atom, and preferably represents CR 3h . In formula (3), A 3a and A 3b may be the same or different from each other, but are preferably the same.
R 3h is preferably a group having a linking group chain length of 3.7 mm or less, more preferably a group having a linking group chain length of 1.0 to 3.7 mm, and a linking group chain length of 1.0 to 3.7 mm. More preferably, it is a 2.1 Å group. The definition of the linking group chain length is as described above.
R 3h is a hydrogen atom, a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted alkynyl group having 2 or less carbon atoms, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a carbon number It is preferably a substituted or unsubstituted acyl group having 2 or less, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 2 or less carbon atoms, and particularly preferably a hydrogen atom.
When R 3h represents a substituted alkyl group having 2 or less carbon atoms, examples of the substituent that the alkyl group can take include a cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by R 3h is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group, more preferably a methyl group or a cyano group-substituted methyl group, A group-substituted methyl group is particularly preferred.
When R 3h represents a substituted alkynyl group having 2 or less carbon atoms, examples of the substituent that the alkynyl group can take include a deuterium atom. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by R 3h include an ethynyl group or a deuterium atom-substituted acetylene group, and an ethynyl group is preferable.
When R 3h represents a substituted alkenyl group having 2 or less carbon atoms, examples of the substituent that the alkenyl group can take include a deuterium atom. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by R 3h include an ethenyl group or a deuterium atom-substituted ethenyl group, and an ethenyl group is preferable.
When R 3h represents a substituted acyl group having 2 or less carbon atoms, examples of the substituent that the acyl group can take include a fluorine atom. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by R 3h include a formyl group, an acetyl group, and a fluorine-substituted acetyl group, and a formyl group is preferable.
－式（４）で表される化合物－ -Compound represented by Formula (4)-
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（４）中、Ｘ４ａ及びＸ４ｂはそれぞれ独立に、Ｏ原子、Ｓ原子又はＳｅ原子を表す。
　Ｘ４ａ及びＸ４ｂはそれぞれ独立に、Ｏ原子又はＳ原子であることが好ましく、Ｘ４ａ及びＸ４ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点からより好ましい。Ｘ４ａ及びＸ４ｂは、同じ連結基であることが好ましい。Ｘ４ａ及びＸ４ｂはいずれもＳ原子であることが特に好ましい。 In formula (4), X 4a and X 4b each independently represent an O atom, an S atom, or a Se atom.
X 4a and X 4b are each independently preferably an O atom or an S atom, and at least one of X 4a and X 4b is preferably an S atom, more preferably from the viewpoint of increasing carrier mobility. X 4a and X 4b are preferably the same linking group. It is particularly preferred that both X 4a and X 4b are S atoms.
　式（４）中、４ｐ及び４ｑはそれぞれ独立に、０～２の整数を表す。４ｐ及び４ｑがそれぞれ独立に、０又は１であることがキャリア移動度と溶解性を両立する観点から好ましく、４ｐ＝４ｑ＝０又は４ｐ＝４ｑ＝１であることがより好ましい。 In formula (4), 4p and 4q each independently represents an integer of 0 to 2. 4p and 4q are each independently 0 or 1 from the viewpoint of achieving both carrier mobility and solubility, and more preferably 4p = 4q = 0 or 4p = 4q = 1.
　式（４）中、Ｒ４ａ～Ｒ４ｋ及びＲ４ｍはそれぞれ独立に、水素原子、ハロゲン原子、又は、式（Ｗ）で表される基を表し、かつ、Ｒ４ａ～Ｒ４ｋ及びＲ４ｍのうち少なくとも一つは式（Ｗ）で表される基であり、ただし、Ｒ４ｅ及びＲ４ｆのうち少なくとも一方が式（Ｗ）で表される基である場合は、Ｒ４ｅとＲ４ｆとが表す式（Ｗ）において、ＬＷは上記式（Ｌ－２）又は式（Ｌ－３）で表される二価の連結基である。なお、式（Ｗ）で表される基の定義は、上述の通りである。 In the formula (4), R 4a to R 4k and R 4m each independently represent a hydrogen atom, a halogen atom, or a group represented by the formula (W), and R 4a to R 4k and R 4m At least one of them is a group represented by the formula (W), provided that when at least one of R 4e and R 4f is a group represented by the formula (W), R 4e and R 4f are In the formula (W), L W is a divalent linking group represented by the above formula (L-2) or formula (L-3). In addition, the definition of group represented by Formula (W) is as above-mentioned.
　Ｒ４ｅ及びＲ４ｆのうち少なくとも一方が式（Ｗ）で表される基である場合は、すなわちＲ４ｅ及びＲ４ｆのうちいずれか一方でも水素原子でもなくハロゲン原子でもない場合に相当する。
　Ｒ４ｅ及びＲ４ｆのうち少なくとも一方が式（Ｗ）で表される基である場合、Ｒ４ｅ及びＲ４ｆが表す式（Ｗ）において、ＬＷは上記式（Ｌ－３）で表される二価の連結基であることが好ましい。
　Ｒ４ｅ及びＲ４ｆのうち少なくとも一方が式（Ｗ）で表される基である場合、Ｒ４ｅ及びＲ４ｆは、いずれも式（Ｗ）で表される基であることが好ましい。
　なお、Ｒ４ｅ及びＲ４ｆがともに水素原子又はハロゲン原子の場合、Ｒ４ａ～Ｒ４ｄ、Ｒ４ｇ～Ｒ４ｋ及びＲ４ｍはそれぞれ独立に、水素原子、ハロゲン原子又は式（Ｗ）で表される基であり、かつ、Ｒ４ａ～Ｒ４ｄ、Ｒ４ｇ～Ｒ４ｋ及びＲ４ｍのうち少なくとも１つ以上は式（Ｗ）で表される基となる。 The case where at least one of R 4e and R 4f is a group represented by the formula (W) corresponds to the case where either one of R 4e and R 4f is neither a hydrogen atom nor a halogen atom.
When at least one of R 4e and R 4f is a group represented by the formula (W), in the formula (W) represented by R 4e and R 4f , L W is represented by the above formula (L-3). A divalent linking group is preferred.
If at least one of R 4e and R 4f are groups represented by the formula (W), R 4e and R 4f are preferably both a group represented by the formula (W).
When R 4e and R 4f are both hydrogen atoms or halogen atoms, R 4a to R 4d , R 4g to R 4k and R 4m are each independently represented by a hydrogen atom, a halogen atom or formula (W). And at least one of R 4a to R 4d , R 4g to R 4k and R 4m is a group represented by the formula (W).
　式（４）中、Ｒ４ａ～Ｒ４ｋ及びＲ４ｍが表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子を挙げることができ、フッ素原子、塩素原子又は臭素原子であることが好ましく、フッ素原子又は塩素原子であることがより好ましく、フッ素原子であることが特に好ましい。 In the formula (4), examples of the halogen atom represented by R 4a to R 4k and R 4m include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and may be a fluorine atom, a chlorine atom or a bromine atom. Preferably, it is a fluorine atom or a chlorine atom, more preferably a fluorine atom.
　式（４）で表される化合物中、Ｒ４ａ～Ｒ４ｋ及びＲ４ｍのうち、ハロゲン原子は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。 In the compound represented by the formula (4), among R 4a to R 4k and R 4m , the halogen atom is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 More preferably, it is particularly preferably 0.
　式（４）で表される化合物中、Ｒ４ａ～Ｒ４ｋ及びＲ４ｍのうち、式（Ｗ）で表される基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ４ａ～Ｒ４ｋ及びＲ４ｍのうち、式（Ｗ）で表される基の位置に特に制限はない。その中でも、本発明では、式（４）中、Ｒ４ａ、Ｒ４ｄ～Ｒ４ｇ、Ｒ４ｊ、Ｒ４ｋ及びＲ４ｍがそれぞれ独立に、水素原子又はハロゲン原子であり、Ｒ４ｂ、Ｒ４ｃ、Ｒ４ｈ及びＲ４ｉがそれぞれ独立に、水素原子、ハロゲン原子又は式（Ｗ）で表される基であり、かつ、Ｒ４ｂ、Ｒ４ｃ、Ｒ４ｈ及びＲ４ｉのうち少なくとも１つは式（Ｗ）で表される基であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましい。
　本発明では、Ｒ４ａ、Ｒ４ｃ～Ｒ４ｈ及びＲ４ｊがそれぞれ独立に、水素原子又はハロゲン原子を表し、Ｒ４ｂ及びＲ４ｉがそれぞれ独立に、水素原子、ハロゲン原子又は式（Ｗ）で表される基であり、かつ、少なくとも１つは式（Ｗ）で表される基であることがより好ましい。
　本発明では、Ｒ４ｂ及びＲ４ｉがともに式（Ｗ）で表される基であり、かつＲ４ｃ及びＲ４ｈがともに水素原子又はハロゲン原子であるか、Ｒ４ｃ及びＲ４ｈがともに式（Ｗ）で表される基であり、かつＲ４ｂ及びＲ４ｉがともに水素原子又はハロゲン原子であることが更に好ましい。
　本発明では、Ｒ４ｂ及びＲ４ｉがともに式（Ｗ）で表される基であり、かつＲ４ｃ及びＲ４ｈがともに水素原子又はハロゲン原子であるか、Ｒ４ｃ及びＲ４ｈがともに式（Ｗ）で表される基であり、かつＲ４ｂ及びＲ４ｉがともに水素原子又はハロゲン原子であることが特に好ましい。
　式（４）において、２以上のＲ４ａ～Ｒ４ｋ及びＲ４ｍは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しない方が好ましい。 In the compound represented by the formula (4), among R 4a to R 4k and R 4m , the number of the group represented by the formula (W) is 1 to 4, which increases the carrier mobility and increases the organic solvent. From the viewpoint of increasing the solubility in water, 1 or 2 is more preferable, and 2 is particularly preferable.
Of R 4a to R 4k and R 4m , the position of the group represented by the formula (W) is not particularly limited. Among them, in the present invention, in the formula (4), R 4a , R 4d to R 4g , R 4j , R 4k and R 4m are each independently a hydrogen atom or a halogen atom, and R 4b , R 4c , R 4 4h and R 4i are each independently a hydrogen atom, a halogen atom or a group represented by formula (W), and at least one of R 4b , R 4c , R 4h and R 4i is represented by formula (W) Is preferable from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent.
In the present invention, R 4a , R 4c to R 4h and R 4j each independently represent a hydrogen atom or a halogen atom, and R 4b and R 4i each independently represent a hydrogen atom, a halogen atom or a formula (W). More preferably, at least one of the groups is a group represented by the formula (W).
In the present invention, both R 4b and R 4i are groups represented by the formula (W), and R 4c and R 4h are both hydrogen atoms or halogen atoms, or R 4c and R 4h are both represented by the formula (W More preferably, R 4b and R 4i are both a hydrogen atom or a halogen atom.
In the present invention, both R 4b and R 4i are groups represented by the formula (W), and R 4c and R 4h are both hydrogen atoms or halogen atoms, or R 4c and R 4h are both represented by the formula (W It is particularly preferred that R 4b and R 4i are both hydrogen atoms or halogen atoms.
In the formula (4), two or more R 4a to R 4k and R 4m may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but may be bonded to each other to form a ring. It is preferable not to form them.
－式（５）で表される化合物－ -Compound represented by Formula (5)-
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（５）中、Ｘ５ａ及びＸ５ｂはそれぞれ独立に、ＮＲ５ｉ、Ｏ原子又はＳ原子を表す。Ｘ５ａ及びＸ５ｂはそれぞれ独立に、Ｏ原子又はＳ原子であることが合成容易性の観点から好ましい。一方、Ｘ５ａ及びＸ５ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ５ａ及びＸ５ｂは、同じ連結基であることが好ましい。Ｘ５ａ及びＸ５ｂはいずれもＳ原子であることがより好ましい。
　Ｒ５ｉは、水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基であることが好ましく、水素原子又はアルキル基であることがより好ましく、炭素数１～１４のアルキル基であることが更に好ましく、炭素数１～４のアルキル基であることが特に好ましい。
　Ｒ５ｉがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。 In formula (5), X 5a and X 5b each independently represent NR 5i , an O atom, or an S atom. X 5a and X 5b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, at least one of X 5a and X 5b is preferably an S atom from the viewpoint of increasing carrier mobility. X 5a and X 5b are preferably the same linking group. It is more preferable that both X 5a and X 5b are S atoms.
R 5i represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, Or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When R 5i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
　式（５）中、Ａ５ａはＣＲ５ｇ又はＮ原子を表し、Ａ５ｂはＣＲ５ｈ又はＮ原子を表し、Ｒ５ｇ及びＲ５ｈはそれぞれ独立に、水素原子又は置換基を表す。Ａ５ａがＣＲ５ｇであるか、Ａ５ｂがＣＲ５ｈであることが好ましく、Ａ５ａがＣＲ５ｇかつＡ５ｂがＣＲ５ｈであることがより好ましい。Ａ５ａ及びＡ５ｂは、同じであっても互いに異なっていてもよいが、同じあることが好ましい。 In formula (5), A 5a represents CR 5g or an N atom, A 5b represents CR 5h or an N atom, and R 5g and R 5h each independently represent a hydrogen atom or a substituent. Or A 5a is CR 5 g, preferably A 5b is CR 5h, A 5a it is more preferably CR 5 g and A 5b is CR 5h. A 5a and A 5b may be the same or different from each other, but are preferably the same.
　式（５）において、Ｒ５ｅとＲ５ｇとは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しないほうが好ましい。
　式（５）において、Ｒ５ｅとＲ５ｉとは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しないほうが好ましい。
　式（５）において、Ｒ５ｆとＲ５ｈとは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しないほうが好ましい。
　式（５）において、Ｒ５ｆとＲ５ｉは互いに結合して環を形成してもよく、互いに結合して環を形成しなくてもよいが、互いに結合して環を形成しないほうが好ましい。 In the formula (5), R 5e and R 5g may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula (5), R 5e and R 5i may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula (5), R 5f and R 5h may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula (5), R 5f and R 5i may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
　式（５）中、Ｒ５ａ～Ｒ５ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ５ａ～Ｒ５ｈのうち少なくとも１つが式（Ｗ）で表される基である。
　なお、Ｒ５ａ～Ｒ５ｈで表される置換基としては、上述した置換基Ｘが挙げられる。また、式（Ｗ）で表される基の定義は、上述の通りである。 In formula (5), R 5a to R 5h each independently represents a hydrogen atom or a substituent, and at least one of R 5a to R 5h is a group represented by formula (W).
Examples of the substituent represented by R 5a to R 5h include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
　式（５）で表される化合物中、Ｒ５ａ～Ｒ５ｈのうち、式（Ｗ）で表される基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ５ａ～Ｒ５ｈのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ５ｅ又はＲ５ｆであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましい。
　Ｒ５ａ～Ｒ５ｈのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。 In the compound represented by the formula (5), among R 5a to R 5h , 1 to 4 groups represented by the formula (W) increase carrier mobility and dissolve in an organic solvent. From the viewpoint of enhancing the properties, it is preferably 1 or 2, more preferably 2.
Among R 5a to R 5h , the position of the group represented by the formula (W) is not particularly limited, but R 5e or R 5f increases carrier mobility and solubility in an organic solvent. It is preferable from the viewpoint.
Of R 5a to R 5h, the number of substituents other than the group represented by formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基は、連結基鎖長が３．７Å以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることがさらに好ましい。連結基鎖長の定義は、上述の通りである。
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基はそれぞれ独立に炭素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、炭素数２以下の置換又は無置換のアルキル基であることがより好ましい。
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される置換基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ５ａ～Ｒ５ｈが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 In the case where R 5a to R 5h are substituents other than the group represented by the formula (W), the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 The group is more preferably a group having a length of 0.0 to 3.7 mm, and further preferably a group having a linking group chain length of 1.0 to 2.1 mm. The definition of the linking group chain length is as described above.
When R 5a to R 5h are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable that
In the case where R 5a to R 5h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group Are preferred, methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
When R 5a to R 5h are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are as follows: And deuterium atoms. In the case of a substituent other than the substituent represented by the formula (W), the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent is an ethynyl group or a deuterium atom-substituted acetylene group. And an ethynyl group is preferred.
When R 5a to R 5h are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
In the case where R 5a to R 5h are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituents that the acyl group can take are as follows: And a fluorine atom. In the case of a substituent other than the group represented by the formula (W), the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
－式（６）で表される化合物－ -Compound represented by Formula (6)-
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（６）中、Ｘ６ａ～Ｘ６ｄはそれぞれ独立に、ＮＲ６ｇ、Ｏ原子又はＳ原子を表し、Ｒ６ｇは水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表す。
　Ｘ６ａ～Ｘ６ｄはそれぞれ独立に、Ｏ原子又はＳ原子であることが合成容易性の観点から好ましい。一方、Ｘ６ａ～Ｘ６ｄのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ６ａ～Ｘ６ｄは、同じ連結基であることが好ましい。Ｘ６ａ～Ｘ６ｄはいずれもＳ原子であることがより好ましい。
　Ｒ６ｇは水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基であることが好ましく、水素原子又はアルキル基であることがより好ましく、炭素数１～１４のアルキル基であることが更に好ましく、炭素数１～４のアルキル基であることが特に好ましい。
　Ｒ６ｇがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。 In the formula (6), X 6a to X 6d each independently represents NR 6g , O atom or S atom, and R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl. Represents a group.
X 6a to X 6d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing carrier mobility that at least one of X 6a to X 6d is an S atom. X 6a to X 6d are preferably the same linking group. X 6a to X 6d are more preferably S atoms.
R 6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, and is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, An alkyl group is more preferable, an alkyl group having 1 to 14 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When R 6g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.
　式（６）中、Ｒ６ａ～Ｒ６ｆはそれぞれ独立に、水素原子又は置換基を表し、少なくとも１つは式（Ｗ）で表される基を表す。
　なお、Ｒ６ａ～Ｒ６ｆで表される置換基としては、上述した置換基Ｘが挙げられる。また、式（Ｗ）で表される基の定義は、上述の通りである。
　これらの中でも、Ｒ６ａ～Ｒ６ｆがそれぞれ独立にとりうる置換基として、アルキル基、アリール基、アルケニル基、アルキニル基、複素環基、アルコキシ基、又は、アルキルチオ基、式（Ｗ）で表される基が好ましく、炭素数１～１２のアルキル基、炭素数６～２０のアリール基、炭素数２～１２のアルケニル基、炭素数２～１２のアルキニル基、炭素数１～１１のアルコキシ基、炭素数５～１２の複素環基、炭素数１～１２のアルキルチオ基、又は、式（Ｗ）で表される基がより好ましく、後述の連結基鎖長が３．７Å以下の基、又は、式（Ｗ）で表される基が更に好ましく、式（Ｗ）で表される基が特に好ましい。 In formula (6), R 6a to R 6f each independently represents a hydrogen atom or a substituent, and at least one represents a group represented by formula (W).
Examples of the substituent represented by R 6a to R 6f include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
Among these, R 6a to R 6f each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a formula (W). A group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, carbon A heterocyclic group having 5 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula (W) is more preferable, a group having a linking group chain length of 3.7 後 述 or less, A group represented by (W) is more preferred, and a group represented by formula (W) is particularly preferred.
　式（６）で表される化合物中、Ｒ６ａ～Ｒ６ｆのうち、式（Ｗ）で表される基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ６ａ～Ｒ６ｆのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ６ｃ～Ｒ６ｆであることが好ましく、Ｒ６ｅ又はＲ６ｆであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点からより好ましい。 Among the compounds represented by formula (6), among R 6a to R 6f , the number of groups represented by formula (W) is 1 to 4, which increases carrier mobility and dissolves in an organic solvent. From the viewpoint of enhancing the properties, it is preferably 1 or 2, more preferably 2.
Among R 6a to R 6f , the position of the group represented by the formula (W) is not particularly limited, but is preferably R 6c to R 6f , and is preferably R 6e or R 6f. Is more preferable from the viewpoint of increasing the solubility in organic solvents.
　Ｒ６ａ～Ｒ６ｆのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基は、連結基鎖長が３．７Å以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることが更に好ましい。連結基鎖長の定義は、上述の通りである。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基はそれぞれ独立に、素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、炭素数２以下の置換又は無置換のアルキル基であることがより好ましい。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ６ａ～Ｒ６ｆが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 Of R 6a to R 6f, the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
In the case where R 6a to R 6f are substituents other than the group represented by the formula (W), the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and further preferably a group having a linking group chain length of 1.0 to 2.1 mm. The definition of the linking group chain length is as described above.
When R 6a to R 6f are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having a prime number of 2 or less, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably a substituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable that
When R 6a to R 6f are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group Are preferred, methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
When R 6a to R 6f are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are as follows: And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
When R 6a to R 6f are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms. And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
When R 6a to R 6f are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituents that the acyl group can take are as follows: And a fluorine atom. In the case of a substituent other than the group represented by the formula (W), the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
－式（７）で表される化合物－ -Compound represented by Formula (7)-
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（７）中、Ｘ７ａ及びＸ７ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ７ｉ（＞Ｎ－Ｒ７ｉ）を表し、Ｘ７ｂ及びＸ７ｄはそれぞれ独立に、Ｓ原子、Ｏ原子又はＳｅ原子を表す。Ｘ７ａ～Ｘ７ｄはそれぞれ独立に、Ｏ原子又はＳ原子であることが合成容易性の観点から好ましい。一方、Ｘ７ａ～Ｘ７ｄのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ７ａ～Ｘ７ｄは、同じ連結基であることが好ましい。Ｘ７ａ～Ｘ７ｄはいずれもＳ原子であることがより好ましい。 In the formula (7), X 7a and X 7c each independently represents an S atom, an O atom, a Se atom or NR 7i (> N—R 7i ), and X 7b and X 7d each independently represent an S atom, O atom or Se atom is represented. X 7a to X 7d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, at least one of X 7a to X 7d is preferably an S atom from the viewpoint of increasing carrier mobility. X 7a to X 7d are preferably the same linking group. X 7a to X 7d are more preferably S atoms.
　式（７）中、Ｒ７ａ～Ｒ７ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ７ａ～Ｒ７ｉのうち少なくとも１つが式（Ｗ）で表される基である。
　なお、Ｒ７ａ～Ｒ７ｉで表される置換基としては、上述した置換基Ｘが挙げられる。また、式（Ｗ）で表される基の定義は、上述の通りである。
　なお、Ｒ７ｉは、水素原子又はアルキル基であることが好ましく、炭素数５～１２のアルキル基であることがより好ましく、炭素数８～１０のアルキル基であることが特に好ましい。
　Ｒ７ｉがアルキル基を表す場合、直鎖のアルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖のアルキル基であることが、ＨＯＭＯ軌道の重なりの観点から好ましい。 In formula (7), R 7a to R 7i each independently represents a hydrogen atom or a substituent, and at least one of R 7a to R 7i is a group represented by formula (W).
Examples of the substituent represented by R 7a to R 7i include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
R 7i is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R 7i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred from the viewpoint of overlapping HOMO orbitals.
　式（７）で表される化合物中、Ｒ７ａ～Ｒ７ｉのうち、式（Ｗ）で表される置換基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ７ａ～Ｒ７ｉのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ７ｄ又はＲ７ｈであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、Ｒ７ｄ及びＲ７ｈがより好ましい。
　式（７）のＲ７ａ～Ｒ７ｉのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基は、連結基鎖長が３．７Å以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることが更に好ましい。連結基鎖長の定義は、上述の通りである。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基はそれぞれ独立に、炭素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、炭素数２以下の置換又は無置換のアルキル基であることがより好ましい。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される置換基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される置換基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ７ａ～Ｒ７ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。式（Ｗ）で表される置換基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 In the compound represented by the formula (7), among R 7a to R 7i , 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
Of R 7a to R 7i , the position of the group represented by the formula (W) is not particularly limited, but R 7d or R 7h increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 7d and R 7h are more preferable.
Of R 7a to R 7i in the formula (7), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2, Or it is more preferable that it is 1 piece, and it is especially preferable that it is 0 piece.
When R 7a to R 7i are substituents other than the group represented by formula (W), the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and even more preferably a group having a linking group chain length of 1.0 to 2.1 mm. The definition of the linking group chain length is as described above.
When R 7a to R 7i are substituents other than the group represented by formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted carbon group having 2 or less carbon atoms, It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms. More preferably, it is a group.
When R 7a to R 7i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group Are preferred, methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
When R 7a to R 7i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are as follows: And deuterium atoms. In the case of a substituent other than the substituent represented by the formula (W), the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent is an ethynyl group or a deuterium atom-substituted acetylene group. And an ethynyl group is preferred.
When R 7a to R 7i are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms. And deuterium atoms. In the case of a substituent other than the substituent represented by the formula (W), the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent includes an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
When R 7a to R 7i are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms. And a fluorine atom. The substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by the formula (W) is a formyl group, an acetyl group, or a fluorine-substituted acetyl group And a formyl group is preferred.
－式（８）で表される化合物－ -Compound represented by Formula (8)-
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（８）中、Ｘ８ａ及びＸ８ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ８ｉを表し、Ｘ８ｂ及びＸ８ｄはそれぞれ独立に、Ｓ原子、Ｏ原子又はＳｅ原子を表す。Ｘ８ａ～Ｘ８ｄはそれぞれ独立に、Ｏ原子又はＳ原子であることが合成容易性の観点から好ましい。一方、Ｘ８ａ～Ｘ８ｄのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ８ａ～Ｘ８ｄは、同じ連結基であることが好ましい。Ｘ８ａ～Ｘ８ｄはいずれもＳ原子であることがより好ましい。 In formula (8), X 8a and X 8c each independently represent an S atom, O atom, Se atom or NR 8i , and X 8b and X 8d each independently represent an S atom, O atom or Se atom. . X 8a to X 8d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, at least one of X 8a to X 8d is preferably an S atom from the viewpoint of increasing carrier mobility. X 8a to X 8d are preferably the same linking group. It is more preferable that all of X 8a to X 8d are S atoms.
　式（８）中、Ｒ８ａ～Ｒ８ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ８ａ～Ｒ８ｉのうち少なくとも１つが式（Ｗ）で表される基である。
　なお、Ｒ８ａ～Ｒ８ｉで表される置換基としては、上述した置換基Ｘが挙げられる。また、式（Ｗ）で表される基の定義は、上述の通りである。
　なお、Ｒ８ｉは、水素原子又はアルキル基であることが好ましく、炭素数５～１２のアルキル基であることがより好ましく、炭素数８～１０のアルキル基であることが特に好ましい。
　Ｒ８ｉがアルキル基を表す場合、直鎖のアルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖のアルキル基であることが、ＨＯＭＯ軌道の重なりの観点から好ましい。 In formula (8), R 8a to R 8i each independently represents a hydrogen atom or a substituent, and at least one of R 8a to R 8i is a group represented by formula (W).
Examples of the substituent represented by R 8a to R 8i include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
R 8i is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R 8i represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferable from the viewpoint of overlapping HOMO orbitals.
　式（８）で表される化合物中、Ｒ８ａ～Ｒ８ｉのうち、式（Ｗ）で表される置換基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ８ａ～Ｒ８ｉのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ８ｃ又はＲ８ｇであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、Ｒ８ｃ及びＲ８ｇがより好ましい。
　また、式（８）のＲ８ａ～Ｒ８ｉのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。 In the compound represented by the formula (8), among R 8a to R 8i , 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
Among R 8a to R 8i , the position of the group represented by the formula (W) is not particularly limited, but R 8c or R 8g increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 8c and R 8g are more preferable.
In addition, among R 8a to R 8i in the formula (8), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is more preferable, and 0 is particularly preferable.
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基は、連結基鎖長が３．７Å以下の基であることが好ましく、連結基鎖長が１．０～３．７Åの基であることがより好ましく、連結基鎖長が１．０～２．１Åの基であることが更に好ましい。連結基鎖長の定義は、上述の通りである。
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基はそれぞれ独立に、炭素数２以下の置換若しくは無置換のアルキル基、炭素数２以下の置換若しくは無置換のアルキニル基、炭素数２以下の置換若しくは無置換のアルケニル基、又は、炭素数２以下の置換若しくは無置換のアシル基であることが好ましく、炭素数２以下の置換又は無置換のアルキル基であることがより好ましい。
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキル基を表す場合、アルキル基がとり得る置換基としては、シアノ基、フッ素原子、又は、重水素原子などを挙げることができ、シアノ基が好ましい。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキル基としては、メチル基、エチル基、又は、シアノ基置換のメチル基が好ましく、メチル基又はシアノ基置換のメチル基がより好ましく、シアノ基置換のメチル基が特に好ましい。
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルキニル基を表す場合、アルキニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルキニル基としては、エチニル基、又は、重水素原子置換のアセチレン基を挙げることができ、エチニル基が好ましい。
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アルケニル基を表す場合、アルケニル基がとり得る置換基としては、重水素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアルケニル基としては、エテニル基、又は、重水素原子置換のエテニル基を挙げることができ、エテニル基が好ましい。
　Ｒ８ａ～Ｒ８ｉが式（Ｗ）で表される基以外の置換基である場合の置換基がそれぞれ独立に炭素数２以下の置換アシル基を表す場合、アシル基がとり得る置換基としては、フッ素原子などを挙げることができる。式（Ｗ）で表される基以外の置換基である場合の置換基が表す炭素数２以下の置換又は無置換のアシル基としては、ホルミル基、アセチル基、又は、フッ素置換のアセチル基を挙げることができ、ホルミル基が好ましい。 In the case where R 8a to R 8i are substituents other than the group represented by the formula (W), the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1 It is more preferably a group having a length of 0.0 to 3.7 mm, and even more preferably a group having a linking group chain length of 1.0 to 2.1 mm. The definition of the linking group chain length is as described above.
When R 8a to R 8i are substituents other than the group represented by the formula (W), the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted carbon group having 2 or less carbon atoms, It is preferably an unsubstituted alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl having 2 or less carbon atoms. More preferably, it is a group.
When R 8a to R 8i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituents that the alkyl group can take are as follows: , A cyano group, a fluorine atom, or a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) is a methyl group, an ethyl group, or a cyano group-substituted methyl group Are preferred, methyl group or methyl group substituted with cyano group is more preferred, and methyl group substituted with cyano group is particularly preferred.
When R 8a to R 8i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are as follows: And deuterium atoms. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by the formula (W) include an ethynyl group or a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
When R 8a to R 8i are substituents other than the group represented by the formula (W), each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, the substituents that the alkenyl group can take are as follows: And deuterium atoms. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by formula (W) include an ethenyl group or a deuterium atom-substituted ethenyl group. And an ethenyl group is preferred.
When R 8a to R 8i are substituents other than the group represented by formula (W), each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituents that the acyl group can take are as follows: And a fluorine atom. In the case of a substituent other than the group represented by the formula (W), the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent is a formyl group, an acetyl group, or a fluorine-substituted acetyl group. And a formyl group is preferred.
－式（９）で表される化合物－ -Compound represented by Formula (9)-
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（９）中、Ｘ９ａ及びＸ９ｂはそれぞれ独立に、Ｏ原子、Ｓ原子又はＳｅ原子を表す。中でも、Ｓ原子が好ましい。
　Ｒ９ｃ、Ｒ９ｄ及びＲ９ｇ～Ｒ９ｊはそれぞれ独立に、水素原子、ハロゲン原子又は式（Ｗ）で表される置換基を表す。式（Ｗ）で表される基の定義は、上述の通りである。
　Ｒ９ａ、Ｒ９ｂ、Ｒ９ｅ及びＲ９ｆは、それぞれ独立に、水素原子又は置換基を表す。なお、Ｒ９ａ、Ｒ９ｂ、Ｒ９ｅ及びＲ９ｆで表される置換基としては、上述した置換基Ｘが挙げられる。
　なお、Ｒ９ｃ、Ｒ９ｄ及びＲ９ｇ～Ｒ９ｊはそれぞれ独立に、水素原子、ハロゲン原子又は式（Ｗ）で表される基（ただし、ＬＷは式（Ｌ－３）、式（Ｌ－５）、式（Ｌ－７）～式（Ｌ－９）、式（Ｌ－１２）～式（Ｌ－２４）のいずれかで表される基である。）を表すことが好ましい。中でも、Ｒ９ｃ、Ｒ９ｄ及びＲ９ｇ～Ｒ９ｊは、水素原子がより好ましい。
　なお、ＬＷとしては、式（Ｌ－３）、式（Ｌ－５）、式（Ｌ－１３）、式（Ｌ－１７）又は式（Ｌ－１８）のいずれかで表される基であることが好ましい。
　Ｒ９ａ～Ｒ９ｉのうち少なくとも１つは、式（Ｗ）で表される基を表すことが好ましい。 In formula (9), X 9a and X 9b each independently represent an O atom, an S atom, or an Se atom. Among these, S atom is preferable.
R 9c , R 9d and R 9g to R 9j each independently represents a hydrogen atom, a halogen atom or a substituent represented by the formula (W). The definition of the group represented by the formula (W) is as described above.
R 9a , R 9b , R 9e and R 9f each independently represent a hydrogen atom or a substituent. In addition, the substituent X mentioned above is mentioned as a substituent represented by R < 9a > , R < 9b> , R <9e> and R <9f> .
R 9c , R 9d and R 9g to R 9j are each independently a hydrogen atom, a halogen atom or a group represented by the formula (W) (where L W is the formula (L-3), the formula (L— 5), a group represented by any one of formulas (L-7) to (L-9) and (L-12) to (L-24). Among these, R 9c , R 9d and R 9g to R 9j are more preferably hydrogen atoms.
Note that L W is a group represented by any one of formula (L-3), formula (L-5), formula (L-13), formula (L-17), or formula (L-18). Preferably there is.
At least one of R 9a to R 9i preferably represents a group represented by the formula (W).
　式（９）で表される化合物中、Ｒ９ａ～Ｒ９ｉのうち、式（Ｗ）で表される置換基は、１～４個であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、１又は２個であることがより好ましく、２個であることが特に好ましい。
　Ｒ９ａ～Ｒ９ｉのうち、式（Ｗ）で表される基の位置に特に制限はないが、Ｒ９ｂ又はＲ９ｆであることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましく、Ｒ９ｂ及びＲ９ｆがより好ましい。
　また、式（９）のＲ９ａ～Ｒ９ｉのうち、式（Ｗ）で表される基以外の置換基は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが特に好ましく、０個であることがより特に好ましい。 In the compound represented by the formula (9), among R 9a to R 9i , 1 to 4 substituents represented by the formula (W) increase carrier mobility, From the viewpoint of enhancing the solubility, it is preferably 1 or 2, more preferably 2.
Of R 9a to R 9i , the position of the group represented by the formula (W) is not particularly limited, but R 9b or R 9f increases carrier mobility and increases solubility in an organic solvent. From the viewpoint, R 9b and R 9f are more preferable.
Further, among R 9a to R 9i of the formula (9), the number of substituents other than the group represented by the formula (W) is preferably 0 to 4, more preferably 0 to 2. 0 or 1 is particularly preferable, and 0 is particularly preferable.
－式（１０）で表される化合物－ -Compound represented by Formula (10)-
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（１０）中、Ｒ１０ａ～Ｒ１０ｈはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１０ａ～Ｒ１０ｈのうち少なくとも１つは式（Ｗ）で表される基を表す。なお、Ｒ１０ａ～Ｒ１０ｈで表される置換基としては、上述した置換基Ｘが挙げられる。また、式（Ｗ）で表される置換基の定義は、上述の通りである。
　中でも、Ｒ１０ａ～Ｒ１０ｈはそれぞれ独立に、水素原子、ハロゲン原子又は置換基を表し、Ｒ１０ａ～Ｒ１０ｈのうち少なくとも１つは、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基であることが好ましい。
　式（１０）のＲ１０ａ～Ｒ１０ｈは、Ｒ１０ｂ及びＲ１０ｆのうち少なくとも１つが、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基であることが好ましく、置換若しくは無置換のアリールチオ基、又は、置換若しくは無置換のヘテロアリールチオ基であることがより好ましく、Ｒ１０ｂ及びＲ１０ｆのいずれもが、置換若しくは無置換のアリールチオ基、又は、置換若しくは無置換のヘテロアリールチオ基であることが更に好ましく、置換若しくは無置換のフェニルチオ基又は下記群Ａから選ばれるヘテロアリールチオ基であることが特に好ましく、置換若しくは無置換のフェニルチオ基又は下記式（Ａ－１７）、式（Ａ－１８）、式（Ａ－２０）で表されるヘテロアリールチオ基であることが最も好ましい。 In formula (10), R 10a to R 10h each independently represents a hydrogen atom or a substituent, and at least one of R 10a to R 10h represents a group represented by formula (W). Examples of the substituent represented by R 10a to R 10h include the substituent X described above. Moreover, the definition of the substituent represented by Formula (W) is as above-mentioned.
Among them, R 10a to R 10h each independently represents a hydrogen atom, a halogen atom or a substituent, and at least one of R 10a to R 10h is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroary It is preferably a ruthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group.
R 10a to R 10h in the formula (10) are such that at least one of R 10b and R 10f is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group A substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, preferably a substituted or unsubstituted arylthio group or a substituted or unsubstituted heteroarylthio group. More preferably, each of R 10b and R 10f is more preferably a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroarylthio group, and a substituted or unsubstituted phenylthio group or the following group A Particularly preferred is a heteroarylthio group selected from Most preferably, it is a substituted or unsubstituted phenylthio group or a heteroarylthio group represented by the following formula (A-17), formula (A-18), or formula (A-20).
　アリールチオ基としては、炭素数６～２０のアリール基に硫黄原子が連結した基が好ましく、ナフチルチオ基又はフェニルチオ基がより好ましく、フェニルチオ基が特に好ましい。
　ヘテロアリールチオ基としては、３～１０員環のヘテロアリール基に硫黄原子が連結した基が好ましく、５又は６員環のヘテロアリール基に硫黄原子が連結した基がより好ましく、下記群Ａ（式（Ａ－１４）～式（Ａ－２７）のいずれかで表される基）が特に好ましい。 The arylthio group is preferably a group having a sulfur atom linked to an aryl group having 6 to 20 carbon atoms, more preferably a naphthylthio group or a phenylthio group, and particularly preferably a phenylthio group.
The heteroarylthio group is preferably a group in which a sulfur atom is linked to a 3- to 10-membered heteroaryl group, more preferably a group in which a sulfur atom is linked to a 5- or 6-membered heteroaryl group. A group represented by any one of formulas (A-14) to (A-27)) is particularly preferable.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　群Ａ中、Ｒ”及びＲ”Ｎはそれぞれ独立に、水素原子又は置換基を表す。
　群Ａ中、Ｒ’はそれぞれ独立に、水素原子又は式（Ｗ）で表される基を表すことが好ましい。
　群Ａ中、Ｒ”Ｎは、置換基を表すことが好ましく、アルキル基、アリール基、又は、ヘテロアリール基がより好ましく、アルキル基、アルキル基で置換されたアリール基、又は、アルキル基で置換されたヘテロアリール基が更に好ましく、炭素数１～４のアルキル基、炭素数１～４のアルキル基で置換されたフェニル基、又は、炭素数１～４のアルキル基で置換された５員のヘテロアリール基が特に好ましい。 In group A, R ″ and R ″ N each independently represent a hydrogen atom or a substituent.
In group A, each R ′ preferably independently represents a hydrogen atom or a group represented by the formula (W).
In group A, R ″ N preferably represents a substituent, more preferably an alkyl group, an aryl group, or a heteroaryl group, and is substituted with an alkyl group, an aryl group substituted with an alkyl group, or an alkyl group. The heteroaryl group is more preferably a 5-membered alkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A heteroaryl group is particularly preferred.
　アルキルオキシカルボニル基としては、炭素数１～２０のアルキル基にカルボニル基が連結した基が好ましい。アルキル基の炭素数は、２～１５がより好ましく、５～１０が特に好ましい。 The alkyloxycarbonyl group is preferably a group in which a carbonyl group is linked to an alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of the alkyl group is more preferably 2-15, and particularly preferably 5-10.
　アリールオキシカルボニル基としては、炭素数６～２０のアリール基にカルボニル基が連結した基が好ましい。アリール基の炭素数は、６～１５がより好ましく、８～１２が特に好ましい。 The aryloxycarbonyl group is preferably a group in which a carbonyl group is linked to an aryl group having 6 to 20 carbon atoms. The number of carbon atoms of the aryl group is more preferably 6-15, and particularly preferably 8-12.
　アルキルアミノ基としては、炭素数１～２０のアルキル基にアミノ基が連結した基が好ましい。アルキル基の炭素数は、２～１５がより好ましく、５～１０が特に好ましい。
　Ｒ１０ａ～Ｒ１０ｈのうち、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基以外の置換基（以下、他の置換基ともいう。）は、０～４個であることが好ましく、０～２個であることがより好ましく、０又は１個であることが更に好ましく、０個であることが特に好ましい。 The alkylamino group is preferably a group in which an amino group is linked to an alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of the alkyl group is more preferably 2-15, and particularly preferably 5-10.
Among R 10a to R 10h , a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted The number of substituents other than the unsubstituted alkylamino group (hereinafter also referred to as other substituents) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is more preferable that the number is 0.
　Ｘ１０ａ及びＸ１０ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲｘ（＞Ｎ－Ｒｘ）を表す。Ｘ１０ａ及びＸ１０ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１０ａ及びＸ１０ｂは、同じ連結基であることが好ましい。Ｘ１０ａ及びＸ１０ｂは、いずれもＳ原子であることがより好ましい。
　Ｒｘはそれぞれ独立に、水素原子又は式（Ｗ）で表される基を表す。式（Ｗ）で表される基の定義は上述の通りである。 X 10a and X 10b each independently represent an S atom, an O atom, a Se atom, or NR x (> N—R x ). It is preferable from the viewpoint of increasing carrier mobility that at least one of X 10a and X 10b is an S atom. X 10a and X 10b are preferably the same linking group. As for X10a and X10b , it is more preferable that all are S atoms.
R x each independently represents a hydrogen atom or a group represented by the formula (W). The definition of the group represented by the formula (W) is as described above.
－式（１１）で表される化合物－ -Compound represented by Formula (11)-
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（１１）中、Ｘ１１ａ及びＸ１１ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１１ｎを表し、Ｒ１１ａ～Ｒ１１ｋ、Ｒ１１ｍ及びＲ１１ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１１ａ～Ｒ１１ｋ、Ｒ１１ｍ及びＲ１１ｎのうち少なくとも１つは、式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される置換基の定義は、上述の通りである。 In formula (11), X 11a and X 11b each independently represent an S atom, O atom, Se atom or NR 11n , and R 11a to R 11k , R 11m and R 11n each independently represent a hydrogen atom or a substituent And at least one of R 11a to R 11k , R 11m and R 11n represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the substituent represented by the formula (W) is as described above.
　式（１１）中、Ｘ１１ａ及びＸ１１ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１１ａ及びＸ１１ｂは、同じ連結基であることが好ましい。Ｘ１１ａ及びＸ１１ｂはいずれもＳ原子であることがより好ましい。
　式（１１）のＲ１１ａ～Ｒ１１ｋ及びＲ１１ｍは、Ｒ１１ｃ及びＲ１１ｉのうち少なくとも１つが、置換若しくは無置換のアルキル基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基であることが好ましく、置換若しくは無置換のアルキル基であることがより好ましく、Ｒ１１ｃ及びＲ１１ｉのいずれもが、置換若しくは無置換のアルキル基であることが更に好ましい。 In formula (11), at least one of X 11a and X 11b is preferably an S atom from the viewpoint of increasing carrier mobility. X 11a and X 11b are preferably the same linking group. It is more preferable that both X 11a and X 11b are S atoms.
R 11a to R 11k and R 11m in the formula (11) are such that at least one of R 11c and R 11i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group. Preferably, both R 11c and R 11i are more preferably substituted or unsubstituted alkyl groups.
－式（１２）で表される化合物－ -Compound represented by Formula (12)-
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（１２）中、Ｘ１２ａ及びＸ１２ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１２ｎを表し、Ｒ１２ａ～Ｒ１２ｋ、Ｒ１２ｍ及びＲ１２ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１２ａ～Ｒ１２ｋ、Ｒ１２ｍ及びＲ１２ｎのうち少なくとも１つは式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される置換基の定義は、上述の通りである。 In the formula (12), X 12a and X 12b each independently represent an S atom, an O atom, a Se atom or NR 12n , and R 12a to R 12k , R 12m and R 12n each independently represent a hydrogen atom or a substituent And at least one of R 12a to R 12k , R 12m and R 12n represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the substituent represented by the formula (W) is as described above.
　式（１２）中、Ｘ１２ａ及びＸ１２ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１２ａ及びＸ１２ｂは、同じ連結基であることが好ましい。Ｘ１２ａ及びＸ１２ｂはいずれもＳ原子であることがより好ましい。
　式（１２）のＲ１２ａ～Ｒ１２ｋ及びＲ１２ｍは、Ｒ１２ｃ及びＲ１２ｉのうち少なくとも１つが、置換若しくは無置換のアルキル基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基であることが好ましく、置換若しくは無置換のアルキル基であることがより好ましく、Ｒ１２ｃ及びＲ１２ｉのいずれもが、置換又は無置換のアルキル基であることが更に好ましい。 In formula (12), it is preferable from the viewpoint of increasing carrier mobility that at least one of X 12a and X 12b is an S atom. X 12a and X 12b are preferably the same linking group. It is more preferable that both X 12a and X 12b are S atoms.
R 12a to R 12k and R 12m in the formula (12) are such that at least one of R 12c and R 12i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group. Preferably, both R 12c and R 12i are more preferably substituted or unsubstituted alkyl groups.
－式（１３）で表される化合物－ -Compound represented by Formula (13)-
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式（１３）中、Ｘ１３ａ及びＸ１３ｂはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１３ｎを表し、Ｒ１３ａ～Ｒ１３ｋ、Ｒ１３ｍ及びＲ１３ｎはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１３ａ～Ｒ１３ｋ、Ｒ１３ｍ及びＲ１３ｎのうち少なくとも１つは、式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される基の定義は、上述の通りである。 In formula (13), X 13a and X 13b each independently represent an S atom, an O atom, a Se atom or NR 13n , and R 13a to R 13k , R 13m and R 13n each independently represent a hydrogen atom or a substituent And at least one of R 13a to R 13k , R 13m and R 13n represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
　式（１３）中、Ｘ１３ａ及びＸ１３ｂのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１３ａ及びＸ１３ｂは、同じ連結基であることが好ましい。Ｘ１３ａ及びＸ１３ｂはいずれもＳ原子であることがより好ましい。
　式（１３）のＲ１３ａ～Ｒ１３ｋ及びＲ１３ｍは、Ｒ１３ｃ及びＲ１３ｉのうち少なくとも１つが、置換若しくは無置換のアルキル基、置換若しくは無置換のアリールチオ基、置換若しくは無置換のヘテロアリールチオ基、置換若しくは無置換のアルキルオキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、又は、置換若しくは無置換のアルキルアミノ基であることが好ましく、置換若しくは無置換のアルキル基であることがより好ましく、Ｒ１３ｃ及びＲ１３ｉのいずれもが、置換若しくは無置換のアルキル基であることが更に好ましい。 In formula (13), at least one of X 13a and X 13b is preferably an S atom, from the viewpoint of increasing carrier mobility. X 13a and X 13b are preferably the same linking group. It is more preferable that both X 13a and X 13b are S atoms.
R 13a to R 13k and R 13m in the formula (13) are such that at least one of R 13c and R 13i is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio It is preferably a group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group, and more preferably a substituted or unsubstituted alkyl group. Preferably, both R 13c and R 13i are more preferably substituted or unsubstituted alkyl groups.
－式（１４）で表される化合物－ -Compound represented by Formula (14)-
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　式（１４）中、Ｘ１４ａ～Ｘ１４ｃはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１４ｉを表し、Ｒ１４ａ～Ｒ１４ｉはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１４ａ～Ｒ１４ｉのうち少なくとも１つは、式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される基の定義は、上述の通りである。
　なお、Ｒ１４ａ～Ｒ１４ｈの少なくとも１つが式（Ｗ）で表される基であり、ＲＷがアルキル基である場合には、ＬＷは式（Ｌ－２）～式（Ｌ－２５）のいずれかで表される基であることが好ましい。 In the formula (14), X 14a to X 14c each independently represents an S atom, O atom, Se atom or NR 14i , R 14a to R 14i each independently represents a hydrogen atom or a substituent, and R 14a At least one of ˜R 14i represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
When at least one of R 14a to R 14h is a group represented by the formula (W) and R W is an alkyl group, L W is a formula (L-2) to a formula (L-25) It is preferable that it is group represented by either.
　式（１４）中、Ｘ１４ａ～Ｘ１４ｃのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１４ａ～Ｘ１４ｃは、同じ連結基であることが好ましい。Ｘ１４ａ～Ｘ１４ｃはいずれもＳ原子であることがより好ましい。
　ＲＷがアルキル基である場合のＬＷとしては、式（Ｌ－２）～式（Ｌ－５）、式（Ｌ－１３）、式（Ｌ－１７）、又は、式（Ｌ－１８）のいずれかで表される基が好ましく、式（Ｌ－３）、式（Ｌ－１３）、又は、式（Ｌ－１８）のいずれかで表される基がより好ましい。
　式（１４）のＲ１４ａ～Ｒ１４ｈは、Ｒ１４ｂ及びＲ１４ｇのうち少なくとも１つが、式（Ｗ）で表される基であることが好ましく、Ｒ１４ｂ及びＲ１４ｇのいずれもが、式（Ｗ）で表される基であることがより好ましい。 In formula (14), at least one of X 14a to X 14c is preferably an S atom from the viewpoint of increasing carrier mobility. X 14a to X 14c are preferably the same linking group. It is more preferable that all of X 14a to X 14c are S atoms.
L W in the case where R W is an alkyl group, is represented by Formula (L-2) to Formula (L-5), Formula (L-13), Formula (L-17), or Formula (L-18). A group represented by any one of formula (L-3), formula (L-13), or formula (L-18) is more preferred.
R 14a ~ R 14h of formula (14), at least one of R 14b and R 14 g, is preferably a group represented by the formula (W), any of R 14b and R 14 g is represented by the formula ( More preferred is a group represented by W).
－式（１５）で表される化合物－ -Compound represented by Formula (15)-
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　式（１５）中、Ｘ１５ａ～Ｘ１５ｄはそれぞれ独立にＳ原子、Ｏ原子、Ｓｅ原子又はＮＲ１５ｇを表し、Ｒ１５ａ～Ｒ１５ｇはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１５ａ～Ｒ１５ｇのうち少なくとも１つは、式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される基の定義は、上述の通りである。 Wherein (15), X 15a ~ X 15d each independently S atom, O atom, a Se atom or a NR 15g, R 15a ~ R 15g each independently represent a hydrogen atom or a substituent, R 15a ~ At least one of R 15g represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
　式（１５）中、Ｘ１５ａ～Ｘ１５ｄのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１５ａ～Ｘ１５ｄは、同じ連結基であることが好ましい。Ｘ１５ａ～Ｘ１５ｄはいずれもＳ原子であることがより好ましい。
　式（１５）のＲ１５ａ～Ｒ１５ｆは、Ｒ１５ｂ及びＲ１５ｅのうち少なくとも１つが、式（Ｗ）で表される基であることが好ましく、Ｒ１５ｂ及びＲ１５ｅのいずれもが、式（Ｗ）で表される基であることがより好ましい。 In formula (15), at least one of X 15a to X 15d is preferably an S atom from the viewpoint of increasing carrier mobility. X 15a to X 15d are preferably the same linking group. It is more preferable that all of X 15a to X 15d are S atoms.
R 15a ~ R 15f of formula (15), at least one of R 15b and R 15e, is preferably a group represented by the formula (W), any of R 15b and R 15e is the formula ( More preferred is a group represented by W).
－式（１６）で表される化合物－ -Compound represented by Formula (16)-
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（１６）中、Ｘ１６ａ～Ｘ１６ｄはそれぞれ独立に、Ｓ原子、Ｏ原子、Ｓｅ原子又はＮＲ１６ｇを表す。Ｒ１６ａ～Ｒ１６ｇはそれぞれ独立に、水素原子又は置換基を表し、Ｒ１６ａ～Ｒ１６ｇのうち少なくとも１つは、式（Ｗ）で表される基を表す。置換基としては、上述した置換基Ｘが挙げられる。式（Ｗ）で表される基の定義は、上述の通りである。
　なお、Ｒ１６ｃ及びＲ１６ｆは、水素原子、ハロゲン原子又は式（Ｗ）で表される基（ただし、ＬＷは、式（Ｌ－３）、式（Ｌ－５）、式（Ｌ－７）～式（Ｌ－９）、式（Ｌ－１２）～式（Ｌ－２４）のいずれかで表される基である。）であることが好ましい。Ｒ１６ａ、Ｒ１６ｂ、Ｒ１６ｄ、Ｒ１６ｅ及びＲ１６ｇはそれぞれ独立に、水素原子又は置換基を表すことが好ましい。
　なお、式（１６）において、ＬＷは、式（Ｌ－３）、式（Ｌ－５）、式（Ｌ－７）～式（Ｌ－９）、式（Ｌ－１２）～式（Ｌ－２４）のいずれかで表される基であり、Ｒ１６ｃ及びＲ１６ｆが式（Ｗ）で表される基の場合、式（Ｌ－３）、式（Ｌ－５）、式（Ｌ－１３）、式（Ｌ－１７）、式（Ｌ－１８）のいずれかで表される基であることが好ましい。 In the formula (16), X 16a to X 16d each independently represents an S atom, an O atom, a Se atom, or NR 16g . R 16a to R 16g each independently represents a hydrogen atom or a substituent, and at least one of R 16a to R 16g represents a group represented by the formula (W). Examples of the substituent include the substituent X described above. The definition of the group represented by the formula (W) is as described above.
R 16c and R 16f are a hydrogen atom, a halogen atom or a group represented by the formula (W) (where L W is a formula (L-3), a formula (L-5), a formula (L-7 To a group represented by any one of formulas (L-9) and (L-12) to (L-24)). R 16a , R 16b , R 16d , R 16e and R 16g each independently preferably represent a hydrogen atom or a substituent.
In Formula (16), L W is expressed by Formula (L-3), Formula (L-5), Formula (L-7) to Formula (L-9), Formula (L-12) to Formula (L -24), and when R 16c and R 16f are groups represented by formula (W), formula (L-3), formula (L-5), formula (L- 13), a group represented by any of formulas (L-17) and (L-18) is preferable.
　式（１６）中、Ｘ１６ａ～Ｘ１６ｄのうち少なくとも１つがＳ原子であることが、キャリア移動度を高める観点から好ましい。Ｘ１６ａ～Ｘ１６ｄは、同じ連結基であることが好ましい。Ｘ１６ａ～Ｘ１６ｄはいずれもＳ原子であることがより好ましい。
　式（１６）のＲ１６ａ～Ｒ１６ｆは、Ｒ１６ａ及びＲ１６ｄのうち少なくとも１つが、式（Ｗ）で表される基であることが好ましく、Ｒ１６ａ及びＲ１６ｄのいずれもが、式（Ｗ）で表される基であることがより好ましい。
　また、Ｒ１６ｃ及びＲ１６ｆは、水素原子であることが好ましい。 In the formula (16), at least one of X 16a to X 16d is preferably an S atom from the viewpoint of increasing carrier mobility. X 16a to X 16d are preferably the same linking group. It is more preferable that all of X 16a to X 16d are S atoms.
R 16a ~ R 16f of formula (16), at least one of R 16a and R 16d, is preferably a group represented by the formula (W), none of R 16a and R 16d is the formula ( More preferred is a group represented by W).
R 16c and R 16f are preferably hydrogen atoms.
　成分Ａは、上記縮合多環芳香族基における縮合多環芳香環上に、アルキル基を有することが好ましく、炭素数６～２０のアルキル基を有することがより好ましく、炭素数７～１４のアルキル基を有することが更に好ましい。上記態様であると、得られる有機薄膜トランジスタのキャリア移動度及び熱安定性により優れる。
　また、成分Ａは、上記縮合多環芳香族基における縮合多環芳香環上に、１つ以上のアルキル基を有することが好ましく、２～４つのアルキル基を有することがより好ましく、２つのアルキル基を有することが更に好ましい。上記態様であると、得られる有機薄膜トランジスタのキャリア移動度及び熱安定性により優れる。 Component A preferably has an alkyl group on the condensed polycyclic aromatic ring in the condensed polycyclic aromatic group, more preferably an alkyl group having 6 to 20 carbon atoms, and an alkyl group having 7 to 14 carbon atoms. More preferably, it has a group. It is excellent in the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.
Component A preferably has one or more alkyl groups on the condensed polycyclic aromatic ring in the above condensed polycyclic aromatic group, more preferably has 2 to 4 alkyl groups, and more preferably 2 alkyl groups. More preferably, it has a group. It is excellent in the carrier mobility and thermal stability of the organic thin-film transistor obtained as it is the said aspect.
　成分Ａの分子量は、特に制限されないが、分子量が３，０００以下であることが好ましく、２，０００以下であることがより好ましく、１，０００以下であることが更に好ましく、８５０以下であることが特に好ましい。分子量を上記上限値以下とすることにより、溶媒への溶解性を高めることができる。一方で、薄膜の膜質安定性の観点からは、分子量は３００以上であることが好ましく、３５０以上であることがより好ましく、４００以上であることが更に好ましい。 The molecular weight of component A is not particularly limited, but the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and 850 or less. Is particularly preferred. By making molecular weight below the said upper limit, the solubility to a solvent can be improved. On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.
　成分Ａの合成方法は、特に制限されず、公知の方法を参照して合成できる。上記式（１）～式（１６）で表される化合物の合成方法としては、例えば、Ｊｏｕｒｎａｌ　ｏｆ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ，１１６，　９２５（１９９４）、Ｊｏｕｒｎａｌ　ｏｆ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ，　２２１（１９５１）、Ｏｒｇ．Ｌｅｔｔ．，２００１，３，３４７１、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２０１０，４３，６２６４、Ｔｅｔｒａｈｅｄｒｏｎ，２００２，５８，１０１９７、特表２０１２－５１３４５９号公報、特開２０１１－４６６８７号公報、Ｊｏｕｒｎａｌ　ｏｆ　Ｃｈｅｍｉｃａｌ　Ｒｅｓｅａｒｃｈ．ｍｉｎｉｐｒｉｎｔ，３，６０１－６３５（１９９１）、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，６４，３６８２－３６８６（１９９１）、Ｔｅｔｒａｈｅｄｒｏｎ　Ｌｅｔｔｅｒｓ，４５，２８０１－２８０３（２００４）、欧州特許公開第２２５１３４２号明細書、欧州特許公開第２３０１９２６号明細書、欧州特許公開第２３０１９２１号明細書、韓国特許公開第１０－２０１２－０１２０８８６号公報、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２０１１，６９６、Ｏｒｇ．Ｌｅｔｔ．，２００１，３，３４７１、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２０１０，４３，６２６４、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２０１３，７８，７７４１、Ｃｈｅｍ．Ｅｕｒ．Ｊ．，２０１３，１９，３７２１、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，１９８７，６０，４１８７、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，２０１１，１３３，５０２４、Ｃｈｅｍ．Ｅｕｒ．Ｊ．２０１３，１９，３７２１、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２０１０，４３，６２６４－６２６７、又は、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，２０１２，１３４，１６５４８－１６５５０などが挙げられる。 The method for synthesizing component A is not particularly limited, and can be synthesized with reference to known methods. Examples of the method for synthesizing the compounds represented by the above formulas (1) to (16) include, for example, Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), Org. Lett. , 2001, 3, 3471, Macromolecules, 2010, 43, 6264, Tetrahedron, 2002, 58, 10197, Japanese translations of PCT publication No. 2012-513659, JP 2011-46687A, Journal of Chemical Research. miniprint, 3, 601-635 (1991), Bull. Chem. Soc. Japan, 64, 3682-3686 (1991), Tetrahedron Letters, 45, 2801-2803 (2004), European Patent Publication No. 2251342, European Patent Publication No. 2301926, European Patent Publication No. 2301921, Korean Patent Publication No. 10-2012-0120886, J. Pat. Org. Chem. , 2011, 696, Org. Lett. 2001, 3, 3471, Macromolecules, 2010, 43, 6264, J. MoI. Org. Chem. , 2013, 78, 7741, Chem. Eur. J. et al. , 2013, 19, 3721, Bull. Chem. Soc. Jpn. 1987, 60, 4187; Am. Chem. Soc. , 2011, 133, 5024, Chem. Eur. J. et al. 2013, 19, 3721, Macromolecules, 2010, 43, 6264-6267, or J. Org. Am. Chem. Soc. 2012, 134, 16548-16550, and the like.
　なお、有機薄膜トランジスタのキャリア移動度の観点から、成分Ａは、式（１）～式（９）、式（１４）又は式（１５）のいずれかで表される化合物を少なくとも１種含むことが好ましく、式（１）～式（９）又は式（１５）のいずれかで表される化合物を少なくとも１種含むことがより好ましい。 From the viewpoint of carrier mobility of the organic thin film transistor, the component A contains at least one compound represented by any one of formulas (1) to (9), formula (14), or formula (15). Preferably, at least one compound represented by any one of formulas (1) to (9) or (15) is included.
　以下に成分Ａの好ましい具体例を示すが、これらに限定されないことは言うまでもない。 Hereinafter, preferred specific examples of Component A are shown, but it goes without saying that the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　有機半導体層形成用組成物中の有機半導体材料の濃度は、特に限定されないが、有機半導体層形成用組成物全質量に対して、０．０１～２０質量％が好ましく、０．１～１０質量％がより好ましく、０．２～５質量％が特に好ましい。 The concentration of the organic semiconductor material in the composition for forming an organic semiconductor layer is not particularly limited, but is preferably 0.01 to 20% by weight, and preferably 0.1 to 10% by weight with respect to the total weight of the composition for forming an organic semiconductor layer. % Is more preferable, and 0.2 to 5% by mass is particularly preferable.
（溶媒）
　溶媒としては、有機半導体材料及び／又は光酸発生樹脂を溶解又は分散させるものであれば特に限定されない。例えば、有機溶媒、水及びこれらの混合溶媒が挙げられる。
　有機溶媒としては、例えば、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、テトラリン、デカリン、若しくは、１－メチルナフタレン等の炭化水素溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、若しくは、シクロヘキサノン等のケトン溶媒、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、ジクロロベンゼン、若しくは、クロロトルエン等のハロゲン化炭化水素溶媒、酢酸エチル、酢酸ブチル、若しくは、酢酸アミル等のエステル溶媒、メタノール、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、若しくは、エチレングリコール等のアルコール溶媒、ジブチルエーテル、テトラヒドロフラン、ジオキサン、若しくは、アニソール等のエーテル溶媒、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、若しくは、１－メチル－２－イミダゾリジノン等のアミド・イミド溶媒、ジメチルスルフォキシド等のスルホキシド溶媒、又は、アセトニトリル、若しくは、ベンゾニトリル等のニトリル溶媒等が挙げられる。 (solvent)
The solvent is not particularly limited as long as it dissolves or disperses the organic semiconductor material and / or the photoacid generating resin. For example, an organic solvent, water, and these mixed solvents are mentioned.
Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, tetralin, decalin, or 1-methylnaphthalene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone. Ketone solvent, halogenated hydrocarbon solvent such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, or chlorotoluene, ester solvent such as ethyl acetate, butyl acetate, or amyl acetate, Methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, or ethylene glycol Alcohol solvent such as dibutyl ether, ether solvent such as dibutyl ether, tetrahydrofuran, dioxane, or anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, or 1-methyl-2 -Amide / imide solvents such as imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, or nitrile solvents such as acetonitrile or benzonitrile.
　有機溶媒は、単独で用いても、２種以上混合して用いてもよい。有機溶媒としては、トルエン、キシレン、メシチレン、テトラリン、メチルエチルケトン、シクロペンタノン、ジクロロメタン、クロロホルム、クロロベンゼン、ジクロロベンゼン、アニソール、又は、ベンゾニトリル等が特に好ましい。 Organic solvents may be used alone or in combination of two or more. As the organic solvent, toluene, xylene, mesitylene, tetralin, methyl ethyl ketone, cyclopentanone, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, anisole, benzonitrile and the like are particularly preferable.
（有機半導体層前駆体層形成方法）
　これらの有機半導体層形成用組成物を塗布する方法は、特に限定されず、インクジェット印刷、フレキソ印刷、グラビア印刷若しくはスクリーン印刷などの印刷法又はスピンコート法が好ましく、スピンコート法がより好ましい。
　塗布条件は、特に限定されない。室温（２５℃）付近で塗布してもよいし、有機半導体材料の塗布溶媒への溶解性を増すために加熱状態で塗布してもよい。塗布温度は、好ましくは１５～１５０℃であり、より好ましくは１５～１００℃であり、さらに好ましくは１５～５０℃であり、特に好ましくは室温付近（２０～３０℃）である。
　スピンコート法では、回転数を１００～３０００ｒｐｍにするのが好ましい。 (Organic semiconductor layer precursor layer forming method)
The method for applying these organic semiconductor layer forming compositions is not particularly limited, and a printing method such as inkjet printing, flexographic printing, gravure printing, or screen printing, or a spin coating method is preferable, and a spin coating method is more preferable.
The application conditions are not particularly limited. You may apply | coat near room temperature (25 degreeC), and may apply | coat in a heated state in order to increase the solubility to the application | coating solvent of an organic-semiconductor material. The coating temperature is preferably 15 to 150 ° C., more preferably 15 to 100 ° C., further preferably 15 to 50 ° C., and particularly preferably around room temperature (20 to 30 ° C.).
In the spin coating method, the rotational speed is preferably set to 100 to 3000 rpm.
　好ましい製造方法においては、塗布した有機半導体層形成用組成物を好ましくは乾燥する。乾燥条件は、溶媒を揮発により除去できる条件であればよく、例えば、室温放置、加熱乾燥、送風乾燥、又は、減圧乾燥等の方法が挙げられる。 In a preferred production method, the applied organic semiconductor layer forming composition is preferably dried. The drying conditions may be any conditions that can remove the solvent by volatilization, and examples include methods such as standing at room temperature, drying by heating, drying by blowing, or drying under reduced pressure.
（光（活性光線又は放射線）照射）
　有機半導体層前駆体層に光（活性光線又は放射線）照射処理をすることにより、有機半導体層前駆体層中の光酸発生樹脂が開裂し、ドーパントである側鎖に酸アニオンを有する主鎖部分と、カチオン部位との分解が生じる。
　光（活性光線又は放射線）照射処理において、光源としては、例えば、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、又は、カーボンアーク灯等がある。放射線としては、電子線、Ｘ線、イオンビーム、又は、遠赤外線などもある。具体的な形態としては、赤外線レーザーによる走査照射、キセノン放電灯などの高照度フラッシュ照射、又は、赤外線ランプ照射などが好適に挙げられる。
　照射時間としては、光酸発生樹脂の反応性及び光源により異なるが、通常、１０秒～５時間の間である。照射エネルギーとしては、１０～８０００ｍＪ程度であればよく、好ましくは５０～３０００ｍＪの範囲である。 (Light (actinic ray or radiation) irradiation)
By subjecting the organic semiconductor layer precursor layer to light (actinic ray or radiation) irradiation treatment, the photoacid generating resin in the organic semiconductor layer precursor layer is cleaved, and the main chain portion having an acid anion in the side chain as a dopant And decomposition with a cation site.
In the light (actinic ray or radiation) irradiation treatment, examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Specific examples of suitable forms include scanning irradiation with an infrared laser, irradiation with a high illuminance flash such as a xenon discharge lamp, or irradiation with an infrared lamp.
The irradiation time varies depending on the reactivity of the photoacid generating resin and the light source, but is usually between 10 seconds and 5 hours. The irradiation energy may be about 10 to 8000 mJ, and is preferably in the range of 50 to 3000 mJ.
＜第２の実施態様＞
　有機半導体層は、さらに、有機半導体材料を含む有機半導体材料層と光酸発生樹脂を含む光酸発生樹脂層との少なくとも２層構成として有機半導体層前駆体層を形成し、この有機半導体層前駆体層に対し活性光線又は放射線を照射することにより形成されてもよい。
　有機半導体材料層と光酸発生樹脂層の形成方法は特に限定されないが、第１の態様と同様に、有機半導体材料及び光酸発生樹脂と、これらを溶解又は分散させる溶剤とを含む形成溶液により形成されることが好ましい。勿論、形成溶液には、その他に溶媒、界面活性剤、又は、バインダー樹脂等の他の添加剤等を含有させてもよい。
　有機半導体材料層形成用組成物中の有機半導体材料の濃度は、特に限定されないが、有機半導体材料層形成用組成物全質量に対して、０．０１～２０質量％が好ましく、０．１～１０質量％がより好ましく、０．２～５質量％が特に好ましく、光酸発生樹脂層形成用組成物中の光酸発生樹脂の濃度は、特に限定されないが、光酸発生樹脂層形成用組成物全質量に対して、０．００１～１０質量％が好ましく、０．０１～５質量％がより好ましく、０．１～３質量％が特に好ましい。
　これらの形成溶液を塗布する方法は、特に限定されず、インクジェット印刷、フレキソ印刷、グラビア印刷若しくはスクリーン印刷などの印刷法又はスピンコート法が好ましく、スピンコート法がより好ましい。
　第２の態様において、上記した以外は第１の態様と同様に実施することができる。 <Second Embodiment>
The organic semiconductor layer further forms an organic semiconductor layer precursor layer as at least two layers of an organic semiconductor material layer containing an organic semiconductor material and a photoacid generating resin layer containing a photoacid generating resin. It may be formed by irradiating the body layer with actinic rays or radiation.
Although the formation method of an organic-semiconductor material layer and a photo-acid generating resin layer is not specifically limited, Like the 1st aspect, by the formation solution containing an organic-semiconductor material, photo-acid generating resin, and the solvent which melt | dissolves or disperses these Preferably it is formed. Of course, the forming solution may contain other additives such as a solvent, a surfactant, or a binder resin.
The concentration of the organic semiconductor material in the composition for forming an organic semiconductor material layer is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total mass of the composition for forming an organic semiconductor material layer, preferably 0.1 to 10% by mass is more preferable, and 0.2 to 5% by mass is particularly preferable. The concentration of the photoacid generating resin in the photoacid generating resin layer forming composition is not particularly limited. The amount is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 3% by mass based on the total mass of the product.
The method for applying these forming solutions is not particularly limited, and a printing method such as inkjet printing, flexographic printing, gravure printing, or screen printing or a spin coating method is preferable, and a spin coating method is more preferable.
The second embodiment can be carried out in the same manner as the first embodiment except as described above.
　以下、本発明のＯＴＦＴの構成ないし材料についてさらに説明する。
[基板]
　基板は、ＯＴＦＴ及びその上に作製される表示パネル等を支持できるものであればよい。基板は、表面に絶縁性があり、シート状で、表面が平坦であれば特に限定されない。なお、基板は後述するゲート電極と一体型になっていてもよい。つまり、基板はゲート電極の機能を兼ねていてもよい。 Hereinafter, the configuration or material of the OTFT of the present invention will be further described.
[substrate]
The substrate may be any substrate as long as it can support the OTFT and the display panel produced thereon. The substrate is not particularly limited as long as the surface is insulative, has a sheet shape, and has a flat surface. Note that the substrate may be integrated with a gate electrode described later. That is, the substrate may also function as a gate electrode.
　基板の材料として、無機材料を用いてもよい。無機材料からなる基板として、例えば、ソーダライムガラス、若しくは、石英ガラス等の各種ガラス基板のほか、表面に絶縁膜が形成された各種ガラス基板、表面に絶縁膜が形成された石英基板、表面に絶縁膜が形成されたシリコン基板、サファイヤ基板、ステンレス鋼、アルミニウム、若しくは、ニッケル等の各種合金若しくはこれらの各種金属からなる金属基板、金属箔、又は、紙等を挙げることができる。
　基板がステンレスシート、アルミ箔、銅箔又はシリコンウェハ等の導電性あるいは半導体性の材料で形成されている場合、通常は、表面に絶縁性の高分子材料あるいは金属酸化物等を塗布又は積層して用いられる。 An inorganic material may be used as the material for the substrate. As a substrate made of an inorganic material, for example, various glass substrates such as soda lime glass or quartz glass, various glass substrates having an insulating film formed on the surface, quartz substrates having an insulating film formed on the surface, Examples thereof include a silicon substrate on which an insulating film is formed, a sapphire substrate, stainless steel, aluminum, various alloys such as nickel, metal substrates made of these various metals, metal foil, or paper.
When the substrate is made of a conductive or semiconducting material such as stainless steel sheet, aluminum foil, copper foil or silicon wafer, an insulating polymer material or metal oxide is usually applied or laminated on the surface. Used.
　また、基板の材料としては、有機材料及び無機材料のいずれであってもよい。
　有機材料としては、例えば、ポリメチルメタクリレート（ポリメタクリル酸メチル又はＰＭＭＡともいう。）、ポリビニルアルコール（ＰＶＡ）、ポリビニルフェノール（ＰＶＰ）、ポリエーテルスルホン（ＰＥＳ）、ポリイミド、ポリアミド、ポリアセタール、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエチルエーテルケトン、ポリオレフィン、ポリシクロオレフィン、又は、エポキシ樹脂に例示される有機ポリマーから構成された可撓性を有するプラスチック基板（プラスチックフィルム又はプラスチックシートともいう）が挙げられる。
　このような可撓性を有する基板等を使用すれば、例えば曲面形状を有するディスプレイ装置又は電子機器へのＯＴＦＴの組込みあるいは一体化が可能となる。 Further, the material of the substrate may be either an organic material or an inorganic material.
Examples of the organic material include polymethyl methacrylate (also referred to as polymethyl methacrylate or PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyether sulfone (PES), polyimide, polyamide, polyacetal, and polycarbonate (PC ), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethyl ether ketone, polyolefin, polycycloolefin, or a flexible plastic substrate composed of an organic polymer exemplified by an epoxy resin (plastic film or Also referred to as a plastic sheet).
If such a flexible substrate or the like is used, for example, the OTFT can be incorporated or integrated into a display device or electronic device having a curved shape.
　基板を形成する有機材料は、他の層の積層時又は加熱時に軟化し難いことから、ガラス転移点が高いことが好ましく、ガラス転移点が４０℃以上であるのが好ましい。また、製造時の熱処理により寸法変化を起こし難く、トランジスタ性能の安定性に優れる点から、線膨張係数が小さいことが好ましい。例えば、線膨張係数が２５×１０－５ｃｍ／ｃｍ・℃以下である材料が好ましく、１０×１０－５ｃｍ／ｃｍ・℃以下である材料がさらに好ましい。
　また、基板を構成する有機材料は、ＯＴＦＴ作製時に用いる溶媒に対する耐性を有する材料が好ましく、また、ゲート絶縁層及び電極との密着性に優れる材料が好ましい。
　さらに、ガスバリア性の高い有機ポリマーからなるプラスチック基板を用いることも好ましい。
　基板の少なくとも片面に緻密なシリコン酸化膜等を設けたり、無機材料を蒸着又は積層したりすることも好ましい。 Since the organic material forming the substrate is difficult to be softened when the other layers are laminated or heated, the glass transition point is preferably high, and the glass transition point is preferably 40 ° C. or higher. In addition, it is preferable that the coefficient of linear expansion is small from the viewpoint that the dimensional change is hardly caused by the heat treatment at the time of manufacture and the transistor performance is stable. For example, a material having a linear expansion coefficient of 25 × 10 −5 cm / cm · ° C. or less is preferable, and a material having a coefficient of 10 × 10 −5 cm / cm · ° C. or less is more preferable.
In addition, the organic material constituting the substrate is preferably a material having resistance to a solvent used at the time of manufacturing the OTFT, and a material having excellent adhesion to the gate insulating layer and the electrode is preferable.
Furthermore, it is also preferable to use a plastic substrate made of an organic polymer having a high gas barrier property.
It is also preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate, or to deposit or laminate an inorganic material.
　基板として、上記の他に、導電性基板（金若しくはアルミニウム等の金属からなる基板、高配向性グラファイトからなる基板、又は、ステンレス鋼製基板等）も挙げることができる。また、有機無機複合物として、ガラスエポキシ樹脂などを挙げることができる。また、無機材料としては、例えば、雲母で形成したもの等を用いることができる。 As the substrate, in addition to the above, a conductive substrate (a substrate made of metal such as gold or aluminum, a substrate made of highly oriented graphite, a stainless steel substrate, or the like) can also be cited. Moreover, a glass epoxy resin etc. can be mentioned as an organic inorganic composite. Moreover, as an inorganic material, what was formed with mica etc. can be used, for example.
　基板には、密着性又は平坦性を改善するためのバッファー層、又は、ガスバリア性を向上させるためのバリア膜等の機能性膜を形成してもよい。また、基板の表面に易接着層等の表面処理層を形成してもよいし、コロナ処理、プラズマ処理又はＵＶ／オゾン処理等の表面処理を施してもよい。 A functional film such as a buffer layer for improving adhesion or flatness or a barrier film for improving gas barrier properties may be formed on the substrate. In addition, a surface treatment layer such as an easy adhesion layer may be formed on the surface of the substrate, or a surface treatment such as corona treatment, plasma treatment or UV / ozone treatment may be performed.
　基板の厚みは、１０ｍｍ以下であるのが好ましく、２ｍｍ以下であるのがさらに好ましく、１ｍｍ以下であるのが特に好ましい。また、一方で、０．０１ｍｍ以上であるのが好ましく、０．０５ｍｍ以上であるのがさらに好ましい。特に、プラスチック基板の場合は、厚みが０．０５～０．１ｍｍ程度であるのが好ましい。また、無機材料からなる基板の場合は、厚みが０．１～１０ｍｍ程度であるのが好ましい。 The thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. On the other hand, it is preferably 0.01 mm or more, and more preferably 0.05 mm or more. In particular, in the case of a plastic substrate, the thickness is preferably about 0.05 to 0.1 mm. In the case of a substrate made of an inorganic material, the thickness is preferably about 0.1 to 10 mm.
［ゲート電極]
　ゲート電極は、ＯＴＦＴのゲート電極として用いられている従来公知の電極を用いることができる。ゲート電極を構成する導電性材料（電極材料ともいう）としては、特に限定されない。例えば、白金、金、銀、アルミニウム、クロム、ニッケル、銅、モリブデン、チタン、マグネシウム、カルシウム、バリウム、ナトリウム、パラジウム、鉄、若しくは、マンガン等の金属；ＩｎＯ２、ＳｎＯ２、インジウム・錫酸化物（ＩＴＯ）、フッ素ドープ酸化錫（ＦＴＯ）、アルミニウムドープ酸化亜鉛（ＡＺＯ）、若しくは、ガリウムドープ酸化亜鉛（ＧＺＯ）等の導電性金属酸化物；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、若しくは、ポリ（３，４－エチレンジオキシチオフェン）／ポリスチレンスルホン酸（ＰＥＤＯＴ／ＰＳＳ）等の導電性高分子；塩酸、硫酸、若しくは、スルホン酸等の酸、ＰＦ６、ＡｓＦ５、若しくは、ＦｅＣｌ３等のルイス酸、ヨウ素等のハロゲン原子、ナトリウム、若しくは、カリウム等の金属原子等のドーパントを添加した上記導電性高分子；又は；カーボンブラック、グラファイト粉、若しくは、金属微粒子等を分散した導電性の複合材料等が挙げられる。これらの材料は、１種のみを用いても、２種以上を任意の組み合わせ及び比率で併用してもよい。
　また、ゲート電極は、上記導電性材料からなる１層でもよく、２層以上を積層してもよい。 [Gate electrode]
As the gate electrode, a conventionally known electrode used as a gate electrode of OTFT can be used. A conductive material (also referred to as an electrode material) constituting the gate electrode is not particularly limited. For example, metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, molybdenum, titanium, magnesium, calcium, barium, sodium, palladium, iron, or manganese; InO 2 , SnO 2 , indium / tin oxide Conductive metal oxides such as (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), or gallium-doped zinc oxide (GZO); polyaniline, polypyrrole, polythiophene, polyacetylene, or poly (3 , 4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS), etc .; acid such as hydrochloric acid, sulfuric acid or sulfonic acid, Lewis acid such as PF 6 , AsF 5 , or FeCl 3 , Halogen atoms such as iodine, sodium, young Ku is the conductive polymer was added dopant such as a metal atom such as potassium, or; carbon black, graphite powder, or a composite material of the conductive dispersed metal fine particles and the like. These materials may be used alone or in combination of two or more in any combination and ratio.
Further, the gate electrode may be a single layer made of the above conductive material, or two or more layers may be stacked.
　ゲート電極の形成方法に制限はない。例えば、真空蒸着法等の物理蒸着法（ＰＶＤ）、化学蒸着法（ＣＶＤ法）、スパッタ法、印刷法（塗布法）、転写法、ゾルゲル法、又は、メッキ法等により形成された膜を、必要に応じて所望の形状にパターンニングする方法が挙げられる。
　塗布法では、上記材料の溶液、ペースト又は分散液を調製して組成物を構成し、得られた組成物を塗布して乾燥した後、焼成、光硬化又はエージング等の処理により膜を形成し、又は、直接電極を形成できる。
　また、インクジェット印刷、スクリーン印刷、（反転）オフセット印刷、凸版印刷、凹版印刷、平版印刷、熱転写印刷、又は、マイクロコンタクトプリンティング法等は、所望のパターニングが可能であり、工程の簡素化、コスト低減、又は、高速化の点で好ましい。
　スピンコート法、ダイコート法、マイクログラビアコート法、又は、ディップコート法を採用する場合も、下記フォトリソグラフィー法等と組み合わせてパターニングすることができる。 There is no limitation on the method of forming the gate electrode. For example, a film formed by physical vapor deposition (PVD) such as vacuum vapor deposition, chemical vapor deposition (CVD), sputtering, printing (coating), transfer, sol-gel, or plating, A method of patterning to a desired shape as needed is mentioned.
In the coating method, a solution, paste or dispersion of the above materials is prepared to form a composition, and the resulting composition is coated and dried, and then a film is formed by treatment such as baking, photocuring or aging. Alternatively, the electrodes can be formed directly.
In addition, ink-jet printing, screen printing, (reversal) offset printing, letterpress printing, intaglio printing, planographic printing, thermal transfer printing, or microcontact printing can be performed with desired patterning, simplifying processes and reducing costs. Or, it is preferable in terms of speeding up.
When a spin coating method, a die coating method, a micro gravure coating method, or a dip coating method is adopted, patterning can be performed in combination with the following photolithography method or the like.
　フォトリソグラフィー法としては、例えば、フォトレジストのパターニングと、エッチング液によるウェットエッチング、若しくは、反応性のプラズマによるドライエッチング等のエッチング、又は、リフトオフ法等とを組み合わせる方法等が挙げられる。
　他のパターニング方法として、上記材料に、レーザー又は電子線等のエネルギー線を照射して、研磨し、又は材料の導電性を変化させる方法も挙げられる。
　さらに、基板以外の支持体に印刷したゲート電極用組成物を基板等の下地層の上に転写させる方法も挙げられる。 Examples of the photolithography method include a method of combining a patterning of a photoresist and an etching such as a wet etching with an etching solution, a dry etching with a reactive plasma, a lift-off method, or the like.
As another patterning method, a method of irradiating the material with an energy beam such as a laser or an electron beam to polish the material or changing the conductivity of the material may be used.
Furthermore, the method of transferring the composition for gate electrodes printed on support bodies other than a board | substrate on base layers, such as a board | substrate, is also mentioned.
　ゲート電極の厚みは、任意であるが、１ｎｍ以上が好ましく、１０ｎｍ以上が特に好ましい。また、５００ｎｍ以下が好ましく、２００ｎｍ以下が特に好ましい。 The thickness of the gate electrode is arbitrary, but is preferably 1 nm or more, particularly preferably 10 nm or more. Moreover, 500 nm or less is preferable and 200 nm or less is especially preferable.
［ゲート絶縁層]
　ゲート絶縁層は、絶縁性を有する層であれば特に限定されず、単層であってもよいし、多層であってもよい。
　ゲート絶縁層は、絶縁性の材料で形成されるのが好ましく、絶縁性の材料として、例えば、有機高分子又は無機酸化物等が好ましく挙げられる。有機高分子及び無機酸化物は、それぞれ１種でも２種以上の併用であってもよく、あるいは有機無機ハイブリッドであってもよい。
　有機高分子及び無機酸化物等は、絶縁性を有するものであれば特に限定されないが、塗布可能な、有機高分子又は有機無機ハイブリッドで形成されることが好ましい。
　ゲート絶縁層の厚みは、任意であるが、１０ｎｍ～１０μｍが好ましく、５０ｎｍ～５μｍがより好ましく、１００ｎｍ～１μｍが特に好ましい。 [Gate insulation layer]
The gate insulating layer is not particularly limited as long as it is an insulating layer, and may be a single layer or a multilayer.
The gate insulating layer is preferably formed of an insulating material, and examples of the insulating material include organic polymers and inorganic oxides. The organic polymer and the inorganic oxide may be used alone or in combination of two or more, or may be an organic-inorganic hybrid.
The organic polymer and the inorganic oxide are not particularly limited as long as they have insulating properties, but are preferably formed of an organic polymer or an organic-inorganic hybrid that can be applied.
The thickness of the gate insulating layer is arbitrary, but is preferably 10 nm to 10 μm, more preferably 50 nm to 5 μm, and particularly preferably 100 nm to 1 μm.
　有機高分子としては、特に限定されるものではないが、例えば、ポリビニルフェノール（ＰＶＰ）、ポリスチレン（ＰＳ）、ポリメチルメタクリレートに代表されるポリ（メタ）アクリレート、ポリビニルアルコール、ポリ塩化ビニル（ＰＶＣ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ＣＹＴＯＰ（登録商標、旭硝子社製）に代表される環状フルオロアルキルポリマー、ポリシクロオレフィン、ポリエステル樹脂、ポリエーテルスルホン、ポリエーテルケトン、ポリイミド、エポキシ樹脂（ガラスエポキシ樹脂を含む）、ポリジメチルシロキサン（ＰＤＭＳ）に代表されるポリオルガノシロキサン、ポリシルセスキオキサン又はブタジエンゴム等が挙げられる。また、高密度ポリエチレン、エチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリプロピレン、アクリロニトリル－ブタジエン－スチレン樹脂（ＡＢＳ樹脂）、メタクリル樹脂、ポリアセタール、ジアリルフタレート、アイオノマー、ポリアミド、ポリカーボネート、ポリフェニレンオキサイド、ポリスルホン、ユリア樹脂、メラミン樹脂、酢酸セルロース、シリコン樹脂、ウレタン樹脂、又は、ポリベンゾオキサゾール等が挙げられる。上記の他にも、フェノール樹脂、ノボラック樹脂、シンナメート樹脂、アクリル樹脂、又は、ポリパラキシリレン樹脂等の熱硬化性樹脂も挙げられる。これらの中でも、ポリイミド、ポリシクロオレフィン、ポリアクリル酸、ポリビニルフェノール、又は、ポリベンゾオキサゾール等が好ましく使用できる。
　また、有機高分子として、低誘電率フッ素系材料も好ましく使用できる。
　有機高分子は、アルコキシシリル基、ビニル基、アクリロイルオキシ基、エポキシ基、又は、メチロール基等の反応性置換基を有する化合物と併用することもできる。 Although it does not specifically limit as an organic polymer, For example, poly (meth) acrylate represented by polyvinylphenol (PVP), polystyrene (PS), polymethylmethacrylate, polyvinyl alcohol, polyvinyl chloride (PVC) , Cyclic fluoroalkyl polymers represented by polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), CYTOP (registered trademark, manufactured by Asahi Glass Co., Ltd.), polycycloolefin, polyester resin, polyethersulfone, polyetherketone, polyimide , Epoxy resins (including glass epoxy resins), polyorganosiloxanes typified by polydimethylsiloxane (PDMS), polysilsesquioxane, butadiene rubber, and the like. High-density polyethylene, ethylene-vinyl acetate copolymer (EVA), polypropylene, acrylonitrile-butadiene-styrene resin (ABS resin), methacrylic resin, polyacetal, diallyl phthalate, ionomer, polyamide, polycarbonate, polyphenylene oxide, polysulfone, urea Examples of the resin include melamine resin, cellulose acetate, silicon resin, urethane resin, and polybenzoxazole. In addition to the above, thermosetting resins such as phenol resin, novolac resin, cinnamate resin, acrylic resin, or polyparaxylylene resin are also included. Among these, polyimide, polycycloolefin, polyacrylic acid, polyvinylphenol, polybenzoxazole, or the like can be preferably used.
Moreover, a low dielectric constant fluorine-based material can also be preferably used as the organic polymer.
The organic polymer can be used in combination with a compound having a reactive substituent such as an alkoxysilyl group, a vinyl group, an acryloyloxy group, an epoxy group, or a methylol group.
　有機高分子でゲート絶縁層を形成する場合、ゲート絶縁層の耐溶媒性又は絶縁耐性を増す目的等で、有機高分子を架橋し、硬化させることも好ましい。架橋は、光、熱又はこれら双方を用いて、酸又はラジカルを発生させることにより実施することが好ましい。 When the gate insulating layer is formed of an organic polymer, the organic polymer is preferably crosslinked and cured for the purpose of increasing the solvent resistance or the insulation resistance of the gate insulating layer. Crosslinking is preferably carried out by generating acid or radical using light, heat or both.
　ラジカルにより架橋する場合、光又は熱によりラジカルを発生させるラジカル発生剤として、例えば、特開２０１３－２１４６４９号公報の［０１８２］～［０１８６］に記載の熱重合開始剤（Ｈ１）及び光重合開始剤（Ｈ２）、特開２０１１－１８６０６９号公報の［００４６］～［００５１］に記載の光ラジカル発生剤、又は、特開２０１０－２８５５１８号公報の［００４２］～［００５６］に記載の光ラジカル重合開始剤等を好適に用いることができ、好ましくはこれらの内容は本明細書に組み込まれる。
　また、特開２０１３－２１４６４９号公報の［０１６７］～［０１７７］に記載の「数平均分子量（Ｍｎ）が１４０～５，０００であり、架橋性官能基を有し、フッ素原子を有さない化合物（Ｇ）」を用いるのも好ましく、これらの内容は好ましくは本明細書に組み込まれる。 In the case of crosslinking by radicals, as a radical generator that generates radicals by light or heat, for example, thermal polymerization initiators (H1) described in [0182] to [0186] of JP2013-214649A and photopolymerization initiation Agent (H2), photo radical generators described in JP-A-2011-186069, [0046] to [0051], or photo-radicals described in JP-A 2010-285518, [0042] to [0056] Polymerization initiators and the like can be suitably used, and preferably the contents thereof are incorporated herein.
In addition, “Number average molecular weight (Mn) is 140 to 5,000, described in JP2013-214649A [0167] to [0177], has a crosslinkable functional group, and does not have a fluorine atom. It is also preferred to use "compound (G)", the contents of which are preferably incorporated herein.
　酸により架橋する場合、光により酸を発生させる光酸発生剤として、例えば、特開２０１０－２８５５１８号公報の［００３３］～［００３４］に記載の光カチオン重合開始剤、又は、特開２０１２－１６３９４６号公報の［０１２０］～［０１３６］に記載の酸発生剤を用いることができ、好ましくはこれらの内容は本明細書に組み込まれる。これらのなかでも、スルホニウム塩又はヨードニウム塩等を好ましく使用することができる。
　熱により酸を発生させる熱酸発生剤（触媒）として、例えば、特開２０１０－２８５５１８号公報の［００３５］～［００３８］に記載の熱カチオン重合開始剤（特にオニウム塩等）、又は、特開２００５－３５４０１２号公報の［００３４］～［００３５］に記載の触媒（特にスルホン酸類及びスルホン酸アミン塩）等を好ましく使用することができ、好ましくはこれらの内容は本明細書に組み込まれる。
　また、特開２００５－３５４０１２号公報の［００３２］～［００３３］に記載の架橋剤（特に二官能以上のエポキシ化合物又はオキセタン化合物）、特開２００６－３０３４６５号公報の［００４６］～［００６２］に記載の架橋剤（特に２個以上の架橋基を有し、この架橋基の少なくとも一つがメチロール基若しくはＮＨ基であることを特徴とする化合物）、又は、特開２０１２－１６３９４６号公報の［０１３７］～［０１４５］に記載の、ヒドロキシメチル基又はアルコキシメチル基を分子内に２個以上有する化合物を用いるのも好ましく、これらの内容は好ましくは本明細書に組み込まれる。 In the case of crosslinking with an acid, as a photoacid generator that generates an acid by light, for example, a photocationic polymerization initiator described in [0033] to [0034] of JP2010-285518A or JP2012-2012A. The acid generators described in [0120] to [0136] of JP-A-163946 can be used, and the contents thereof are preferably incorporated herein. Among these, a sulfonium salt or an iodonium salt can be preferably used.
As a thermal acid generator (catalyst) that generates an acid by heat, for example, a thermal cationic polymerization initiator (particularly an onium salt) described in [0035] to [0038] of JP-A-2010-285518, or a special The catalysts (especially sulfonic acids and sulfonic acid amine salts) described in [0034] to [0035] of JP-A-2005-354012 can be preferably used, and the contents thereof are preferably incorporated herein.
Further, a crosslinking agent (particularly a bifunctional or higher functional epoxy compound or oxetane compound) described in JP-A-2005-354012 [0032] to [0033], [0046]-[0062] in JP-A-2006-303465. (In particular, a compound having two or more crosslinking groups, and at least one of the crosslinking groups is a methylol group or an NH group), or JP 2012-163946 A [ It is also preferable to use compounds having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule described in [0137] to [0145], the contents of which are preferably incorporated herein.
　ゲート絶縁層を有機高分子で形成する方法としては、例えば、有機高分子を塗布（塗工）した後、これを硬化する方法が挙げられる。塗布方法は、特に限定されず、上記の各印刷法が挙げられる。なかでも、マイクログラビアコート法、ディップコート法、スクリーンコート印刷、ダイコート法又はスピンコート法等のウエットコーティング法が好ましい。 As a method for forming the gate insulating layer with an organic polymer, for example, there is a method in which an organic polymer is applied (coated) and then cured. The coating method is not particularly limited, and examples thereof include the above printing methods. Of these, a wet coating method such as a micro gravure coating method, a dip coating method, a screen coating printing, a die coating method or a spin coating method is preferable.
　上記無機酸化物としては、特に限定されるものではないが、例えば、酸化ケイ素、窒化ケイ素（ＳｉＮＹ）、酸化ハフニウム、酸化チタン、酸化タンタル、酸化アルミニウム、酸化ニオブ、酸化ジルコニウム、酸化銅、若しくは、酸化ニッケル等の酸化物、ＳｒＴｉＯ３、ＣａＴｉＯ３、ＢａＴｉＯ３、ＭｇＴｉＯ３、若しくは、ＳｒＮｂ２Ｏ６のようなペロブスカイト化合物、又は、これらの複合酸化物若しくは混合物等が挙げられる。
　ここで、酸化ケイ素としては、酸化シリコン（ＳｉＯＸ）の他に、ＢＰＳＧ（Ｂｏｒｏｎ　Ｐｈｏｓｐｈｏｒｕｓ　Ｓｉｌｉｃｏｎ　Ｇｌａｓｓ）、ＰＳＧ（Ｐｈｏｓｐｈｏｒｕｓ　Ｓｉｌｉｃｏｎ　Ｇｌａｓｓ）、ＢＳＧ（Ｂｏｒｏｎ　Ｓｉｌｉｃｏｎ　Ｇｌａｓｓ）、ＡｓＳＧ（Ａｓがドープされたシリカガラス）酸化窒化シリコン（ＳｉＯＮ）、ＳＯＧ（スピンオングラス）が含まれる。 The inorganic oxide is not particularly limited. For example, silicon oxide, silicon nitride (SiN Y ), hafnium oxide, titanium oxide, tantalum oxide, aluminum oxide, niobium oxide, zirconium oxide, copper oxide, or And oxides such as nickel oxide, perovskite compounds such as SrTiO 3 , CaTiO 3 , BaTiO 3 , MgTiO 3 , or SrNb 2 O 6 , or complex oxides or mixtures thereof.
Here, as silicon oxide, in addition to silicon oxide (SiO X ), BPSG (Boron Phosphorus Silicon Glass), PSG (Phosphorus Silicon Glass), BSG (Boron Silicon Glass), AsSG (As-doped silica glass) Silicon oxynitride (SiON) and SOG (spin on glass) are included.
　ゲート絶縁層を無機酸化物で形成する方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング又はＣＶＤ法等の真空成膜法を用いることができ、また成膜中に任意のガスを用いたプラズマ又はイオン銃若しくはラジカル銃等でアシストを行ってもよい。
　また、それぞれの金属酸化物に対応する前駆体、具体的には塩化物若しくは臭化物等の金属ハロゲン化物、金属アルコキシド、又は、金属水酸化物等を、アルコール又は水中で塩酸、硫酸若しくは硝酸等の酸、又は、水酸化ナトリウム若しくは水酸化カリウム等の塩基と反応させて加水分解することにより、形成してもよい。このような溶液系のプロセスを用いる場合、上記ウエットコーティング法を用いることができる。 As a method for forming the gate insulating layer with an inorganic oxide, for example, a vacuum film formation method such as a vacuum evaporation method, a sputtering method, an ion plating method, a CVD method, or the like can be used. Assist may be performed with the plasma, ion gun or radical gun used.
In addition, a precursor corresponding to each metal oxide, specifically, a metal halide such as chloride or bromide, a metal alkoxide, or a metal hydroxide, such as hydrochloric acid, sulfuric acid or nitric acid in alcohol or water. You may form by reacting with an acid or bases, such as sodium hydroxide or potassium hydroxide, and hydrolyzing. When such a solution process is used, the above wet coating method can be used.
　ゲート絶縁層は、上記の方法以外にも、リフトオフ法、ゾル－ゲル法、電着法及びシャドウマスク法のいずれかと、必要に応じてパターニング法とを組み合わせた方法により、設けることもできる。 In addition to the above method, the gate insulating layer can also be provided by a method that combines any one of the lift-off method, the sol-gel method, the electrodeposition method, and the shadow mask method, and, if necessary, the patterning method.
　また、無機有機ハイブリッドとして、上記に挙げた有機高分子と、有機修飾された無機微粒子とを併用してもよい。 Further, as the inorganic-organic hybrid, the above-described organic polymers and organically modified inorganic fine particles may be used in combination.
［ソース電極、ドレイン電極]
　本発明のＯＴＦＴ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り、通常、上記有機半導体層に接して設けられる。
　ソース電極及びドレイン電極の材料としては、従来の有機薄膜トランジスタに用いられている導電性材料を用いることができ、例えば、上記ゲート電極で説明した導電性材料等が挙げられる。 [Source electrode, drain electrode]
In the OTFT of the present invention, the source electrode is an electrode through which current flows from the outside through the wiring. Further, the drain electrode is an electrode that sends current to the outside through wiring, and is usually provided in contact with the organic semiconductor layer.
As a material of the source electrode and the drain electrode, a conductive material used in a conventional organic thin film transistor can be used, and examples thereof include the conductive material described for the gate electrode.
　ソース電極及びドレイン電極は、それぞれ、上記ゲート電極の形成方法と同様の方法により形成することができる。 The source electrode and the drain electrode can be formed by a method similar to the method for forming the gate electrode, respectively.
　上記フォトリソグラフィー法としては、リフトオフ法又はエッチング法を採用できる。
　特に、ゲート絶縁層がエッチング液又は剥離液に対する耐性に優れていることから、ソース電極及びドレイン電極はエッチング法でも好適に形成することができる。エッチング法は、導電性材料を成膜した後に不要部分をエッチングにより除去する方法である。エッチング法によりパターニングすると、レジスト除去時に下地に残った導電性材料の剥がれ、レジスト残渣又は除去された導電性材料等の下地への再付着を防止でき、電極エッジ部の形状に優れる。この点で、リフトオフ法よりも好ましい。 As the photolithography method, a lift-off method or an etching method can be employed.
In particular, since the gate insulating layer is excellent in resistance to an etching solution or a stripping solution, the source electrode and the drain electrode can be preferably formed by an etching method. The etching method is a method of removing unnecessary portions by etching after forming a conductive material. When patterning is performed by an etching method, the conductive material remaining on the base when the resist is removed can be prevented, and the resist residue or the removed conductive material can be prevented from reattaching to the base, so that the shape of the electrode edge portion is excellent. This is preferable to the lift-off method.
　リフトオフ法は、下地の一部にレジストを塗布し、この上に導電性材料を成膜し、レジスト等を溶媒により溶出又は剥離等することにより、レジスト上の導電性材料ごと除去して、レジストが塗布されていなかった部分にのみ導電性材料の膜を形成する方法である。 In the lift-off method, a resist is applied to a part of the base, a conductive material is formed thereon, and the resist is removed together with the solvent by elution or peeling with a solvent. This is a method of forming a film of a conductive material only on a portion where no is applied.
　ソース電極及びドレイン電極の厚みは、任意であるが、それぞれ、１ｎｍ以上が好ましく、１０ｎｍ以上が特に好ましい。また、５００ｎｍ以下が好ましく、３００ｎｍ以下が特に好ましい。
　ソース電極とドレイン電極との間の間隔（チャネル長）は、任意であるが、５００μｍ以下が好ましく、２００μｍ以下が特に好ましい。また、チャネル幅は、５０００μｍ以下が好ましく、１０００μｍ以下が特に好ましい。 Although the thickness of a source electrode and a drain electrode is arbitrary, 1 nm or more is preferable respectively and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
The interval (channel length) between the source electrode and the drain electrode is arbitrary, but is preferably 500 μm or less, and particularly preferably 200 μm or less. The channel width is preferably 5000 μm or less, and particularly preferably 1000 μm or less.
［オーバーコート層］
　本発明のＯＴＦＴは、オーバーコート層を有していてもよい。オーバーコート層は、通常、ＯＴＦＴの表面に保護層として形成される層である。単層構造でも多層構造でもよい。
　オーバーコート層は、有機系のオーバーコート層でも無機系のオーバーコート層でもよい。
　有機系のオーバーコート層を形成する材料としては、特に限定されないが、例えば、ポリスチレン、アクリル樹脂、ポリビニルアルコール、ポリオレフィン、ポリイミド、ポリウレタン、ポリアセナチレン、若しくは、エポキシ樹脂等の有機ポリマー、又は、これらの有機ポリマーに架橋性基若しくは撥水基等を導入した誘導体等が挙げられる。これらの有機ポリマー又はその誘導体は、架橋成分、フッ素化合物又はシリコン化合物等と併用することもできる。
　無機系のオーバーコート層を形成する材料としては、特に限定されないが、酸化ケイ素若しくは酸化アルミニウム等の金属酸化物又は窒化ケイ素等の金属窒化物等が挙げられる。
　これらの材料は、１種を用いても、２種以上を任意の組み合わせ及び比率で併用してもよい。 [Overcoat layer]
The OTFT of the present invention may have an overcoat layer. The overcoat layer is usually a layer formed as a protective layer on the surface of the OTFT. A single layer structure or a multilayer structure may be used.
The overcoat layer may be an organic overcoat layer or an inorganic overcoat layer.
The material for forming the organic overcoat layer is not particularly limited, but for example, an organic polymer such as polystyrene, acrylic resin, polyvinyl alcohol, polyolefin, polyimide, polyurethane, polyacetylene, or epoxy resin, or an organic polymer thereof. Examples thereof include a derivative in which a crosslinkable group or a water repellent group is introduced into the polymer. These organic polymers or derivatives thereof can be used in combination with a crosslinking component, a fluorine compound, a silicon compound, or the like.
The material for forming the inorganic overcoat layer is not particularly limited, and examples thereof include metal oxides such as silicon oxide and aluminum oxide, and metal nitrides such as silicon nitride.
These materials may be used alone or in combination of two or more in any combination and ratio.
　オーバーコート層の形成方法に制限はなく、公知の各種の方法により形成することができる。
　例えば、有機系のオーバーコート層は、例えば、その下地となる層に、オーバーコート層となる材料を含む溶液を塗布後に乾燥させる、オーバーコート層となる材料を含む溶液を塗布して乾燥した後に、露光及び現像してパターニングする等の方法により形成することができる。なお、オーバーコート層のパターニングは、印刷法又はインクジェット法等により直接形成することもできる。また、オーバーコート層のパターニング後に、露光又は加熱することにより、オーバーコート層を架橋させてもよい。
　一方、無機系のオーバーコート層は、スパッタリング法若しくは蒸着法等の乾式法、又は、ゾルゲル法のような湿式法により形成することができる。 There is no restriction | limiting in the formation method of an overcoat layer, It can form by well-known various methods.
For example, the organic overcoat layer is formed by, for example, applying a solution containing a material to be an overcoat layer to the underlying layer and then drying the solution containing the material to be an overcoat layer. It can be formed by a method such as patterning by exposure and development. Note that the patterning of the overcoat layer can also be directly formed by a printing method, an inkjet method, or the like. Further, the overcoat layer may be crosslinked by exposure or heating after the patterning of the overcoat layer.
On the other hand, the inorganic overcoat layer can be formed by a dry method such as a sputtering method or an evaporation method, or a wet method such as a sol-gel method.
［その他の層］
　本発明のＯＴＦＴは、上記以外の層又は部材を設けてもよい。
　その他の層又は部材としては、例えば、バンク等が挙げられる。バンクは、インクジェット法等により半導体層又はオーバーコート層等を形成するときに、吐出液を所定の位置に塞き止める目的等で用いられる。このため、バンクには、通常、撥液性がある。バンクの形成方法としては、フォトリソグラフィー法等によりパターニングした後にフッ素プラズマ法等の撥液処理を施す方法、フッ素化合物等の撥液成分を含む感光性組成物等を硬化させる方法等が挙げられる。
　本発明の有機薄膜トランジスタの場合、ゲート絶縁層が有機層であることから、後者の撥液成分を含む感光性組成物を硬化させる方法が、ゲート絶縁層が撥液処理の影響を受ける可能性がなく、好ましい。なお、バンクを用いずに下地に撥液性のコントラストを持たせてバンクと同じ役割を持たせる技術を用いてもよい。 [Other layers]
The OTFT of the present invention may be provided with layers or members other than those described above.
Examples of other layers or members include banks. The bank is used for the purpose of blocking the discharge liquid at a predetermined position when a semiconductor layer or an overcoat layer is formed by an inkjet method or the like. For this reason, the bank usually has liquid repellency. Examples of the bank forming method include a method of performing liquid repellency treatment such as a fluorine plasma method after patterning by a photolithography method or the like, a method of curing a photosensitive composition containing a liquid repellent component such as a fluorine compound, and the like.
In the case of the organic thin film transistor of the present invention, since the gate insulating layer is an organic layer, the method of curing the photosensitive composition containing the latter liquid repellent component may cause the gate insulating layer to be affected by the liquid repellent treatment. Not preferred. A technique may be used in which a liquid repellent contrast is given to the base without using the bank so as to have the same role as the bank.
　本発明のＯＴＦＴは、図１Ａに示されるボトムゲート・ボトムコンタクト構造、図１Ｂは、ボトムゲート・トップコンタクト構造、図１Ｃはトップゲート・ボトムコンタクト構造、図１Ｄはトップゲート・トップコンタクト構造のいずれにも適用することができる。 The OTFT of the present invention has a bottom gate / bottom contact structure shown in FIG. 1A, FIG. 1B shows a bottom gate / top contact structure, FIG. 1C shows a top gate / bottom contact structure, and FIG. 1D shows a top gate / top contact structure. It can also be applied to.
〔ＯＴＦＴの用途〕
　本発明のＯＴＦＴは好ましくは表示パネルに搭載して使用される。表示パネルとしては、例えば、液晶パネル、有機ＥＬパネル、電子ペーパーパネル等が挙げられる。 [Use of OTFT]
The OTFT of the present invention is preferably used by being mounted on a display panel. Examples of the display panel include a liquid crystal panel, an organic EL panel, and an electronic paper panel.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
［有機薄膜トランジスタＩの製造と評価（実施例１～２０、比較例１～３）］
＜有機半導体層形成用組成物の調製＞
　有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造を側鎖に含む繰り返し単位を有する樹脂（以下、「光酸発生樹脂」という）とを下記表１に示す配合比となるように混合、攪拌して、実施例及び比較例の各有機半導体層形成用組成物を調製した。
　なお、いずれの有機半導体層形成用組成物においてもトルエンを溶剤とする固形分濃度０．５質量％溶液として調製し、有機半導体材料又は光酸発生樹脂が溶解しくにい場合には、必要に応じて５０℃程度の加熱をしながら攪拌して、各成分を溶解させた。 [Production and Evaluation of Organic Thin Film Transistor I (Examples 1 to 20, Comparative Examples 1 to 3)]
<Preparation of composition for forming organic semiconductor layer>
The organic semiconductor material and the resin (hereinafter referred to as “photoacid generator resin”) having a repeating unit containing a structure that generates an acid anion by irradiation with actinic rays or radiation in the side chain (hereinafter referred to as “photoacid generating resin”) have a blending ratio shown in Table 1 below. The organic semiconductor layer forming compositions of Examples and Comparative Examples were prepared by mixing and stirring.
In addition, in any organic semiconductor layer forming composition, it is prepared as a solution having a solid content concentration of 0.5% by mass using toluene as a solvent, and is necessary when the organic semiconductor material or the photoacid generator resin is difficult to dissolve. Accordingly, stirring was performed while heating at about 50 ° C. to dissolve each component.
　下記に使用した化合物を示す。
（Ａ）　有機半導体材料
Figure JPOXMLDOC01-appb-C000052
 The compounds used are shown below.
(A) Organic semiconductor materials
Figure JPOXMLDOC01-appb-C000052
（Ｂ）光酸発生樹脂
Figure JPOXMLDOC01-appb-C000053
 (B) Photoacid generator resin
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
（Ｃ）光酸発生剤（比較用）
Figure JPOXMLDOC01-appb-C000055
 (C) Photoacid generator (for comparison)
Figure JPOXMLDOC01-appb-C000055
＜有機薄膜トランジスタＩの製造＞
　上記のようにして得られた実施例及び比較例の各有機半導体層形成用組成物を用いて、図１Ａに示すボトムゲート・ボトムコンタクト構造の有機薄膜トランジスタを以下の手順にて作製した後、キャリア移動度及び絶縁信頼性の評価を行った。 <Manufacture of organic thin film transistor I>
Using the organic semiconductor layer forming compositions of Examples and Comparative Examples obtained as described above, the organic thin film transistor having the bottom gate / bottom contact structure shown in FIG. Mobility and insulation reliability were evaluated.
　基板６として厚さ１ｍｍのドープシリコン基板（ゲート電極５を兼ねる）を用い、その上にゲート絶縁層２を形成した。
　ゲート絶縁層２は以下のように形成した。
　ポリ（４－ビニルフェノール）（日本曹達社製、商品名：ＶＰ－８０００、Ｍｎ１１０００、分散度１．１）を６．３ｇと、架橋剤として２，２－ビス（３，５－ジヒドロキシメチル－４－ヒドロキシ）プロパン２．７ｇとを、９１ｇの１－ブタノール／エタノール＝１／１の混合溶媒に室温で溶解した。この溶解液をφ０．２μｍのＰＴＦＥ製メンブランフィルタでろ過した。得られたろ液に酸触媒としてジフェニルヨードニウムヘキサフルオロホスフェート塩０．１８ｇを加え、基板６上に塗布し、乾燥して成膜した。その後、１００℃に加熱して架橋構造を形成させ、厚さ０．７μｍのゲート絶縁層２を形成した。 A doped silicon substrate (also serving as the gate electrode 5) having a thickness of 1 mm was used as the substrate 6, and the gate insulating layer 2 was formed thereon.
The gate insulating layer 2 was formed as follows.
6.3 g of poly (4-vinylphenol) (manufactured by Nippon Soda Co., Ltd., trade names: VP-8000, Mn 11000, dispersity 1.1) and 2,2-bis (3,5-dihydroxymethyl-) as a crosslinking agent 2.7 g of 4-hydroxy) propane was dissolved in 91 g of 1-butanol / ethanol = 1/1 mixed solvent at room temperature. The solution was filtered through a PTFE membrane filter with a diameter of 0.2 μm. To the obtained filtrate, 0.18 g of diphenyliodonium hexafluorophosphate salt was added as an acid catalyst, applied on the substrate 6, and dried to form a film. Then, it heated at 100 degreeC, the crosslinked structure was formed, and the 0.7-micrometer-thick gate insulating layer 2 was formed.
　次いで、図１Ａに示すようにソース電極３及びドレイン電極４として、くし型に配置された銀からなる電極（厚み１５０ｎｍ、ゲート幅Ｗ＝１００μｍ、ゲート長Ｌ＝１００μｍ）を、マスクを用いて真空蒸着により形成した。 Next, as shown in FIG. 1A, as the source electrode 3 and the drain electrode 4, an electrode made of silver (thickness 150 nm, gate width W = 100 μm, gate length L = 100 μm) arranged in a comb shape is vacuumed using a mask. It was formed by vapor deposition.
　次いで、ゲート絶縁層２、ソース電極３及びドレイン電極４を覆うように、上記有機半導体層形成用組成物を、２５℃でスピンコート（回転数１０００ｒｐｍ）により塗布した。その後、ホットプレート上にて１５０℃で３０分加熱して、有機半導体層前駆体層を成膜した。次いで、得られた有機半導体層前駆体層に対し、高圧ＵＶランプ（ウシオ電機社製）を用いて２５４～３６５ｎｍの波長の光（照射量３０ｍＷ/ｃｍ２）を１０秒照射し、光酸発生樹脂を分解して系内に側鎖に酸アニオンを有する主鎖成分を生成し、有機半導体層を形成した。
　こうして、厚さ１５０ｎｍの有機半導体層１を成膜し、実施例１～２０及び比較例１～３の有機薄膜トランジスタ（ボトムゲート・ボトムコンタクト型）を得た。 Subsequently, the said composition for organic-semiconductor layer formation was apply | coated by spin coating (rotation speed 1000rpm) at 25 degreeC so that the gate insulating layer 2, the source electrode 3, and the drain electrode 4 might be covered. Then, it heated at 150 degreeC on the hotplate for 30 minutes, and formed the organic-semiconductor layer precursor layer into a film. Next, the organic semiconductor layer precursor layer obtained was irradiated with light having a wavelength of 254 to 365 nm (irradiation amount 30 mW / cm 2 ) for 10 seconds using a high pressure UV lamp (manufactured by USHIO INC.) To generate photoacid The organic semiconductor layer was formed by decomposing the resin to produce a main chain component having an acid anion in the side chain in the system.
Thus, an organic semiconductor layer 1 having a thickness of 150 nm was formed, and organic thin film transistors (bottom gate / bottom contact type) of Examples 1 to 20 and Comparative Examples 1 to 3 were obtained.
＜評価試験＞
　得られた各有機薄膜トランジスタについて、キャリア移動度μとｏｎ／ｏｆｆ比を下記方法により評価することでその性能を調べた。 <Evaluation test>
About each obtained organic thin-film transistor, the performance was investigated by evaluating carrier mobility (micro | micron | mu) and on / off ratio by the following method.
（キャリア移動度の評価）
　ソース電極３及びドレイン電極４間に－４０Ｖの電圧を印加し、ゲート電圧Ｖｇを４０Ｖ～－４０Ｖ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、Ｃiはゲート絶縁層２の単位面積当たりの容量、Ｖgはゲート電圧、Ｖｔｈは閾値電圧 (Evaluation of carrier mobility)
A voltage of −40 V is applied between the source electrode 3 and the drain electrode 4, the gate voltage Vg is changed in the range of 40 V to −40 V, and the carrier mobility μ (cm 2 / Vs) is expressed using the following formula representing the drain current Id. ) Was calculated.
Id = (w / 2L) μCi (Vg−Vth) 2
In the formula, L is the gate length, w is the gate width, Ci is the capacitance per unit area of the gate insulating layer 2, Vg is the gate voltage, and Vth is the threshold voltage.
（ｏｎ／ｏｆｆ比の評価）
　ソース電極３及びドレイン電極４間にかかる電圧を－４０Ｖに固定し、ゲート電圧Ｖｇを４０～－４０Ｖまで変化（スイープ）させたときの（｜Ｉｄ｜の最大値）／（｜Ｉｄ｜の最小値）をｏｎ／ｏｆｆ比とした。結果を表１に示す。 (Evaluation of on / off ratio)
When the voltage applied between the source electrode 3 and the drain electrode 4 is fixed at −40V and the gate voltage Vg is changed (swept) from 40 to −40V (maximum value of | Id |) / (minimum of | Id |) Value) was defined as the on / off ratio. The results are shown in Table 1.
［有機薄膜トランジスタＩＩの製造と評価（実施例２１～２８）］
　上記有機薄膜トランジスタＩの作製において、有機半導体層前駆体層を、有機半導体材料を含む有機半導体材料層と光酸発生樹脂を含む光酸発生樹脂層との２層構成として形成した以外は同様の方法により、表１に示す配合で有機薄膜トランジスタＩＩを作製した。詳細は下記の通りである。
　まず、ゲート絶縁層２、ソース電極３及びドレイン電極４を覆うように、下記表１において化合物番号Ｎ７で表される有機半導体材料をトルエン１ｍＬに溶解した有機半導体材料層形成用組成物（有機半導体材料層形成用組成物における有機半導体材料の濃度：０．５質量％)を、２５℃でスピンコート（回転数１０００ｒｐｍ）により塗布した。その後、ホットプレート上にて１５０℃で３０分加熱して厚さ１５０ｎｍの有機半導体材料層を成膜した。
　次いで、上記で成膜した有機半導体材料層上に、下記表１に示される光酸発生樹脂（Ａ-１～８）をそれぞれトルエン１ｍＬに溶解した各光酸発生樹脂層形成組成物（各光酸発生樹脂層形成組成物における光酸発生樹脂の濃度：０．１質量％）を、２５℃でスピンコート（回転数１０００ｒｐｍ）により塗布した。その後、ホットプレート上にて１５０℃で３０分加熱して、光酸発生樹脂層を成膜した。こうして、厚さ１５０ｎｍの有機半導体層前駆体層を成膜し、ＯＴＦＴを製造した。
　次いで、得られた有機半導体層前駆体層に対し、高圧ＵＶランプ（ウシオ電機社製）を用いて２５４～３６５ｎｍの波長の光（照射量３０ｍＷ/ｃｍ２）を１０秒照射し、光酸発生樹脂を分解して系内に側鎖に酸アニオンを有する主鎖成分を生成し、有機半導体層１を形成した。
　こうして、厚さ１５０ｎｍの有機半導体層１を成膜し、実施例２１～２８の有機薄膜トランジスタ（ボトムゲート・ボトムコンタクト型）を得た。 [Production and Evaluation of Organic Thin Film Transistor II (Examples 21 to 28)]
In the production of the organic thin film transistor I, the same method except that the organic semiconductor layer precursor layer is formed as a two-layer structure of an organic semiconductor material layer containing an organic semiconductor material and a photoacid generating resin layer containing a photoacid generating resin. Thus, an organic thin film transistor II was prepared with the formulation shown in Table 1. Details are as follows.
First, a composition for forming an organic semiconductor material layer (organic semiconductor) obtained by dissolving an organic semiconductor material represented by Compound No. N7 in Table 1 below in 1 mL of toluene so as to cover the gate insulating layer 2, the source electrode 3, and the drain electrode 4. The organic semiconductor material concentration in the composition for forming a material layer: 0.5 mass%) was applied by spin coating (rotation speed: 1000 rpm) at 25 ° C. Thereafter, an organic semiconductor material layer having a thickness of 150 nm was formed by heating on a hot plate at 150 ° C. for 30 minutes.
Next, on each organic semiconductor material layer formed as described above, each photoacid-generating resin layer forming composition (each light having a photoacid-generating resin (A-1 to 8) shown in Table 1 below dissolved in 1 mL of toluene) The photoacid generating resin concentration in the acid generating resin layer forming composition: 0.1% by mass) was applied at 25 ° C. by spin coating (rotation speed: 1000 rpm). Then, it heated at 150 degreeC on the hotplate for 30 minutes, and formed the photo-acid generating resin layer into a film. Thus, an organic semiconductor layer precursor layer having a thickness of 150 nm was formed to produce an OTFT.
Next, the organic semiconductor layer precursor layer obtained was irradiated with light having a wavelength of 254 to 365 nm (irradiation amount 30 mW / cm 2 ) for 10 seconds using a high pressure UV lamp (manufactured by USHIO INC.) To generate photoacid The organic semiconductor layer 1 was formed by decomposing the resin to produce a main chain component having an acid anion in the side chain in the system.
Thus, an organic semiconductor layer 1 having a thickness of 150 nm was formed, and organic thin film transistors (bottom gate / bottom contact type) of Examples 21 to 28 were obtained.
　得られた各有機薄膜トランジスタについて、上述の有機薄膜トランジスタＩと同様の方法によりキャリア移動度μとｏｎ／ｏｆｆ比を評価することでその性能を調べた。結果を表１に示す。
　尚、表１において、光酸発生樹脂のｐＫａとは、「光酸発生樹脂の酸アニオンを生じる構造部位を有するユニット（一般式（ＩＩＩ）～（Ｖ）で表される繰り返し単位の単量体）のｐＫａ」を意味する。また、１０＾６は、「１０の６乗」（１０６）を意図する。 About each obtained organic thin-film transistor, the performance was investigated by evaluating carrier mobility (micro | micron | mu) and on / off ratio by the method similar to the above-mentioned organic thin-film transistor I. The results are shown in Table 1.
In Table 1, the pKa of the photoacid generator resin is “a unit having a structural site that generates an acid anion of the photoacid generator resin (a monomer of a repeating unit represented by formulas (III) to (V)”). ) PKa ". Also, 10 ^ 6 is intended to be “10 to the sixth power” (10 6 ).
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
　表１に示す結果から、以下のことが分かる。
　実施例１～２８の有機薄膜トランジスタは、いずれも、光酸発生樹脂を用いた有機半導体層形成用組成物を用いて作製しているため、光酸発生樹脂の光照射により解離した主鎖の酸成分が絶縁層へ拡散せず、これによりｏｎ／ｏｆｆ比が優れていた。また、有機半導体層形成用組成物により形成される有機半導体層は、有機半導体材料による結晶構造が形成された後に光照射により系内で光酸発生樹脂を分解する構成をとり、また、分解によって生じた側鎖に酸アニオンを有する主鎖部分が系内で有機半導体材料の結晶構造と相分離して存在するため、すなわち、結晶性を乱さず、且つ、均一にドープされるため、キャリア移動度μにも優れていた。
　特に、光酸発生樹脂の中でも、対カチオンとしてスルホニウム塩又はヨードニウム塩を有する化合物を用いた場合には、より優れたキャリア移動度μが得られることが分かった。
　また、光酸発生樹脂として、側鎖の酸アニオン発生構造部位に連結するＸ１～Ｘ３の位置に電子吸引性基を導入してｐＫａを－１０以下としたＡ－２，３，４を用いた場合には、より優れたキャリア移動度μが得られることが分かった。
　また、実施例１、１７～２０との比較により、有機半導体材料に対する光酸発生樹脂の添加量を適切なものとすることで（有機半導体材料１００質量部に対して、０．００１～３０質量部であるのが好ましく、０．０１～２０質量部であるのがより好ましく、０．１～５質量部であるのがさらに好ましい。）、キャリア移動度μをさらに高めることができた。 From the results shown in Table 1, the following can be understood.
Since the organic thin film transistors of Examples 1 to 28 are all produced using a composition for forming an organic semiconductor layer using a photoacid generating resin, the main chain acid dissociated by light irradiation of the photoacid generating resin is used. The component did not diffuse into the insulating layer, which resulted in an excellent on / off ratio. In addition, the organic semiconductor layer formed by the composition for forming an organic semiconductor layer has a structure in which the photoacid-generating resin is decomposed in the system by light irradiation after the crystal structure is formed by the organic semiconductor material. The main chain portion having an acid anion in the generated side chain exists in the system in phase separation from the crystal structure of the organic semiconductor material, that is, it does not disturb the crystallinity and is uniformly doped. The degree μ was also excellent.
In particular, it has been found that when a compound having a sulfonium salt or an iodonium salt as a counter cation is used among the photoacid generating resins, a better carrier mobility μ can be obtained.
Further, as a photoacid generating resin, A-2, 3, and 4 having pKa of −10 or less by introducing an electron withdrawing group into the position of X 1 to X 3 linked to the side chain acid anion generating structure site. When used, it was found that a better carrier mobility μ can be obtained.
Further, by comparing the amount of the photoacid-generating resin with respect to the organic semiconductor material by comparison with Examples 1 and 17 to 20 (0.001 to 30 mass relative to 100 mass parts of the organic semiconductor material). The carrier mobility μ can be further increased. The carrier mobility μ is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight.
　これに対して、光酸発生樹脂を添加しない比較例１は、キャリア移動度μが十分ではなかった。一方、引用文献１に記載されるような低分子タイプの光酸発生剤を用いた比較例２、３においては、いずれも、キャリア移動度μ及びｏｎ／ｏｆｆ比が十分ではなかった。 In contrast, Comparative Example 1 in which no photoacid-generating resin was added did not have sufficient carrier mobility μ. On the other hand, in Comparative Examples 2 and 3 using the low molecular type photoacid generator as described in the cited document 1, the carrier mobility μ and the on / off ratio were not sufficient.
　１　有機半導体層、　２　ゲート絶縁層、　３　ソース電極、　４　ドレイン電極、　５　ゲート電極、　６　基板 1 organic semiconductor layer 2 gate insulating layer 3 source electrode 4 drain electrode 5 gate electrode 6 substrate

Claims (9)

  1. 　ゲート電極と、有機半導体層と、前記ゲート電極及び前記有機半導体層の間に設けられたゲート絶縁層と、前記有機半導体層に接して設けられ、前記有機半導体層を介して連結されたソース電極及びドレイン電極と、を有する有機薄膜トランジスタであって、
    　前記有機半導体層が、有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造部位を側鎖に含む繰り返し単位を有する樹脂と、を含む有機半導体層前駆体層に対して活性光線又は放射線を照射することにより得られる層である、有機薄膜トランジスタ。     A gate electrode; an organic semiconductor layer; a gate insulating layer provided between the gate electrode and the organic semiconductor layer; and a source electrode provided in contact with the organic semiconductor layer and connected via the organic semiconductor layer And an organic thin film transistor having a drain electrode,
    The organic semiconductor layer contains an organic semiconductor material and an active light ray or an organic light source with respect to the organic semiconductor layer precursor layer containing a resin having a repeating unit containing a structural site that generates an acid anion upon irradiation with active light or radiation. An organic thin film transistor which is a layer obtained by irradiation with radiation.
  2. 　前記繰り返し単位が、下記式（ＩＩＩ）～（Ｖ）から選択される少なくとも１種類である、請求項１に記載の有機薄膜トランジスタ。
    Figure JPOXMLDOC01-appb-C000001
     式（ＩＩＩ）～（Ｖ）中、
    　Ａは、活性光線又は放射線の照射により分解して酸アニオンを生じる構造部位を表す。
    　Ｒ０４、Ｒ０５及びＲ０７～Ｒ０９は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
    　Ｒ０６は、シアノ基、カルボキシル基、－ＣＯ－ＯＲ２５又は－ＣＯ－Ｎ（Ｒ２６）（Ｒ２７）を表す。Ｒ２６とＲ２７が結合して窒素原子とともに環を形成してもよい。
    　Ｒ０６とＸ２とが互いに連結して環を形成してもよい。
    　Ｘ１～Ｘ３は、各々独立に、単結合、アリーレン基、アルキレン基、シクロアルキレン基、－Ｏ－、－ＳＯ２－、－ＣＯ－、－Ｎ（Ｒ３３）－又はこれらの複数を組み合わせた２価の連結基を表す。
    　Ｒ２５は、アルキル基、シクロアルキル基、アルケニル基、アリール基又はアラルキル基を表す。
    　Ｒ２６、Ｒ２７及びＲ３３は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、アリール基又はアラルキル基を表す。     The organic thin film transistor according to claim 1, wherein the repeating unit is at least one selected from the following formulas (III) to (V).
    Figure JPOXMLDOC01-appb-C000001
     In formulas (III) to (V),
    A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
    R 04 , R 05 and R 07 to R 09 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
    R 06 represents a cyano group, a carboxyl group, —CO—OR 25 or —CO—N (R 26 ) (R 27 ). R 26 and R 27 may combine to form a ring together with the nitrogen atom.
    R 06 and X 2 may be linked to each other to form a ring.
    X 1 to X 3 each independently represents a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R 33 ) —, or a combination thereof. Represents a divalent linking group.
    R 25 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
    R 26 , R 27 and R 33 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
  3. 　前記繰り返し単位中の酸アニオンを生じる構造部位が、スルホニウム塩構造又はヨードニウム塩構造を有する、請求項１又は２に記載の有機薄膜トランジスタ。 The organic thin film transistor according to claim 1 or 2, wherein the structural site that generates an acid anion in the repeating unit has a sulfonium salt structure or an iodonium salt structure.
  4. 　前記有機半導体材料が、縮合多環芳香族基を有し、前記縮合多環芳香族基中の環数が４つ以上であり、前記縮合多環芳香族基中の少なくとも２つの環が、硫黄原子、窒素原子、セレン原子及び酸素原子よりなる群から選択される少なくとも１つの原子を含み、前記縮合多環芳香族基中の部分構造として、ベンゼン環、ナフタレン環、及び、フェナントレン環よりなる群から選択される少なくともいずれか１つの構造を含む、請求項１～３のいずれか１項に記載の有機薄膜トランジスタ。 The organic semiconductor material has a condensed polycyclic aromatic group, the condensed polycyclic aromatic group has 4 or more rings, and at least two rings in the condensed polycyclic aromatic group are sulfur. A group comprising at least one atom selected from the group consisting of an atom, a nitrogen atom, a selenium atom, and an oxygen atom, the partial structure in the condensed polycyclic aromatic group being a benzene ring, a naphthalene ring, and a phenanthrene ring The organic thin film transistor according to any one of claims 1 to 3, comprising at least one structure selected from the group consisting of:
  5. 　前記有機半導体材料における前記縮合多環芳香族基中の環数が、４～６である、請求項４に記載の有機薄膜トランジスタ。 The organic thin film transistor according to claim 4, wherein the condensed polycyclic aromatic group in the organic semiconductor material has 4 to 6 rings.
  6. 　前記有機半導体材料の前記縮合多環芳香族基中に少なくとも２つの複素環が含まれ、前記複素環がそれぞれ、ヘテロ原子を１つのみ有する複素環である、請求項４又は５に記載の有機薄膜トランジスタ。 The organic according to claim 4 or 5, wherein the condensed polycyclic aromatic group of the organic semiconductor material contains at least two heterocycles, and each of the heterocycles is a heterocycle having only one heteroatom. Thin film transistor.
  7. 　前記有機半導体層において、前記樹脂の含有量が、有機半導体材料１００質量部に対して０．００１～３０質量部である、請求項１～６のいずれか１項に記載の有機薄膜トランジスタ。 The organic thin film transistor according to any one of claims 1 to 6, wherein the content of the resin in the organic semiconductor layer is 0.001 to 30 parts by mass with respect to 100 parts by mass of the organic semiconductor material.
  8. 　前記ゲート絶縁層が有機高分子を少なくとも含む、請求項１～７のいずれか１項に記載の有機薄膜トランジスタ。 The organic thin film transistor according to any one of claims 1 to 7, wherein the gate insulating layer contains at least an organic polymer.
  9. 　有機半導体材料と、活性光線又は放射線の照射により酸アニオンを生じる構造を側鎖に含む繰り返し単位を有する樹脂と、を含む、有機半導体層形成用組成物。 A composition for forming an organic semiconductor layer, comprising: an organic semiconductor material; and a resin having a repeating unit containing a structure that generates acid anions upon irradiation with actinic rays or radiation in the side chain.
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