WO2023003038A1 - Matériau électronique organique et élément électronique organique - Google Patents

Matériau électronique organique et élément électronique organique Download PDF

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WO2023003038A1
WO2023003038A1 PCT/JP2022/028328 JP2022028328W WO2023003038A1 WO 2023003038 A1 WO2023003038 A1 WO 2023003038A1 JP 2022028328 W JP2022028328 W JP 2022028328W WO 2023003038 A1 WO2023003038 A1 WO 2023003038A1
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group
charge
structural unit
organic
organic electronic
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和幸 加茂
尚幹 田村
伊織 福島
悟史 黒澤
貴紀 宮
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昭和電工マテリアルズ株式会社
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Publication of WO2023003038A1 publication Critical patent/WO2023003038A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to organic electronic materials, ink compositions, organic layers, organic electronic elements, organic electroluminescence elements (organic EL elements), display elements, lighting devices, and display devices.
  • Organic electronic elements are elements that operate electrically using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility.
  • Examples of organic electronic elements include organic EL elements, organic photoelectric conversion elements, organic transistors, and the like.
  • organic electronic elements are desired to be further improved in various element characteristics.
  • improvements have been made to multiply the organic layers and separate the functions of each layer.
  • the lower layer is required to have solvent resistance to the solvent of the coating liquid used for forming the upper layer.
  • the present disclosure provides an organic electronic material and an ink composition capable of forming an organic layer with excellent solvent resistance. Further, the present disclosure provides an organic layer having excellent solvent resistance, and an organic electronic device, an organic EL device, a display device, a lighting device, and a display device including the organic layer.
  • the present disclosure includes various embodiments of the present invention. Examples of embodiments are listed below. The present invention is not limited to the following embodiments.
  • One embodiment contains an ionic compound containing an anion (A1) having at least two tri(fluoroaryl)borane structures and an ammonium cation, and a charge-transporting compound having at least one polymerizable functional group. , on organic electronic materials.
  • Another embodiment is an anion having at least two tri(fluoroaryl)borane structures and at least one heterocyclic ring, wherein said heterocyclic ring has one or more nitrilo groups and one or more heteroatoms ( It relates to an organic electronic material containing an ionic compound containing A2) and a cation, and a charge-transporting compound having at least one polymerizable functional group.
  • Another embodiment relates to an ink composition containing any of the organic electronic materials described above and a solvent. Another embodiment relates to an organic layer formed using any of the organic electronic materials or the ink composition. Another embodiment relates to an organic electronic device comprising said organic layer. Another embodiment relates to an organic electroluminescent device having the organic layer. Other embodiments relate to a display device having the organic electroluminescence element; a lighting device having the organic electroluminescence device; and a display device having the lighting device and a liquid crystal element as display means.
  • an organic electronic material and an ink composition capable of forming an organic layer with excellent solvent resistance. Further, according to the present disclosure, it is possible to obtain an organic layer having excellent solvent resistance, and an organic electronic device, an organic EL device, a display device, a lighting device, and a display device including the organic layer.
  • a numerical range indicated using "to” indicates a range including the numerical values described before and after "to" as the minimum and maximum values, respectively.
  • the upper limit or lower limit of the numerical range in one step can be arbitrarily combined with the upper limit or lower limit of the numerical range in another step.
  • the materials exemplified in the present disclosure can be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means.
  • layer includes continuous and discontinuous layers.
  • the "layer” thickness may be uniform or non-uniform.
  • the in-plane and thickness-wise outer edges of a “layer” can each be distinct or indistinct. The same applies to "membrane”.
  • Organic electronic materials contain an ionic compound and a charge-transporting compound.
  • Ionic compounds include anions and cations.
  • the charge-transporting compound has at least one polymerizable functional group in its molecule.
  • An ionic compound comprises at least one anion and at least one cation. Ionic compounds usually contain anions and cations so that their charges are balanced.
  • the ionic compound includes an anion (A1) having at least two tri(fluoroaryl)borane structures (hereinafter sometimes simply referred to as "anion (A1)").
  • the anion (A1) may further contain a linking group.
  • Each of the at least two tri(fluoroaryl)borane structures may be bonded to a linking group, and a boron atom contained in each of the at least two tri(fluoroaryl)borane structures may be bonded to the linking group. .
  • the ionic compound has at least two tri(fluoroaryl)borane structures and at least one heterocyclic ring, wherein said heterocyclic ring comprises one or more nitrilo groups and one or more heteroatoms. and an anion (A2) (hereinafter sometimes simply referred to as “anion (A2)”).
  • A2 an anion
  • Each of the at least two tri(fluoroaryl)borane structures may be bonded to a heterocyclic ring, and the boron atom contained in each of the at least two tri(fluoroaryl)borane structures is a nitrilo group contained in the heterocyclic ring or It may be attached to a heteroatom.
  • Anions (A2) are included in the embodiments of anions (A1).
  • At least two tri(fluoroaryl)borane structures of the anion (A1) or the anion (A2) may be the same or different.
  • the tri(fluoroaryl)borane structure may be a structure containing a boron atom and three "substituted or unsubstituted fluoroaryl groups" bonded to the boron atom. Three "substituted or unsubstituted fluoroaryl groups" may be the same or different.
  • a fluoroaryl group is an aryl group substituted with at least one fluoro group.
  • a fluoroaryl group may be a perfluoroaryl group.
  • a substituted fluoroaryl group is an aryl group substituted with at least one fluoro group and at least one substituent other than a fluoro group.
  • An unsubstituted fluoroaryl group is an aryl group that is substituted only with at least one fluoro group.
  • the number of carbon atoms in the aryl group in the substituted or unsubstituted fluoroaryl group is, for example, 6-60, 6-40, 6-25, 6-18, or 6-12.
  • An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
  • the aromatic hydrocarbon herein is selected from the group consisting of monocyclic rings, condensed rings, and polycyclic rings in which two or more rings selected from monocyclic and condensed rings are chemically bonded.
  • Aromatic hydrocarbons are, for example, selected from the group consisting of benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, triphenylene, pyrene, chrysene, perylene, triphenylene, pentacene, and benzopyrene.
  • the aromatic hydrocarbon can be benzene, naphthalene, fluorene, anthracene, or phenanthrene, can be benzene or naphthalene, can be benzene.
  • substituted fluoroaryl group may have includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, an alkylaryl group, an alkylheteroaryl group, halogen group (excluding fluoro group), nitro group, cyano group, amino group, silyl group, sulfo group, hydroxyl group, mercapto group, formyl group, carboxyl group, alkoxy group, aryloxy group, heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an acyl group, an acyloxy group, and an alkyloxycarbonyl group.
  • an alkyl group an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a
  • substituted or unsubstituted “substituents” may be substituted or unsubstituted “substituents", and the "substituent” that the substituted “substituent” may have is, for example, at least one selected from the above group and in said group the halogen group may comprise a fluoro group.
  • halogen groups include fluoro, chloro, bromo, iodo groups, and the like.
  • the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.
  • the carbon number of the alkyl group is, for example, 1-24, 1-20, 1-18, 1-16, or 1-12.
  • Alkyl groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl.
  • n-undecyl group n-dodecyl group
  • isopropyl group isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, cycloheptyl group, and cyclo It contains at least one selected from the group consisting of octyl groups.
  • Alkenyl may be a straight-chain alkenyl group, a branched alkenyl group, or a cyclic alkenyl group.
  • the number of carbon atoms in the alkenyl group is, for example, 1-24, 1-20, 1-18, 1-16, or 1-12.
  • Alkenyl groups include, for example, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, and It contains at least one selected from the group consisting of 1-octenyl groups.
  • the alkynyl group may be a straight-chain alkynyl group, a branched alkynyl group, or a cyclic alkynyl group.
  • the number of carbon atoms in the alkynyl group is, for example, 1-24, 1-20, 1-18, 1-16, or 1-12.
  • Alkenyl groups include, for example, at least one selected from the group consisting of ethynyl and 2-propynyl groups.
  • the aryl group is as described above.
  • the carbon number of the aryl group is, for example, 6-60, 6-40, 6-25, 6-18, or 6-12.
  • a heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound.
  • the carbon number of the heteroaryl group is, for example, 2-60, 2-40, 2-25, 2-18, or 2-12.
  • the aromatic heterocyclic compound herein is selected from the group consisting of monocyclic rings, condensed rings, and polycyclic rings in which two or more selected from monocyclic and condensed rings are chemically bonded.
  • Aromatic heterocyclic compounds are, for example, pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole, benzothiadiazole, It contains at least one selected from the group consisting of benzotriazole and benzothiophene.
  • An arylalkyl group is an alkyl group substituted with an aryl group.
  • the carbon number of the arylalkyl group is, for example, 7-60, 7-40, 7-25, 7-18, or 7-12.
  • Examples of the aryl group include the aryl groups described above, and examples of the alkyl group include the alkyl groups described above.
  • Arylalkyl groups include, for example, at least one selected from the group consisting of a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a diphenylmethyl group.
  • An alkylaryl group is an aryl group substituted with an alkyl group.
  • the carbon number of the alkylaryl group is, for example, 7-60, 7-40, 7-25, 7-18, or 7-12.
  • Examples of the alkyl group include the aforementioned alkyl groups, and examples of the aryl group include the aforementioned aryl groups.
  • the alkylaryl group includes, for example, at least one selected from the group consisting of a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, an ethylnaphthyl group, and a dimethylphenyl group.
  • heteroarylalkyl group alkylheteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, acyl group, acyloxy group or alkyloxycarbonyl group, alkyl group, aryl
  • the groups and heteroaryl groups are as described above.
  • the tri(fluoroaryl)borane structure may be a structure represented by the following formula (b).
  • each Ar F independently represents a substituted or unsubstituted fluoroaryl group.
  • "*" represents a binding site with another atom in this disclosure.
  • the tri(fluoroaryl)borane structure examples include a tri(pentafluorophenyl)borane structure and a tri(pentafluoronaphthyl)borane structure.
  • the tri(fluoroaryl)borane structure comprises a tri(pentafluorophenyl)borane structure.
  • Anion (A1) contains at least two tri(fluoroaryl)borane structures and may further contain a linking group.
  • the linking group may be a positively charged group.
  • the linking group is selected from the group consisting of, for example, an alkylene group, an imino group (-NH-), an oxy group (-O-), a thio group (-S-), -CN + -, an aromatic ring, and a heterocyclic ring.
  • the linking group is a heterocyclic ring-containing group having one or more nitrilo groups, a heterocyclic ring-containing group having one or more heteroatoms, or one or more nitrilo groups and one or more heteroatoms. It may be a group containing a heterocycle.
  • the anion (A2) contains at least two tri(fluoroaryl)borane structures and at least one heterocyclic ring, and the heterocyclic ring contains one or more nitrilo groups and one or more heteroatoms.
  • the one or more heteroatoms include, for example, at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms.
  • the "hetero atom" of the heterocyclic ring does not include the nitrogen atom contained in the nitrilo group. That is, “heteroatom” means a heteroatom other than the nitrogen atom contained in the nitrilo group.
  • a nitrilo group is a group represented by the following formula.
  • heterocyclic rings having one or more nitrilo groups and one or more heteroatoms are imidazole, pyrazole, benzimidazole, benzopyrazole, purine, perimidine, phenothiazine, and phenoxazine rings. mentioned.
  • the heterocyclic ring preferably contains at least one selected from the group consisting of an imidazole ring, a pyrazole ring, a benzimidazole ring, and a benzopyrazole ring, and preferably contains an imidazole ring.
  • the anion (A1) may include an anion represented by formula (a1) below.
  • X1 represents a linking group
  • n may be 0 or 1
  • each Ar 2 F independently represents a substituted or unsubstituted fluoroaryl group.
  • the anion (A2) may include an anion represented by formula (a2) below.
  • the anion represented by formula (a2) below is included in embodiments of the anion represented by formula (a1).
  • X2 represents a heterocyclic ring having one or more nitrilo groups and one or more heteroatoms, and each Ar 2 F independently represents a substituted or unsubstituted fluoroaryl group.
  • Ar 2 F may each independently be a group represented by formula (Ar1) below.
  • each R independently represents a hydrogen atom or a substituent, and at least one R is a fluoro group.
  • substituents other than the fluoro group include the "substituent" that the above-mentioned substituted fluoroaryl group may have.
  • the anion (A1) when n is 0, the anion (A1) is a divalent anion, and when n is 1, the anion (A1) is a monovalent anion.
  • X1 is selected from the group consisting of an alkylene group, an imino group (-NH-), an oxy group (-O-), a thio group (-S-), -CN + -, an aromatic ring, and a heterocyclic ring. At least one may be used.
  • Ar 2 F when Ar 2 F is a group represented by formula (Ar1), for example, all R may be fluoro groups.
  • X2 may be an imidazole ring, pyrazole ring, benzimidazole ring, benzopyrazole ring, purine ring, perimidine ring, phenothiazine ring, or phenoxazine ring, imidazole ring, pyrazole ring, benzo It may be an imidazole ring, a benzopyrazole ring, or an imidazole ring.
  • Ar 2 F is a group represented by formula (Ar1), for example, all R may be fluoro groups.
  • the ionic compound is a cation of an element belonging to Groups 1 and 2 of the IUPAC Periodic Table of the Elements, and a cation represented by formula (c1) to formula (c3). at least one cation selected from the group consisting of cations
  • "IUPAC Periodic Table of the Elements” refers to "IUPAC Periodic Table of the Elements (dated 1 Dec 2018)”.
  • the cation may include, for example, at least one cation selected from the group consisting of cations represented by formula (c1) to cations represented by formula (c3).
  • Elements belonging to Group 1 of the IUPAC periodic table of elements include lithium, sodium, and potassium.
  • Beryllium, magnesium, calcium, etc. are examples of elements belonging to Group 2 of the IUPAC Periodic Table of Elements.
  • R 1 to R 9 each independently represent a hydrogen atom or an organic group (at least two groups selected from R 1 and R 2 , R 3 to R 5 , and at least two groups selected from R 6 to R 9 may be bonded to each other.).
  • R 1 to R 9 each independently represent a hydrogen atom or an organic group.
  • R 1 to R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted It may be a substituted alkynyl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. These groups may have a substituent. at least one group selected from R 1 and R 2 , at least one group selected from R 3 to R 5 and at least one group selected from R 6 to R 9 are organic groups is preferred.
  • substituted or unsubstituted alkyl group substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heteroaryl
  • substituted or unsubstituted alkyl group substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heteroaryl
  • substituted or unsubstituted alkyl group substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryl group
  • a 1 in formula (c1) may be a chlorine atom, a bromine atom, or an iodine atom
  • a 2 in formula (c2) may be It may be a carbon atom, an oxygen atom, a sulfur atom, or a selenium atom
  • A3 in formula (c3) may be a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, or a bismuth atom.
  • Examples of the cation represented by formula (c1) to the cation represented by formula (c3) include chloronium, bromonium, iodonium, carbenium, oxonium, sulfonium, selenonium, ammonium, phosphonium, arsonium, stivonium, bismuthonium, and the like. .
  • the ionic compound may include an ammonium cation.
  • ammonium cation may include a cation represented by formula (c3) above (where A3 is a nitrogen atom).
  • Ammonium cations may include cations represented by the following formula (c4).
  • R a to R c each independently represent a hydrogen atom, an alkyl group, an arylalkyl group, or an aryl group.
  • alkyl group, arylalkyl group, and aryl group are as described above.
  • Alkyl groups, arylalkyl groups, and aryl groups can be unsubstituted.
  • R a to R c may all be alkyl groups, for example. Of R a to R c , for example, two may be alkyl groups and one may be an aryl group.
  • cations include N,N-diisopropylethylammonium, N,N-diisopropylanilinium, and triethylammonium.
  • the ionic compound comprises an anion (A1) and an ammonium cation.
  • the ionic compound may comprise an anion represented by formula (a1) and an ammonium cation; good. According to these embodiments, an organic layer having excellent solvent resistance can be formed.
  • the ionic compound comprises an anion (A2) and a cation.
  • the ionic compound may contain an anion and a cation represented by formula (a2); may contain an anion and an ammonium cation represented by formula (a2); and an anion (A2) and an ammonium cation. well; it may contain an anion represented by formula (a2) wherein X2 is an imidazole ring and an ammonium cation.
  • an organic layer having excellent solvent resistance can be formed.
  • the charge-transporting compound may be a charge-transporting polymer or a charge-transporting low molecular weight compound.
  • the charge-transporting compound preferably has at least one polymerizable functional group.
  • Polymerizable functional groups are functional groups that can form bonds with each other by the application of heat, light, or both heat and light.
  • the charge-transporting compound exhibits curability by containing a polymerizable functional group.
  • the organic layer can be imparted with solvent resistance necessary for laminating an upper layer by a wet process.
  • a layer formed using an organic electronic material and containing a charge-transporting compound and an ionic compound before curing may be referred to as a coating film.
  • the hole-transporting layer becomes a solvent-resistant layer.
  • the charge-transporting compound having a polymerizable functional group is preferably a charge-transporting compound that can form a charge-transporting layer that is difficult to dissolve even when immersed in an aromatic hydrocarbon solvent such as toluene. .
  • a group having a carbon-carbon multiple bond e.g., vinyl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino groups, vinyloxy groups, vinylamino groups, etc.
  • groups having small rings e.g., cyclic alkyl groups such as cyclopropyl groups and cyclobutyl groups; epoxy groups (oxiranyl groups), cyclic ether groups such as oxetane groups (oxetanyl groups) cyclic thioether groups such as episulfide groups; cyclic ester groups such as diketene groups and lactone groups; cyclic amide groups such as lactam groups), heterocyclic groups (e.g., furan-yl, pyrrol-yl,
  • the polymerizable functional group may be a substituted or unsubstituted polymerizable functional group, and examples of substituents that the polymerizable functional group may have include alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group. is mentioned.
  • the polymerizable functional group preferably contains one or more selected from the group consisting of a group having a carbon-carbon multiple bond, a group having a small membered ring, and a heterocyclic group. - It is more preferable to include one or more selected from the group consisting of a group having a carbon double bond, a cyclic ether group, and a heterocyclic group.
  • the polymerizable functional group is preferably at least one selected from the group consisting of a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, an oxetane group, a pyrrol-yl group, and a thiophene-yl group, At least one selected from the group consisting of a vinyl group, an oxetane group, and a thiophen-yl group is more preferable from the viewpoint of the solubility and curability of the charge-transporting compound.
  • the polymerizable functional group preferably contains a group having a small ring, and more preferably contains a cyclic ether group.
  • the polymerizable functional group preferably contains one or more selected from the group consisting of an epoxy group and an oxetane group. It is more preferable to include
  • the charge-transporting compound preferably contains a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a benzene structure, a pyrrole structure, a furan structure, and a fluorene structure. .
  • a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a benzene structure, a pyrrole structure, a furan structure, and a fluorene structure.
  • charge transport properties particularly hole transport properties are improved.
  • the charge-transporting compound comprises a structural unit comprising an aromatic amine structure.
  • the structural unit containing an aromatic amine structure is a structural unit represented by formula (1) below, a structural unit represented by formula (2-1) below, and a structural unit represented by formula (2-2 ) contains at least one structural unit selected from the group consisting of structural units represented by
  • the “structural unit represented by formula (1)” may be referred to as “structural unit (1)”.
  • "At least one structural unit selected from the group consisting of structural units represented by formula (2-1) and structural units represented by formula (2-2)" is referred to as "structural unit (2)".
  • each Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group.
  • At least one Ar may be an aromatic hydrocarbon group having a substituent containing at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.
  • Ar is each independently preferably a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted anthracene group, a substituted or unsubstituted benzene group, or a substituted or More preferably, it is an unsubstituted naphthalene group.
  • the aromatic hydrocarbon group may have a substituent.
  • substituents include -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 , and substituents selected from the group consisting of halogen groups (hereinafter , sometimes referred to as “substituent Ra”).
  • R 1 is, for example, selected from the group consisting of alkyl groups, aryl groups, and heteroaryl groups.
  • R 2 -R 8 are, for example, each independently selected from the group consisting of hydrogen atoms, alkyl groups, aryl groups, and heteroaryl groups.
  • Alkyl groups, aryl groups, and heteroaryl groups are as described above.
  • Alkyl groups, aryl groups, and heteroaryl groups may have substituents.
  • substituents include the aforementioned substituent Ra, preferably -R 1 .
  • substituted alkyl groups include arylalkyl groups, heteroarylalkyl groups, and fluoroalkyl groups.
  • substituted aryl groups include alkylaryl groups and fluoroaryl groups.
  • heteroaryl groups having substituents include alkylheteroaryl groups and the like.
  • At least one Ar may be an aromatic hydrocarbon group having a substituent containing at least one selected from the group consisting of fluoro groups and fluoroalkyl groups.
  • the fluoroalkyl group may have 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.
  • the fluoroalkyl group is preferably a perfluoroalkyl group.
  • At least one Ar is an aromatic hydrocarbon group having a fluoro group, and all may be an aromatic hydrocarbon group having no fluoroalkyl group.
  • At least one Ar may be an aromatic hydrocarbon group having a fluoroalkyl group.
  • the total number of fluoro groups or fluoroalkyl groups contained in structural unit (1) is, for example, 1 to 8, 1 to 6, 1 to 4, or 1 to 3. With the above number, there is a tendency that the effect of deepening the HOMO level is likely to be obtained. When the number is within the above range, it tends to be easy to prevent the solubility of the charge-transporting polymer from becoming too low.
  • Structural unit (1) includes, for example, a structural unit represented by formula (1a) below.
  • each R independently represents a hydrogen atom or a substituent, and at least one R is a fluoro group or a fluoroalkyl group.
  • the number of carbon atoms in the fluoroalkyl group is, for example, 1 to 4, preferably 1 or 2.
  • the fluoroalkyl group is preferably a perfluoroalkyl group.
  • the number of Rs that are fluoro groups or fluoroalkyl groups is, for example, 1 to 8, 1 to 6, 1 to 4, or 1 to 3.
  • R that is not a fluoro group or a fluoroalkyl group is a hydrogen atom or a substituent.
  • substituents include the above-mentioned substituents Ra (excluding fluoro groups and fluoroalkyl groups). From the viewpoint of suppressing the influence of substituents, all Rs other than fluoro groups or fluoroalkyl groups may be hydrogen atoms.
  • each Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group.
  • At least one Ar may be an aromatic hydrocarbon group having a substituent containing at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.
  • each Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group.
  • At least one Ar may be an aromatic hydrocarbon group having a substituent containing at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.
  • Ar is preferably an unsubstituted aromatic hydrocarbon group.
  • each Ar is independently preferably a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted anthracene group.
  • a substituted benzene group or a substituted or unsubstituted naphthalene group is more preferred, and a substituted or unsubstituted benzene group is even more preferred.
  • each Ar is independently preferably a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted anthracene group.
  • a substituted benzene group or a substituted or unsubstituted naphthalene group is more preferred, and a substituted or unsubstituted benzene group is even more preferred.
  • Structural unit (2) includes, for example, at least one structural unit selected from the group consisting of structural units represented by formulas (2-1a) and (2-2a) below.
  • each R independently represents a hydrogen atom or a substituent.
  • substituent include the substituent Ra described above.
  • each R independently represents a hydrogen atom or a substituent.
  • substituent include the substituent Ra described above.
  • the charge-transporting compound may have a terminal group P containing a polymerizable functional group.
  • the terminal group P may contain any group other than the polymerizable functional group. Examples of the terminal group P include a "polymerizable functional group" and an "aromatic ring group substituted with a group containing a polymerizable functional group”.
  • Aromatic ring group is, for example, an aromatic ring group having 2 to 30 carbon atoms.
  • aromatic rings include aromatic hydrocarbons and aromatic heterocycles.
  • aromatic rings include single rings, condensed polycyclic aromatic hydrocarbons, and condensed polycyclic aromatic heterocycles.
  • Aromatic hydrocarbons and aromatic heterocyclic compounds are as described above.
  • the aromatic ring may be a structure in which two or more selected from independent single rings or condensed rings are bonded. Such structures include biphenyl, terphenyl, triphenylbenzene, bithiophene, and the like.
  • the aromatic ring group may have a substituent, and examples of the substituent include the substituent Ra.
  • the aromatic ring is preferably an aromatic hydrocarbon, more preferably benzene, from the viewpoint of commercial availability and ease of synthesis of the monomer for introducing the terminal group P.
  • terminal groups P include terminal groups represented by the following formula (P).
  • Ar represents a substituted or unsubstituted aromatic ring group
  • PGG represents a group containing a polymerizable functional group
  • a represents 0 or 1
  • z represents an integer of 1 or more.
  • the upper limit of z is determined by the structure of Ar.
  • Ar is a benzene ring
  • z is 5 or less, and may be 2 or less.
  • terminal groups P include terminal groups represented by the following formula (P1).
  • the terminal group represented by formula (P1) is a preferred group from the viewpoint of obtaining good heat resistance.
  • Ar represents a substituted or unsubstituted aromatic ring group
  • L represents a linking group
  • PG represents a substituted or unsubstituted polymerizable functional group.
  • a and x each independently represent 0 or 1
  • y represents an integer of 1 or more.
  • terminal groups represented by formula (P1) include terminal groups represented by the following formula (P2).
  • the terminal group represented by formula (P2) is a preferred group from the viewpoint of obtaining good heat resistance.
  • Ar represents a substituted or unsubstituted aromatic ring group having 2 to 30 carbon atoms
  • X represents a divalent group represented by any one of the following formulas (X1) to (X10)
  • Y represents an alkylene group having 1 to 10 carbon atoms
  • PG represents a substituted or unsubstituted polymerizable functional group.
  • a to c each independently represent 0 or 1, and d represents 1 or 2; However, when d is 2, a is 1.
  • each R independently represents a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl or heteroaryl group having 2 to 30 carbon atoms.
  • the charge transport compound comprises a charge transport polymer.
  • a charge-transporting polymer contains two or more structural units in the molecule.
  • polymer also includes so-called “oligomers” having a small number of structural units.
  • the charge-transporting polymer may be a linear polymer or a branched polymer having a branched structure.
  • the charge-transporting polymer includes, for example, at least a divalent structural unit L and a monovalent structural unit T having charge-transporting properties, and may further include a trivalent or higher structural unit B contained in a branched portion.
  • the charge-transporting polymer has, for example, a charge-transporting property, contains at least a trivalent or higher structural unit B and a monovalent structural unit T, and may further contain a divalent structural unit.
  • the molecular chain has a chain structure containing at least one selected from the group consisting of divalent structural units and trivalent structural units.
  • a branched charge-transporting polymer is excellent in heat resistance and exhibits good solubility and curability because a large number of terminal groups can be introduced therein.
  • the charge-transporting polymer may contain only one type of each structural unit, or may contain a plurality of types of each structural unit. In the charge-transporting polymer, each structural unit is attached to each other at one to three or more binding sites.
  • the charge-transporting polymer has a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a benzene structure, a pyrrole structure, a furan structure, and a fluorene structure. Included in unit L, structural unit B, or both structural unit L and structural unit B.
  • the charge-transporting polymer contains a branched structure having at least one structural unit B and three or more structural units L bonded to the one structural unit B.
  • the charge-transporting polymer has one structural unit B and three or more structural units L bonded to the one structural unit B, and further, for each of the three or more structural units L, It includes a multi-branched structure having at least another structural unit B bonded to the structural unit L and two or more structural units L bonded to the structural unit B.
  • Examples of multi-branched structures contained in charge-transporting polymers include the following.
  • L represents a divalent structural unit
  • B represents a trivalent or higher structural unit
  • T represents a monovalent structural unit.
  • a plurality of L's may be the same structural unit or different structural units.
  • a plurality of B's may be structural units that are the same as each other or structural units that are different from each other.
  • a plurality of T's may be structural units that are the same as each other or structural units that are different from each other.
  • the charge-transporting polymer is not limited to polymers having the following structures.
  • Structural unit L is a divalent structural unit having charge transport properties. Structural unit L is not particularly limited as long as it contains an atomic group capable of transporting charge.
  • the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, bithiophene structure, fluorene structure, benzene structure, biphenylene structure, terphenylene structure, naphthalene structure, anthracene structure, tetracene structure, phenanthrene.
  • the aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.
  • Examples of the structural unit L containing an aromatic amine structure include structural unit (1) described above.
  • the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, benzene structure, pyrrole structure, furan structure, and It preferably contains one or more structures selected from the group consisting of a fluorene structure, and is selected from the group consisting of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, a furan structure, and a fluorene structure. It more preferably contains one or more structures, and more preferably contains one or more structures selected from the group consisting of substituted or unsubstituted aromatic amine structures and carbazole structures.
  • the structural unit L is selected from the group consisting of a substituted or unsubstituted fluorene structure, benzene structure, phenanthrene structure, pyridine structure, and quinoline structure from the viewpoint of obtaining excellent electron transport properties. It preferably contains more than one species of structure.
  • Structural unit B is a structural unit having a valence of 3 or higher contained in a branched portion when the charge-transporting polymer has a branched structure.
  • Structural unit B is, for example, hexavalent or less, preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic element.
  • Structural unit B may be a unit having charge transport properties.
  • the structural unit B may be a substituted or unsubstituted aromatic amine structure, a carbazole structure, a condensed polycyclic aromatic hydrocarbon structure, and one or two of these. It is selected from structures containing more than one species.
  • structural unit B is selected from substituted or unsubstituted aromatic amine structures, carbazole structures, condensed polycyclic aromatic hydrocarbon structures, and structures containing one or more of these.
  • structural unit B containing an aromatic amine structure include structural unit (2) described above.
  • Structural unit T is a monovalent structural unit contained at the end of the charge-transporting polymer and is a structural unit containing a terminal group.
  • the structural unit T may include at least a structural unit TP containing the terminal group P and any structural unit TO different from the structural unit TP.
  • the structural unit TO does not contain a terminal group P.
  • Structural unit TP is a structural unit containing terminal group P.
  • the terminal group P described above may be the structural unit TP, and examples of the structural unit TP include groups represented by formula (P1).
  • the structural unit TO is not particularly limited, and is selected from, for example, substituted or unsubstituted aromatic hydrocarbon structures, aromatic heterocyclic structures, and structures containing one or more of these.
  • the structural unit TO is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without reducing charge transportability, and substituted or unsubstituted benzene A structure is more preferred.
  • Structural unit TO may have the same structure as structural unit L except for the valence.
  • the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without reducing charge transportability, and substituted or unsubstituted benzene A structure is more preferred.
  • a specific example of the structural unit TO is a structural unit represented by the following formula (3).
  • the structural unit TO is not limited to the following.
  • Each R independently represents a hydrogen atom or a substituent.
  • each R is independently selected from the group consisting of -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 and a halogen group.
  • R 1 to R 8 are as described in structural unit (1).
  • Structural unit TO includes, for example, at least one structural unit selected from the group consisting of structural units represented by the following formula (3-1) and structural units represented by (3-2).
  • n and m each independently represent an integer of 1 to 4.
  • n and m may be the same or different, and are preferably the same.
  • n represents an integer of 4-20. n is, for example, 4-16, preferably 4-12.
  • the polymerizable functional group is introduced at least at the end of the charge-transporting polymer (that is, the structural unit T).
  • the polymerizable functional group may be introduced into a portion other than the terminal (that is, the structural unit L or B), or may be introduced into both the terminal and the portion other than the terminal. From the viewpoint of achieving both curability and charge-transporting properties, it is preferable to introduce them only at the end portion.
  • the polymerizable functional group may be introduced into the main chain or side chain of the charge-transporting polymer, or may be introduced into both the main chain and the side chain. may have been
  • the number of polymerizable functional groups per charge-transporting polymer molecule may be 2 or more, 3 or more, 5 or more, 10 or more, or 20 or more from the viewpoint of obtaining a sufficient change in solubility.
  • the number of polymerizable functional groups may be 1,000 or less, 800 or less, 700 or less, 600 or less, or 500 or less from the viewpoint of maintaining charge transport properties.
  • the ratio of the structural unit TP is, for example, 5 mol % or more, 10 mol, based on the total of the terminal structural units. % or more, 20 mol % or more, 30 mol % or more, or 40 mol % or more. From the viewpoint of obtaining good charge transport properties, the ratio of the structural unit TP is, for example, 85 mol% or less, 80 mol% or less, 75 mol% or less, 65 mol% or less, based on the total number of terminal structural units. Alternatively, it may be 60 mol % or less.
  • the content and ratio of the polymerizable functional group per molecule of the charge-transporting polymer can be determined according to the amount of the polymerizable functional group used to synthesize the charge-transporting polymer (for example, the amount of the monomer having a polymerizable functional group). It can be determined as an average value using (amount ⁇ number of polymerizable functional groups per monomer), amount of monomer charged corresponding to each structural unit, weight average molecular weight of the charge-transporting polymer, and the like.
  • the content of the polymerizable functional group is the ratio of the integral value of the signal derived from the polymerizable functional group in the 1 H NMR (nuclear magnetic resonance) spectrum of the charge-transporting polymer to the integral value of the entire spectrum. It can be calculated as an average value using a mass average molecular weight or the like. For convenience, when the charge amount is known, the value obtained using the charge amount is preferably adopted.
  • the number-average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming properties, and the like.
  • the number average molecular weight may be, for example, 500 or more, 1,000 or more, 2,000 or more, or 3,000 or more from the viewpoint of excellent charge transportability.
  • the number average molecular weight is, for example, 200,000 or less, 100,000 or less, 50,000 or less, or 20,000 or less from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the ink composition. can be
  • the number-average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in solvents, film-forming properties, and the like.
  • the number average molecular weight may be, for example, 500 or more, 1,000 or more, 2,000 or more, or 5,000 or more from the viewpoint of excellent charge transportability.
  • the number average molecular weight is, for example, 1,000,000 or less, 100,000 or less, 50,000 or less, or 30,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the ink composition. 000 or less.
  • the mass-average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming properties, and the like.
  • the weight average molecular weight may be, for example, 1,000 or more, 3,000 or more, 5,000 or more, or 10,000 or more from the viewpoint of excellent charge transportability.
  • the weight average molecular weight is, for example, 500,000 or less, 300,000 or less, 150,000 or less, 100,000 or less, Or it may be 50,000 or less.
  • the weight-average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in solvents, film-forming properties, and the like.
  • the weight average molecular weight may be, for example, 1,000 or more, 5,000 or more, 10,000 or more, or 30,000 or more from the viewpoint of excellent charge transportability.
  • the weight average molecular weight is, for example, 1,000,000 or less, 700,000 or less, 400,000 or less, 200,000. or less, or 100,000 or less.
  • the number average molecular weight and mass average molecular weight can be determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
  • the ratio of the structural unit L is, for example, 10 mol % or more, 20 mol % or more, or 30 mol % or more, based on all structural units, from the viewpoint of obtaining sufficient charge-transporting properties. It may be mol % or more.
  • the ratio of the structural unit L may be, for example, 97 mol % or less, 92 mol % or less, or 85 mol % or less, considering the structural unit T and the structural unit B introduced as necessary.
  • the ratio of the structural unit T contained in the charge-transporting polymer is, for example, 3 mol % or more, 8 mol % or more, or 15 mol % or more based on the total structural units. good.
  • the above range is a preferable range from the viewpoint of improving the characteristics of the organic electronic device, or from the viewpoint of suppressing an increase in viscosity and performing good synthesis of the charge-transporting polymer.
  • the ratio of the structural unit T may be, for example, 60 mol % or less, 55 mol % or less, or 50 mol % or less.
  • the ratio of the structural unit B is, for example, 1 mol % or more, 5 mol % or more, or It may be 10 mol % or more.
  • the ratio of the structural unit B is, for example, 50 mol % or less, 40 mol % or less, or It may be 30 mol % or less.
  • the ratio of structural units can be determined using the amount of charged monomer corresponding to each structural unit used to synthesize the charge-transporting polymer.
  • the ratio of the structural units can be calculated as an average value using the integrated values of the spectrum derived from each structural unit in the 1 H NMR spectrum of the charge-transporting polymer. For convenience, when the charge amount is known, the value obtained using the charge amount is preferably adopted.
  • the ratio of the terminal groups described above can also be determined by a method using the amounts charged or 1 H NMR spectra.
  • the degree of polymerization (the number of structural units) of the charge-transporting polymer may be, for example, 5 or more, 10 or more, or 20 or more from the viewpoint of stabilizing the film quality of the coating film.
  • the degree of polymerization may be, for example, 1,000 or less, 700 or less, or 500 or less from the viewpoint of solubility in a solvent.
  • the degree of polymerization can be determined as an average value using the mass average molecular weight of the charge-transporting polymer, the molecular weight of the structural units, and the ratio of the structural units.
  • the charge-transporting compound preferably contains a charge-transporting compound whose thermal mass reduction upon heating at 300°C is 5% by mass or less relative to the mass before heating.
  • the thermal mass reduction may be 4.5 wt% or less, 4.3 wt% or less, 4.1 wt% or less, or 3.5 wt% or less.
  • the rate of thermal mass reduction when the charge-transporting compound is heated to 300° C. refers to the thermal mass reduction (% by mass) when the compound to be measured is heated up to 300° C. in air at a temperature increase of 5° C./min.
  • 10 mg of the compound to be measured can be used for measurement using a thermogravimetric-thermal differential (TG-DTA) analyzer.
  • TG-DTA thermogravimetric-thermal differential
  • the charge-transporting polymer can be produced by various synthetic methods and is not particularly limited. For example, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Stille coupling, and Buchwald-Hartwig coupling can be used. Suzuki coupling causes a Pd-catalyzed cross-coupling reaction between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki coupling, a charge-transporting polymer can be easily produced by bonding desired aromatic rings.
  • Pd(0) compounds, Pd(II) compounds, Ni compounds, etc. are used as catalysts. It is also possible to use a catalytic species generated by mixing a precursor such as tris(dibenzylideneacetone)dipalladium(0), palladium(II) acetate, etc. with a phosphine ligand.
  • a precursor such as tris(dibenzylideneacetone)dipalladium(0), palladium(II) acetate, etc.
  • phosphine ligand for the method for synthesizing the charge-transporting polymer, reference can be made to, for example, International Publication No. 2010/140553.
  • the charge-transporting compound comprises a charge-transporting small molecule compound.
  • a charge-transporting low-molecular-weight compound may be a compound containing one structural unit in the molecule. Examples of structural units include structural unit (1), structural unit (2), structural unit L, and structural unit B described above.
  • the charge-transporting low-molecular-weight compound has, for example, a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a benzene structure, a pyrrole structure, a furan structure, and a fluorene structure. include.
  • the organic electronic material may further contain optional components other than the ionic compound and the charge-transporting compound, such as dopants, polymerization initiators, charge-transporting compounds, and additives.
  • Additives include, for example, polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reducing agents, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Dispersants, surfactants and the like are included.
  • the content of the ionic compound may be, for example, 1% by mass or more, 10% by mass or more, or 20% by mass or more relative to the charge-transporting compound. From the viewpoint of maintaining good film formability, it may be, for example, 10% by mass or less, 5% by mass or less, or 3% by mass or less relative to the charge-transporting compound.
  • the content of the charge-transporting compound may be, for example, 50% by mass or more, 70% by mass or more, or 80% by mass or more with respect to the mass of the organic electronic material.
  • the total content of the charge-transporting compound and the ionic compound can be 100% by mass with respect to the mass of the organic electronic material.
  • the ink composition contains the organic electronic material and a solvent capable of dissolving or dispersing the material.
  • the organic layer can be easily formed by a simple method such as a coating method.
  • solvent Water, an organic solvent, or a mixed solvent thereof can be used as the solvent.
  • organic solvents include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, phenylcyclohexane and diphenylmethane.
  • aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3- Aromatic ethers such as methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and 3-phenoxytoluene; Fats such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate group esters; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; amides such as N,N-dimethylformamide and N,
  • the ink composition may further contain additives as optional components.
  • Additives include, for example, polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reducing agents, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Dispersants, surfactants and the like are included.
  • the content of the solvent in the ink composition can be determined in consideration of application to various coating methods.
  • the content of the solvent is such that the content of the charge-transporting polymer with respect to the solvent is, for example, 0.1% by mass or more, 0.2% by mass or more, or 0.5% by mass or more. can be any amount.
  • the content of the solvent may be such that the content of the charge-transporting polymer with respect to the solvent is, for example, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
  • the organic layer is a layer formed using the organic electronic material or the ink composition, and includes a cured product of the charge-transporting polymer.
  • the organic layer can be satisfactorily formed by a coating method.
  • the coating method includes, for example, a spin coating method; a casting method; an immersion method; A known method such as a plateless printing method can be used.
  • the coating film obtained after coating and before curing may be dried using a hot plate or an oven to remove the solvent.
  • the polymerization reaction of the charge-transporting polymer can be advanced and the solubility of the coating film can be changed.
  • laminating another layer on the cured organic layer (cured film) obtained after the change it becomes possible to easily achieve multilayering of the organic electronic element.
  • the heat treatment of the coating film can be performed under an air atmosphere or a nitrogen atmosphere. From the viewpoint of improving the charge transport property, it is preferable to heat-treat the coating film in a nitrogen atmosphere.
  • the ionic compound can particularly improve the solvent resistance of the organic layer when the coating film is heat-treated in a nitrogen atmosphere.
  • the thickness of the cured organic layer is, for example, 0.1 nm or more, 1 nm or more, or 3 nm or more from the viewpoint of improving the efficiency of charge transport. From the viewpoint of reducing electrical resistance, the thickness of the organic layer is, for example, 300 nm or less, 200 nm or less, or 100 nm or less.
  • Organic electronic device has at least the organic layer.
  • Organic electronic elements include, for example, organic EL elements such as organic light emitting diodes (OLED), organic photoelectric conversion elements, organic transistors, and the like.
  • the organic electronic device preferably has a structure in which an organic layer is arranged between at least a pair of electrodes.
  • the organic EL element has at least the organic layer.
  • An organic EL device usually comprises a light-emitting layer, an anode, a cathode, and a substrate, and optionally functional layers such as a hole-injection layer, an electron-injection layer, a hole-transport layer, and an electron-transport layer.
  • Each layer may be formed by a vapor deposition method, or may be formed by a coating method.
  • a known material can be used to form each layer. For known materials, reference can be made to, for example, the description of WO 2010/140553.
  • the organic EL device preferably has an organic layer as a light-emitting layer or a functional layer, more preferably as a functional layer, and even more preferably as at least one of a hole injection layer and a hole transport layer.
  • an organic layer as a light-emitting layer or a functional layer, more preferably as a functional layer, and even more preferably as at least one of a hole injection layer and a hole transport layer.
  • the organic layer formed using the organic electronic material is preferably used as at least one of a hole injection layer and a hole transport layer, and more preferably used as at least a hole injection layer. As described above, these layers can be easily formed by using an ink composition containing an organic electronic material.
  • the organic EL device has an organic layer formed using the organic electronic material as a hole transport layer and further has a hole injection layer
  • a known material can be used for the hole injection layer.
  • a known material can be used for the hole transport layer. It is also preferred to use organic electronic materials for both the hole injection layer and the hole transport layer.
  • a display element includes the organic EL element.
  • a color display element can be obtained by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB).
  • Image forming methods include a simple matrix type in which individual organic EL elements arranged on a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which each element is driven by a thin film transistor.
  • the lighting device includes the organic EL element.
  • the display device includes an illumination device and a liquid crystal element as display means.
  • the display device can be a display device using the lighting device as a backlight and using a known liquid crystal element as display means, that is, a liquid crystal display device.
  • An organic electronic material comprising an ionic compound containing a cation and a charge-transporting compound having at least one polymerizable functional group.
  • the anion (A1) includes an anion represented by the following formula (a1).
  • each R independently represents a hydrogen atom or a substituent, and at least one R is a fluoro group.
  • the polymerizable functional group includes at least one selected from the group consisting of a group having a carbon-carbon multiple bond, a group having a small ring, and a heterocyclic group.
  • the organic electronic material according to any one of the above.
  • the organic electronics according to any one of [1] to [7] above, wherein the polymerizable functional group contains a group having a small ring, and the group having a small ring contains a cyclic ether group. material.
  • the charge-transporting compound has a structural unit containing at least one structure selected from the group consisting of an aromatic amine structure, a carbazole structure, a thiophene structure, a benzene structure, a pyrrole structure, a furan structure, and a fluorene structure.
  • the organic electronic material according to any one of [1] to [8] above.
  • the organic electronic material according to any one of [1] to [9] above, wherein the charge-transporting compound contains a charge-transporting polymer.
  • the ionic compound 1 was obtained by recrystallizing the precipitate with a mixed solvent containing THF and hexane.
  • the chemical structure of ionic compound 1 is shown below.
  • the solvent was distilled off under reduced pressure until the solvent volume was reduced to about one-third, and 10 mL of hexane was added.
  • the precipitate was filtered and washed with hexane.
  • the ionic compound 2 was obtained by recrystallizing the precipitate with a mixed solvent containing THF and hexane. The chemical structure of ionic compound 2 is shown below.
  • the reaction solution was stirred overnight at room temperature, the solvent was distilled off under reduced pressure until the solvent volume was reduced to about one-third, and 10 mL of hexane was added. The precipitate was filtered and washed with hexane.
  • the ionic compound 3 was obtained by recrystallizing the precipitate with a mixed solvent containing THF and hexane. The chemical structure of ionic compound 3 is shown below.
  • ionic compound 4 The chemical structure of ionic compound 4 is shown below.
  • a reflux condenser and a nitrogen gas flow tube were attached to the flask containing the reaction solution, and the flask was immersed in an oil bath heated to 60° C. and stirred for 30 minutes. Subsequently, 2.0 mL of the Pd catalyst liquid prepared above was added, and the temperature of the oil bath was set to 120° C. to carry out the reaction. The reaction was heated to reflux for 2 hours. The operations up to this point were performed under a nitrogen stream.
  • the charge-transporting polymer 1 had a number average molecular weight of 18,000 and a weight average molecular weight of 55,000.
  • the charge-transporting polymer 1 had a thermal mass decrease of 5% by mass or less when heated at 300° C. with respect to the mass before heating.
  • GL-A160S (serial number: 686-1J27)
  • GL-A150S (serial number: 685-1J27)
  • Eluent Tetrahydrofuran (THF) (for HPLC, containing stabilizer) Fuji Film Wako Pure Chemical Industries, Ltd.
  • Sample concentration Polymer 20 mg/THF 18 mL
  • Injection volume 20 ⁇ L
  • Flow rate 1 mL/min
  • Molecular weight standards PStQuick A/B/C Tosoh Corporation
  • Example 1 (Formation of organic layer) Charge-transporting polymer 1 (30.0 mg) and ionic compound 1 (3.1 ⁇ 10 ⁇ 7 mol) (1.25% by mass relative to charge-transporting polymer 1) were dissolved in 2.7 mL of chlorobenzene to prepare an ink composition. prepared the product. The ink composition was dropped on a quartz substrate (length 22 mm, width 29 mm, thickness 0.7 mm) in the atmosphere, and a coating film was formed by a spin coater (rotation speed 3,000 min -1 ). Subsequently, curing was performed by heating in a nitrogen atmosphere at 200° C. for 30 minutes to form an organic layer having a thickness of 30 nm on the quartz substrate.
  • the absorbance A of the organic layer formed on the quartz substrate was measured.
  • the film was immersed in toluene (10 mL, 25° C.) in an environment of 25° C. and allowed to stand for 10 minutes so that the organic layer after the measurement faced up.
  • the absorbance B of the organic layer after immersion in toluene was measured. From the absorbance A of the formed organic layer and the absorbance B of the organic layer after immersion in toluene, the residual film ratio was calculated using the following formula. As the absorbance value, the value at the maximum absorption wavelength of the organic layer was used. The higher the residual film ratio, the better the solvent resistance.
  • Example 2 and 3 An organic layer was formed in the same manner as in Example 1, except that the ionic compound shown in Table 1 was used, and the residual film ratio was measured. Table 1 shows the results.
  • Example 3 An organic layer was formed in the same manner as in Example 1, except that no ionic compound was used, and the residual film rate was measured. Table 1 shows the results.

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Abstract

Un mode de réalisation de la présente invention concerne un matériau électronique organique qui contient : un composé ionique contenant un cation ammonium et un anion (A1) ayant au moins deux structures tri(fluoroaryl)borane ; et un composé de transport de charge ayant au moins un groupe fonctionnel polymérisable.
PCT/JP2022/028328 2021-07-21 2022-07-21 Matériau électronique organique et élément électronique organique WO2023003038A1 (fr)

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JP2002504485A (ja) * 1998-02-20 2002-02-12 ザ ダウ ケミカル カンパニー 拡大したアニオンを含む触媒活性化剤
WO2003062208A1 (fr) * 2002-01-17 2003-07-31 General Electric Company Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques
JP2010171373A (ja) * 2008-12-25 2010-08-05 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子
WO2019049867A1 (fr) * 2017-09-06 2019-03-14 日産化学株式会社 Composition d'encre
WO2020012601A1 (fr) * 2018-07-12 2020-01-16 日立化成株式会社 Polymère de transport de charges et élément électronique organique
WO2020090294A1 (fr) * 2018-10-31 2020-05-07 日立化成株式会社 Composé ionique, matériau électronique organique, composition d'encre et dispositif électronique organique
WO2020158410A1 (fr) * 2019-01-31 2020-08-06 日産化学株式会社 Vernis de transport de charges

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002504485A (ja) * 1998-02-20 2002-02-12 ザ ダウ ケミカル カンパニー 拡大したアニオンを含む触媒活性化剤
WO2003062208A1 (fr) * 2002-01-17 2003-07-31 General Electric Company Sels d'onium avec un anion d'imidazolidine a faible coordination utilises comme initiateurs cationiques
JP2010171373A (ja) * 2008-12-25 2010-08-05 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子
WO2019049867A1 (fr) * 2017-09-06 2019-03-14 日産化学株式会社 Composition d'encre
WO2020012601A1 (fr) * 2018-07-12 2020-01-16 日立化成株式会社 Polymère de transport de charges et élément électronique organique
WO2020090294A1 (fr) * 2018-10-31 2020-05-07 日立化成株式会社 Composé ionique, matériau électronique organique, composition d'encre et dispositif électronique organique
WO2020158410A1 (fr) * 2019-01-31 2020-08-06 日産化学株式会社 Vernis de transport de charges

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