WO2020027014A1 - Polymère et son utilisation - Google Patents

Polymère et son utilisation Download PDF

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Publication number
WO2020027014A1
WO2020027014A1 PCT/JP2019/029571 JP2019029571W WO2020027014A1 WO 2020027014 A1 WO2020027014 A1 WO 2020027014A1 JP 2019029571 W JP2019029571 W JP 2019029571W WO 2020027014 A1 WO2020027014 A1 WO 2020027014A1
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group
substituted
carbon atoms
fluorine atom
atom
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PCT/JP2019/029571
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English (en)
Japanese (ja)
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博史 太田
倉田　陽介
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日産化学株式会社
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Priority to KR1020217005350A priority Critical patent/KR20210037688A/ko
Priority to JP2020533514A priority patent/JP7322884B2/ja
Priority to CN201980050008.XA priority patent/CN112513140B/zh
Publication of WO2020027014A1 publication Critical patent/WO2020027014A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants

Definitions

  • the present invention relates to a polymer and its use.
  • Low molecular weight compounds and high molecular weight compounds having a charge transporting property are used in various electronic devices such as organic electroluminescence (EL) devices and organic solar cells.
  • EL organic electroluminescence
  • a polymer having a triarylamine as a repeating unit such as triphenylamine which contributes to a high charge transport property
  • a triarylamine polymer has many related reports because of its high charge transport property.
  • organic EL devices that are put into practical use in the field of displays and the like include organic functional layers such as a hole injection layer and a hole transport layer. These organic functional layers reduce the driving voltage of the device and improve the lifetime. It plays an important role to realize high performance such as.
  • the method for forming the organic functional layer of the organic EL element can be roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. It is necessary to form an organic functional layer. Under these circumstances, development of an organic EL element in which an organic functional layer is formed by a wet process has been advanced (for example, Patent Documents 4 to 6).
  • the present invention has been made in view of the above circumstances, a polymer having good solubility in an organic solvent and a method for producing the same, and a charge transporting composition containing a charge transporting substance comprising the polymer, It is an object to provide a charge transporting thin film obtained from the charge transporting composition and an organic EL device having the charge transporting thin film.
  • the present inventors have conducted intensive studies in order to achieve the above object, and as a result, a polymer containing a predetermined triphenylamine structure and a —NH— structure in a repeating unit has good solubility in an organic solvent. The inventors have found that the present invention has been completed.
  • L 01 represents —S—, —O—, —CO—, —CH 2 —, — (CH 2 ) 2 —, —C (CH 3 ) 2 —, —CF 2 —, — (CF 2 ) 2— , —C (CF 3 ) 2 — or a fluorene-9,9-diyl group
  • L 02 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, a fluorine atom Represents an alkynyl group having 2 to 20 carbon atoms which may be substituted by or an aryl group having 6 to 20 carbon atoms which may be substituted by R, L 03 and L 04 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom
  • R represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, or a carbon atom which may be substituted by a fluorine atom.
  • Ar represents a group represented by any of formulas (S1) to (S6), a 011 to a 183 are each independently an integer indicating the number of substituents to be substituted on the aromatic ring; a 071 , a 081 , a 091 , a 101 and a 111 are from 0 to 3, a 051, a 061, a 072 , a 082, a 092, a 102, a 112, a 113, a 114, a 121, a 131, a 141, a 151, a 161, a 171, a 181, a 182 And a 183 is from 0 to 4, a 011 , a 052 , a 062 , a 122 , a 123 and a 132 are from 0 to 5, a 021 , a 133 , a 142 , a 143 , a 152 ,
  • a charge-transporting composition comprising a charge-transporting substance comprising the polymer according to any one of 1 to 3, and an organic solvent; 5.
  • the charge-transporting composition further comprising a charge-receiving substance or a charge-receiving substance precursor, 6.
  • X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group, and Ph and G have the same meanings as described above.
  • the polymer of the present invention contains an —NH— structure together with a predetermined triphenylamine structure in its repeating unit, the polymer has both excellent charge transporting properties and excellent solubility in an organic solvent.
  • a charge-transporting composition that provides a charge-transporting thin film capable of achieving excellent properties when applied to an electronic device such as an organic EL device by being dissolved alone or together with a dopant substance or a dopant substance precursor in an organic solvent. Can be easily prepared.
  • the charge transporting thin film of the present invention as a hole injection layer of an organic EL device, an organic EL device having excellent characteristics can be obtained.
  • the polymer of the present invention contains a repeating unit represented by the formula (P1).
  • Ph represents a 1,4-phenylene group
  • G represents a monovalent group represented by any of formulas (A01) to (A18).
  • L 01 represents —S—, —O—, —CO—, —CH 2 —, — (CH 2 ) 2 —, —C (CH 3 ) 2 —, —CF 2 —, — (CF 2 ) 2 — , -C (CF 3 ) 2 -or fluorene-9,9-diyl group.
  • L 02 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, a fluorine atom Represents an alkynyl group having 2 to 20 carbon atoms which may be substituted by an aryl group or an aryl group having 6 to 20 carbon atoms which may be substituted by R.
  • the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • the alkenyl group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include an ethenyl group, an n-1-propenyl group, an n-2-propenyl group, and a 1-methylethenyl group. , N-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1 -Propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group and the like.
  • the alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, and an n-1- Butynyl group, n-2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4 -Pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n -1-decynyl group and the like.
  • aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, and 2-phenanthryl.
  • L 03 and L 04 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, or an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom Represents an alkynyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, or an aryl group having 6 to 20 carbon atoms which may be substituted by R.
  • Z 01 to Z 18 each independently represent a substituent substituted on an aromatic ring, and each independently represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, or a carbon atom which may be substituted by a fluorine atom.
  • R represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, or a carbon atom which may be substituted by a fluorine atom. Represents 2 to 20 alkynyl groups.
  • L 03 and L 04 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms and an alkynyl group having 2 to 20 carbon atoms in Z 01 to Z 18 and R, and 6 carbon atoms in L 03 and L 04
  • Specific examples of the 20 to 20 aryl groups are the same as those described above.
  • Preferred examples of the group represented by the formula (A01) include, but are not limited to, the following. (In the formula, Z 01 has the same meaning as described above.)
  • Z 01 represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom.
  • An alkenyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom, and an alkynyl group having 2 to 20 carbon atoms which may be substituted by a fluorine atom are preferable.
  • an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom is more preferable, and an alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom is preferable. More preferred.
  • the substituent Z 01 in the formulas (A01-1) to (A01-3) is an alkyl group having 1 to 20 carbon atoms which may be substituted by a fluorine atom
  • the alkyl group is bonded to an aromatic ring.
  • the bond to be formed is preferably on a secondary or tertiary carbon atom of the alkyl group, more preferably on a secondary carbon atom.
  • Z 01 represents an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentan-2-yl group, an n- Pentan-3-yl group, n-hexane-2-yl group, n-hexane-3-yl group, n-heptane-2-yl group, n-heptane-3-yl group, n-heptan-4-yl Groups, n-octan-2-yl group, n-octan-3-yl group, n-octan-4-yl group, and the like, but are not limited thereto.
  • the number of carbon atoms of the alkyl group, alkenyl group and alkynyl group in the formula (P1) is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less, from the viewpoint of solubility in an organic solvent. More preferably, it is 5 or less, and the carbon number of the aryl group is preferably 15 or less, more preferably 10 or less.
  • Ar represents a group represented by any of formulas (S1) to (S6).
  • a 011 to a 183 are integers each independently indicating the number of substituents to be substituted on the aromatic ring.
  • a 071 , a 081 , a 091 , a 101 and a 111 are 0 to 3.
  • a 183 is 0-4 .
  • a 011 , a 052 , a 062 , a 122 , a 123 and a 132 are 0 to 5.
  • a 021 , a 133 , a 142 , a 143 , a 152 , a 153 , a 162 and a 163 are from 0 to 7.
  • a 031 and a 041 are 0 to 9;
  • a 011 is preferably 0 to 3, more preferably 1 or 2.
  • a 021 to a 183 are preferably 0 or 1, and more preferably 0.
  • the polymer of the present invention does not necessarily need to have all the repeating units having the same structure, and may contain repeating units having different structures included in the formula (P1). Further, each unit may be bonded randomly or as a block polymer.
  • the content of the repeating unit represented by the formula (P1) in the polymer of the present invention is preferably 50 mol in all the repeating units contained in the polymer, from the viewpoint of obtaining a polymer having excellent charge transportability and solubility. %, More preferably at least 70 mol%, even more preferably at least 90 mol%, further preferably at least 95 mol%, and most preferably 100 mol%.
  • the weight average molecular weight of the polymer of the present invention is usually 1,000 to 100,000, but from the viewpoint of solubility in an organic solvent, is preferably 20,000 or less, more preferably 10,000 or less, From the viewpoint of charge transportability, it is preferably at least 3,000, more preferably at least 5,000.
  • the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter, referred to as GPC) analysis in terms of standard polystyrene.
  • the polymer of the present invention can be produced by reacting a triphenylamine derivative represented by the formula (A1) with a triphenylamine derivative represented by the formula (H1).
  • X independently represents a chlorine atom, a bromine atom, an iodine atom or a pseudohalogen group
  • Ph and G have the same meanings as described above.
  • pseudohalogen group examples include (fluoro) alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group and nonafluorobutanesulfonyloxy group; aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group. Is mentioned.
  • the charging ratio of the triphenylamine derivative represented by the formula (A1) and the triphenylamine derivative represented by the formula (H1) is the same as that of the triphenylamine derivative represented by the formula (H1).
  • the triphenylamine derivative represented by the formula can be used in an amount of 1 equivalent or more, but about 1 to 1.5 equivalents is preferable.
  • Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, and copper iodide; Pd (PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium), Pd (PPh 3 ) 2 Cl 2 (bis (triphenylphosphine) dichloropalladium), Pd (dba) 2 (bis (dibenzylideneacetone) palladium), Pd 2 (dba) 3 (tris (dibenzylideneacetone) dipalladium), Pd (Pt And palladium catalysts such as —Bu 3 ) 2 (bis (tri (t-butylphosphine)) palladium) and Pd (OAc) 2 (palladium acetate).
  • copper catalysts such as copper chloride, copper bromide, and copper iodide
  • Pd (PPh 3 ) 4 tetrakis (triphenylphosphine) palladium
  • These catalysts may be used alone or in combination of two or more. Further, these catalysts may be used together with a known suitable ligand.
  • ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine.
  • the amount of the catalyst used can be about 0.01 to 0.2 mol, preferably about 0.1 mol, per 1 mol of the triphenylamine derivative represented by the formula (H1).
  • the amount of the ligand used can be 0.1 to 5 equivalents to the metal complex (catalyst) to be used, but is preferably 1 to 2 equivalents.
  • each of the above reactions is carried out in a solvent.
  • a solvent its type is not particularly limited as long as it does not adversely affect the reaction.
  • Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatics Aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenz
  • the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is preferably about 0 to 200 ° C, more preferably 20 to 150 ° C.
  • a post-treatment is carried out according to a conventional method to obtain a desired polymer.
  • triphenylamine derivative represented by the formula (A1) used in the production of the polymer of the present invention a commercially available product may be used, or it may be produced by the following method according to the scheme shown below. According to a known method, the following predetermined aniline derivative is reacted with, for example, 4-fluoronitrobenzene to obtain a corresponding dinitro compound. Then, the nitro group of the obtained dinitro compound is converted into an amino group by a hydrogenation reaction using, for example, Pd / C.
  • the triphenylamine derivative represented by the formula (H1) used in the production of the polymer of the present invention may be a commercially available product, and the corresponding triphenylamine derivative is halogenated or pseudo-halogenated according to the scheme shown below. You may. Halogenation or pseudohalogenation can be performed using a halogenating reagent or a pseudohalogenating reagent according to a standard method.
  • K is an integer indicating a repeating unit and is determined according to the molecular weight of the polymer.
  • the polymer of the present invention exhibits good solubility in an organic solvent, and a charge transporting composition can be produced by dissolving the polymer of the present invention in an organic solvent as a charge transporting substance.
  • an organic solvent a highly soluble organic solvent that can satisfactorily dissolve the polymer of the present invention can be used.
  • low polar and highly soluble organic solvents such as chlorinated solvents such as chloroform and chlorobenzene, and aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene and 3-phenoxytoluene;
  • Amide solvents such as dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutylamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, ketone solvents such as isophorone and cyclohexanone, acetic acid
  • Highly polar organic solvents such as ester solvents such as ethyl and methyl benzoate, polyhydric alcohol solvents such as ethylene glycol and diethylene glycol, ether solvents such as tetrahydrofuran, dioxan
  • the organic solvent has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a high viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure). At least one solvent may be contained. By adding such a solvent, the viscosity of the charge transporting composition can be easily adjusted, and a composition can be prepared according to a coating method to be used, which gives a highly flat thin film with good reproducibility.
  • high-viscosity organic solvent examples include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, Examples include, but are not limited to, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, and the like.
  • the high-viscosity organic solvent may also serve as the high-solubility organic solvent, which depends on the structure of the polymer as the charge transporting substance.
  • a high-viscosity organic solvent When a high-viscosity organic solvent is added, its addition ratio is preferably within a range in which no solid precipitates. As long as no solid precipitates, 5 to 90% by mass of the total solvent used in the charge transporting composition is used. preferable.
  • other solvents are used in an amount of 1 to 90% by mass based on the total solvent used in the charge transporting composition. Preferably, they can be mixed at a ratio of 1 to 50% by mass.
  • Examples of such a solvent include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether.
  • Examples include, but are not limited to, ether acetate, diethylene glycol monoethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, n-hexyl acetate, and the like. These solvents can be used alone or in combination of two or more.
  • the solvent used for the same purpose may also have the function of a highly soluble organic solvent.
  • the charge transporting composition of the present invention may contain a dopant substance (charge accepting substance) or a dopant substance precursor (charge accepting substance precursor) for the purpose of improving the charge transporting property of the obtained charge transporting thin film. Good.
  • the dopant substance is not particularly limited as long as it is soluble in at least one solvent used for the charge transporting composition.
  • the organic charge receiving substance include arylsulfonic acid, anion and a counter cation thereof.
  • One preferred example of the charge transporting composition of the present invention contains a dopant substance precursor comprising a sulfonic acid ester compound represented by the formula (1).
  • R 1 and R 2 independently represent a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group
  • R 3 represents a linear or branched monovalent aliphatic hydrocarbon. Represents a group.
  • the total number of carbon atoms of R 1 , R 2 and R 3 is 6 or more.
  • the upper limit of the total number of carbon atoms of R 1 , R 2 and R 3 is not particularly limited, but is preferably 20 or less, more preferably 10 or less.
  • the linear or branched monovalent aliphatic hydrocarbon group is not particularly limited, but may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, C1-C18 alkyl groups such as n-hexyl group, n-octyl group, 2-ethylhexyl group and decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2 And alkenyl groups having 2 to 18 carbon atoms such as -propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and hexenyl group.
  • R 1 is preferably a hydrogen atom
  • R 2 and R 3 are preferably alkyl groups having 1 to 6 carbon atoms. In this case, R 2 and R 3 may be the same or different.
  • a 1 represents -O- or -S-, preferably -O-.
  • a 2 represents an (n + 1) -valent aromatic hydrocarbon group.
  • a 3 represents a substituted or unsubstituted m-valent hydrocarbon group containing one or more aromatic rings.
  • the (n + 1) -valent aromatic hydrocarbon group represented by A 2 is a group obtained by removing (n + 1) hydrogen atoms from the aromatic ring of the aromatic hydrocarbon compound.
  • the aromatic hydrocarbon compound include benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene.
  • a 2 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
  • a substituted or unsubstituted m-valent hydrocarbon group containing one or more aromatic rings represented by A 3 is an atom bonded to a carbon skeleton from a substituted or unsubstituted hydrocarbon compound containing one or more aromatic rings. Or a group obtained by removing m atomic groups.
  • the hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene, and some or all of the hydrogen atoms of these groups further have a hydroxy group, an amino group, a silanol group, and a thiol group.
  • a 3 is a divalent or trivalent derivative derived from 1,3,5-triazine.
  • a divalent group, a divalent or trivalent group derived from substituted or unsubstituted naphthalene, a divalent to tetravalent group derived from perfluorobiphenyl, and the like are preferable, and a divalent perfluorobiphenyl group is more preferable. preferable.
  • M represents an integer satisfying 2 ⁇ m ⁇ 4, preferably 2.
  • n represents an integer satisfying 1 ⁇ n ⁇ 4, preferably 2.
  • the sulfonic acid ester compound represented by the formula (1) can also be synthesized by the method described in WO 2017/217457.
  • the charge transporting composition of the present invention contains a dopant substance or a dopant substance precursor, the content thereof cannot be unconditionally defined because it is appropriately determined according to the kind or the desired charge transporting property.
  • the total of the dopant substance and the dopant substance precursor is in the range of 0.01 to 10 with respect to the polymer 1 of the present invention.
  • the charge transporting substance, the dopant substance, and the dopant substance precursor are preferably completely dissolved in the solvent or are in a state of being uniformly dispersed. It is.
  • the charge transporting composition of the present invention can also contain water as a solvent, but when the charge transporting thin film obtained from the composition is used as a hole injection layer of an organic EL device, a highly durable device can be reproducibly prepared.
  • the content of water is preferably 10% by mass or less, more preferably 5% by mass or less of the whole solvent, and it is optimal to use only an organic solvent as the solvent.
  • “only organic solvent” means that only the organic solvent is used as the solvent, and denies the existence of “water” contained in a trace amount in the organic solvent or solid content used. It does not do.
  • the solid content means components other than the solvent contained in the charge transporting composition.
  • the charge transporting composition is dissolved in an organic solvent, and then filtered using a submicrometer-order filter or the like. It is desirable to do.
  • the solid concentration in the charge transporting composition of the present invention is usually about 0.1 to 20% by mass, preferably 0.5 to 20% by mass, from the viewpoint of securing a sufficient film thickness while suppressing the deposition of the charge transporting substance. 1515% by mass.
  • the viscosity of the charge transporting composition of the present invention is usually 1 to 50 mPa ⁇ s at 25 ° C., and the surface tension is usually 20 to 50 mN / m at 25 ° C.
  • the viscosity and surface tension of the charge transporting composition of the present invention are determined by changing the type of the organic solvent used, their ratio, the solid content, and the like, in consideration of various factors such as a coating method to be used and a desired film thickness. Can be adjusted.
  • the charge transporting composition of the present invention can be produced by dissolving the polymer of the present invention in an organic solvent.
  • the polymer of the present invention may be dissolved in an organic solvent in advance, and another organic solvent may be sequentially added thereto.
  • a mixed solvent of all the solvents to be used may be prepared in advance, and the polymer of the present invention may be dissolved therein.
  • the charge transporting composition of the present invention contains components other than the polymer of the present invention and a solvent. If necessary, the composition may be heated to promote the dissolution of the polymer or the like, while taking care not to decompose or alter the components contained in the composition.
  • the charge transporting thin film of the present invention can be formed on a substrate by applying the charge transporting composition of the present invention on a substrate and baking it.
  • Examples of the method for applying the charge transporting composition include, but are not limited to, a dip method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an ink jet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the charge transporting composition according to the coating method.
  • the firing conditions are not particularly limited. For example, heating and firing are performed using a hot plate. Usually, the firing temperature is in the range of 100 to 260 ° C., and the firing time is in the range of 1 minute to 1 hour.
  • the firing atmosphere is also not particularly limited, but is preferably under air. Further, if necessary, multi-stage firing may be performed at two or more different temperatures.
  • the thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 300 nm when used as a functional layer of an organic EL device.
  • a method of changing the film thickness there are a method of changing a solid concentration in the charge transporting composition, a method of changing a liquid amount at the time of coating, and the like.
  • the organic EL device of the present invention has a pair of electrodes, and has the above-described charge transporting thin film of the present invention between these electrodes.
  • Representative configurations of the organic EL device include the following (a) to (f), but are not limited thereto.
  • an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode as necessary.
  • the hole injection layer, the hole transport layer, or the hole injection / transport layer may also have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection / transport layer may be a hole (hole).
  • anode / hole injection layer / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / emission layer / electron injection transport layer / Cathode (c) anode / hole injection / transport layer / emission layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / emission layer / cathode (f) anode / hole injection / transport layer / emission layer / cathode
  • Hole injection layer “hole transport layer” and “hole injection transport layer” are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. It has a function, when only one layer of a hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and between the light emitting layer and the anode, When two or more layers of the hole transporting material are provided, a layer close to the anode is a “hole injection layer”, and the other layers are a “hole transport layer”.
  • the hole injection (transport) layer a thin film that is excellent in not only the property of accepting holes from the anode but also the property of injecting holes into the hole transport (emission) layer is used.
  • Electrode injection layer is layers formed between the light emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light emitting layer.
  • an electron injecting and transporting layer When only one layer of an electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injecting and transporting layer”, and the layer of the electron transporting material is provided between the light emitting layer and the cathode.
  • the “electron injection layer” is an organic layer having a light-emitting function, and includes a host material and a dopant material when a doping system is employed.
  • the host material mainly has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material efficiently emits excitons obtained by the recombination.
  • a host material has a function of mainly confining excitons generated by a dopant in a light-emitting layer.
  • the charge transporting thin film of the present invention can be suitably used as an organic functional film provided between an anode and a light emitting layer in an organic EL device. And more preferably as a hole injection layer.
  • One example of a method for producing an OLED element having a hole injection layer formed of a thin film obtained from the charge transporting composition of the present invention is as follows.
  • the electrode is preferably subjected to cleaning with alcohol, pure water, or the like, or surface treatment such as UV ozone treatment or oxygen-plasma treatment in advance within a range that does not adversely affect the electrode.
  • the hole injection layer composed of the charge transporting thin film of the present invention is formed on the anode substrate by the above method. This is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron transport layer / hole block layer, and a cathode metal are sequentially deposited.
  • a hole transporting layer forming composition including a hole transporting polymer and a light emitting layer forming composition including a light emitting polymer are included. These layers are formed using a wet process. Note that, if necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
  • anode material examples include a transparent electrode typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode composed of a metal typified by aluminum, an alloy thereof, and the like. It is preferable that the material has been subjected to a chemical treatment. A polythiophene derivative or a polyaniline derivative having a high charge transporting property can also be used.
  • the other metal constituting the metal anode includes, but is not limited to, gold, silver, copper, indium and alloys thereof.
  • Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N, N′-bis (naphthalen-1-yl) -N, N′-bis (Phenyl) -benzidine ( ⁇ -NPD), 4,4 ′, 4 ′′ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ′′ -tris [1 -Naphthyl (phenyl) amino] triphenylamine (1-TNATA) and the like, and 5,5 ′′ -bis- ⁇ 4- [bis (4-methylphenyl) amino] phenyl ⁇ -2,2 ′: Oligothiophenes such as 5 ′, 2 ′′ -terthiophene (BMA-3T) are exemplified.
  • Materials for forming the light emitting layer include metal complexes such as 8-hydroxyquinoline aluminum complexes, metal complexes of 10-hydroxybenzo [h] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, (2-hydroxyphenyl) benzo.
  • Low molecular light emitting materials such as thiazole metal complexes and silole derivatives; poly (p-phenylenevinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly (3-alkyl Examples thereof include a system in which a light-emitting material and an electron transfer material are mixed with a high molecular compound such as thiophene) and polyvinyl carbazole, but are not limited thereto.
  • the light emitting layer may be co-deposited with a light emitting dopant.
  • a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) may be used.
  • naphthacene derivatives such as rubrene, quinacridone derivatives, condensed polycyclic aromatic rings such as perylene, and the like, but are not limited thereto.
  • Materials for forming the electron transport layer / hole block layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.
  • Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). But not limited thereto.
  • Cathode materials include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
  • Materials for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.
  • the luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV); polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
  • polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV)
  • polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
  • the used apparatus is as follows. (1) Substrate cleaning: Choshu Sangyo Co., Ltd. substrate cleaning system (reduced pressure plasma method) (2) Application of composition: Spin coater MS-A100 manufactured by Mikasa Corporation (3) Fabrication of element: Multifunctional vapor deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
  • Multi-channel IVL measuring device manufactured by ECH Corporation (5) Life measurement of EL element (measurement of half-life): Organic EL luminance life evaluation system PEL manufactured by ECH Corporation -105S (6) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn): manufactured by Shimadzu Corporation (column: SHOdex GPC KF-803L + GPC KF-804L, column temperature: 40 ° C., detector: UV detector (254 nm) ) And RI detector, eluent: 0.5% Et 3 N / THF, column flow rate: 1.0 mL / min.) (7) 1 H-NMR: Ascend500 manufactured by Bruker (8) LC / MS: ZQ2000 manufactured by Waters
  • the cooled reaction solution was mixed with water (34 mL), liquid separation was performed using the obtained mixture and toluene (17 mL ⁇ 2), and the organic layer was recovered and sulfuric acid was collected. Dried with sodium. Next, the dried organic layer was concentrated, and the obtained concentrate was diluted with tetrahydrofuran (17 mL), and the obtained diluted substance was dropped into methanol (340 mL) and stirred for 1 hour. Thereafter, the precipitated powder was collected by suction filtration, the obtained residue was dissolved in tetrahydrofuran (17 mL), and this solution was added dropwise to methanol (340 mL), stirred for 1 hour, and the precipitated powder was collected by suction filtration.
  • the polymer A was obtained by drying under reduced pressure (2.20 g).
  • Compound 3 was prepared according to the method described in J. Am. Mater. Chem. , 2011, 21, 11800.
  • Example 3 Fabrication of single-layer device and evaluation of characteristics
  • the charge transporting composition obtained in Example 2 was applied to an ITO substrate using a spin coater, dried at 120 ° C. for 1 minute in the atmosphere, and then baked at 230 ° C. for 15 minutes to form a film on the ITO substrate. A uniform thin film of 40 nm was formed.
  • As the ITO substrate a 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate having a patterned indium tin oxide (ITO) film with a thickness of 50 nm formed on the surface was used. Before use, an O 2 plasma cleaning device (150 W) was used. , 30 seconds) to remove impurities on the surface.
  • ITO indium tin oxide
  • an aluminum film was formed thereon with a thickness of 80 nm at a rate of 0.2 nm / sec using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa) to obtain a single-layer element.
  • a vapor deposition apparatus degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa
  • the characteristics of the single-layer element were evaluated after being sealed with a sealing substrate. Sealing was performed in the following procedure. In a nitrogen atmosphere having an oxygen concentration of 2 ppm or less and a dew point of -76 ° C. or less, the element is placed between sealing substrates, and the sealing substrates are bonded with an adhesive (Moresco Moisture Cut WB90US (P), manufactured by MORESCO Corporation).
  • a water catching agent (HD-071010W-40, manufactured by Dynic Corp.) was housed in the sealing substrate together with the device.
  • the bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
  • the thin film obtained from the charge transporting composition of the present invention exhibited excellent charge transporting properties.
  • Example 4 Production of organic EL element and evaluation of characteristics [Example 4] A thin film was formed on an ITO substrate using the charge transporting composition obtained in Example 2 in the same manner as in Example 3 except that the film thickness was changed to 50 nm. Then, a 30 nm film of ⁇ -NPD was formed on the formed thin film at a rate of 0.2 nm / sec using an evaporation apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa). An electron block material HTEB-01 manufactured by the company was formed into a film having a thickness of 10 nm.
  • a light-emitting layer host material NS60 and a light-emitting layer dopant material Ir (PPy) 3 manufactured by Nippon Steel & Sumikin Chemical Co. were co-evaporated thereon.
  • the deposition rate was controlled so that the concentration of Ir (PPy) 3 became 6%, and the layers were stacked to a thickness of 40 nm.
  • a thin film of Alq 3 , lithium fluoride and aluminum was sequentially laminated to obtain an organic EL device.
  • the deposition rate was 0.2 nm / sec for Alq 3 and aluminum, and 0.02 nm / sec for lithium fluoride, and the film thickness was 20 nm, 0.5 nm and 80 nm, respectively.
  • the element was sealed in the same manner as in Example 3, and the characteristic was evaluated.
  • the organic EL device provided with the charge transporting thin film obtained from the charge transporting composition of the present invention was suitably driven and had excellent durability.

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  • Medicinal Chemistry (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Selon la présente invention, un polymère qui contient, par exemple, une unité de répétition représentée par la formule AA présente à la fois d'excellentes propriétés de transport de charge et une excellente solubilité dans des solvants organiques ; et d'excellentes caractéristiques peuvent être obtenues dans des cas où ce polymère est dissous dans un solvant organique par lui-même ou conjointement avec une substance dopante, puis appliqué à des éléments électroniques comprenant un élément EL organique.
PCT/JP2019/029571 2018-08-01 2019-07-29 Polymère et son utilisation WO2020027014A1 (fr)

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