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WO2016039360A1 - Vernis à transport de charge - Google Patents

Vernis à transport de charge Download PDF

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Publication number
WO2016039360A1
WO2016039360A1 PCT/JP2015/075541 JP2015075541W WO2016039360A1 WO 2016039360 A1 WO2016039360 A1 WO 2016039360A1 JP 2015075541 W JP2015075541 W JP 2015075541W WO 2016039360 A1 WO2016039360 A1 WO 2016039360A1
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Prior art keywords
group
charge transporting
bis
carbon atoms
thin film
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PCT/JP2015/075541
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English (en)
Japanese (ja)
Inventor
春香 古賀
直樹 中家
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日産化学工業株式会社
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Priority to KR1020177002213A priority Critical patent/KR102388046B1/ko
Priority to JP2016547466A priority patent/JP6558373B2/ja
Priority to CN201580048660.XA priority patent/CN106688120B/zh
Publication of WO2016039360A1 publication Critical patent/WO2016039360A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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]
    • H10K50/17—Carrier injection layers
    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Definitions

  • the present invention relates to a charge transporting varnish.
  • Organic electroluminescence (EL) elements are expected to be put to practical use in fields such as displays and lighting, and various developments regarding materials and element structures have been made for the purpose of low voltage driving, high luminance, long life, etc. .
  • a plurality of functional thin films are used in the organic EL element, and the hole injection layer, which is one of them, bears charge transfer between the anode and the hole transport layer or the light emitting layer, and the low voltage of the organic EL element. It performs important functions to achieve drive and high brightness.
  • This hole injection layer forming method is roughly classified into a dry process typified by vapor deposition and a wet process typified by spin coating. Compared to these processes, the wet process can efficiently produce a thin film with a large area and high flatness. Therefore, particularly in the display field, not only the hole injection layer but also the hole transport layer and the light emitting layer are used. For example, a wet process is often used to form an upper layer (see Patent Document 1).
  • JP 2008-78181 A International Publication No. 2006/025342 International Publication No. 2008/032616 International Publication No. 2008/129947 International Publication No. 2010/041701 International Publication No. 2010/058777 International Publication No. 2013/042623 JP 2008-27646 A
  • the present invention has been made in view of the above circumstances, has high flatness and high charge transportability, is excellent in coatability of the upper layer material, and exhibits excellent luminance characteristics when applied to an organic EL element.
  • An object of the present invention is to provide a charge transporting varnish capable of providing a thin film.
  • Patent Documents 3 and 4 disclose a thin film obtained from a charge transporting varnish comprising an oligoaniline derivative, an electron-accepting or hole-accepting dopant substance, a silane compound, and an organic solvent, and an organic EL device comprising the same.
  • the silane compound used in the present invention and the charge transporting varnish containing the silane compound are not specifically disclosed, and the thin film obtained from the varnish is excellent in the applicability of the upper layer material applied thereon. There is neither a description teaching nor a suggestion.
  • a charge transporting varnish comprising a charge transporting material, a dopant material, an organosilane compound having a chlorine-containing monovalent hydrocarbon group as a substituent, and an organic solvent, 2.
  • a method for producing a charge transporting thin film which comprises applying a charge transporting varnish of any one of 1 to 5 on a substrate and evaporating a solvent.
  • the thin film obtained from the charge transporting varnish of the present invention has high flatness and high charge transportability, and an organic EL device capable of realizing good luminance characteristics when the thin film is applied to a hole injection layer. can get. Further, the thin film obtained from the charge transporting varnish of the present invention contains a chlorine atom-containing monovalent hydrocarbon group derived from a silane compound, but the contact angle of the solvent used for the upper layer material of the surface is silane. There is no difference from the thin film obtained without adding the compound.
  • the charge transporting varnish of the present invention can produce a thin film excellent in charge transporting properties with good reproducibility even when using various wet processes capable of forming a film over a large area such as a spin coating method or a slit coating method, It can sufficiently cope with recent progress in the field of organic EL elements.
  • the thin film obtained from the charge transporting varnish of the present invention can also be used as an antistatic film, an anode buffer layer of an organic thin film solar cell, or the like.
  • the charge transporting varnish according to the present invention includes a charge transporting substance, a dopant substance, an organic silane compound having a chlorine-containing monovalent hydrocarbon group as a substituent, and an organic solvent.
  • the charge transportability is synonymous with conductivity and is synonymous with hole transportability.
  • the charge transporting substance itself may be charge transporting, or may be charge transporting when used together with a dopant substance (electron accepting substance).
  • the charge transporting varnish may itself have a charge transporting property, and the resulting solid film may have a charge transporting property.
  • the charge transporting substance used in the present invention is not particularly limited as long as it is a substance having a charge transporting property.
  • charge transporting monomers, charge transporting oligomers or polymers used in the field of organic EL devices and the like are used.
  • a charge transporting oligomer is preferable because a charge transporting varnish that gives a highly flat charge transporting thin film can be prepared with good reproducibility.
  • charge transporting oligomers include oligoaniline derivatives, N, N′-diarylbenzidine derivatives, N, N, N ′, N′-tetraarylbenzidine derivatives and other aniline derivatives (arylamine derivatives), oligothiophene derivatives
  • arylamine derivatives oligoaniline derivatives
  • thiophene derivatives such as thienothiophene derivatives and thienobenzothiophene derivatives
  • pyrrole derivatives such as oligopyrrole derivatives.
  • arylamine derivatives and thiophene derivatives are preferable, and arylamine derivatives are more preferable. preferable.
  • the molecular weight of the charge transporting oligomer is not particularly limited as long as it dissolves in an organic solvent, but is usually 200 to 9,000. From the viewpoint of obtaining a thin film with higher charge transportability with a high reproducibility, the molecular weight is preferably 300 or more, more preferably 400 or more, from the viewpoint of preparing a uniform varnish that gives a highly flat thin film with a good reproducibility. 8,000 or less, more preferably 7,000 or less, even more preferably 6,000 or less, and even more preferably 5,000 or less.
  • the charge transporting material such as the charge transporting oligomer preferably has no molecular weight distribution (dispersity of 1) (that is, a single Preferably molecular weight).
  • aniline derivative examples include those represented by the formula (1), but are not limited thereto.
  • X 1 represents —NY 1 —, —O—, —S—, — (CR 7 R 8 ) L —, or a single bond, and when m1 or m2 is 0, —NY 1 — is represented.
  • Y 1 is independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 , or It represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 2 .
  • alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic.
  • Straight chain having 1 to 20 carbon atoms such as a group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.
  • Chain or branched alkyl group cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group
  • cyclic alkyl groups having 3 to 20 carbon atoms such as a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group.
  • alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 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- Examples thereof include a 1-pentenyl group, an n-1-decenyl group, and an n-1-eicosenyl group.
  • alkynyl group having 2 to 20 carbon atoms examples include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl.
  • aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
  • heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, Examples include 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, and the like.
  • R 7 and R 8 are independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z 1.
  • Y 2 to Y 13 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 , or It represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z 2 .
  • Z 1 is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an aryl having 6 to 20 carbon atoms which may be substituted with Z 3 Or a heteroaryl group having 2 to 20 carbon atoms.
  • Z 2 is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or an alkyl having 1 to 20 carbon atoms which may be substituted with Z 3 A alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms.
  • Z 3 is a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, or a carboxylic acid group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group of R 7 , R 8 and Y 2 to Y 13 are the same as those described above.
  • R 7 and R 8 a hydrogen atom or an alkyl group of Z 1 is optionally ⁇ 1 to 20 carbon atoms substituted by are preferred, and a methyl group which may be substituted with a hydrogen atom or Z 1 More preferred are both hydrogen atoms.
  • L represents the number of repeating units of a divalent alkylene group represented by — (CR 7 R 8 ) — and is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, ⁇ 2 is even more preferred, with 1 being optimal.
  • the plurality of R 7 may be the same as or different from each other, and the plurality of R 8 may be the same as or different from each other.
  • X 1 is preferably —NY 1 — or a single bond.
  • Y 1 hydrogen atom or an alkyl group of Z 1 is optionally ⁇ 1 to 20 carbon atoms substituted with, more preferably a methyl group which may be substituted with a hydrogen atom or Z 1, hydrogen atom Is the best.
  • R 1 to R 4 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z 1.
  • R 1 to R 4 may be substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , or Z 2.
  • An aryl group having 6 to 14 carbon atoms is preferable, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is more preferable, and all hydrogen atoms are optimal.
  • R 5 and R 6 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms that may be substituted with Z 1 , or an aryl group having 6 to 14 carbon atoms that may be substituted with Z 2 Or a diphenylamino group optionally substituted with Z 2 (Y 3 and Y 4 are phenyl groups optionally substituted with Z 2 —NY 3 Y 4 group), preferably a hydrogen atom, a fluorine atom Or a diphenylamino group optionally substituted with a fluorine atom, more preferably a hydrogen atom or a diphenylamino group.
  • R 1 to R 4 are hydrogen atoms, fluorine atoms, alkyl groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms
  • R 5 and R 6 are hydrogen atoms, fluorine atoms, fluorine atoms
  • a diphenylamino group which may be substituted with X 1 is —NY 1 — or a single bond
  • Y 1 is preferably a hydrogen atom or a combination of methyl groups
  • R 1 to R 4 are hydrogen atoms
  • R 5 and R 5 6 is more preferably a hydrogen atom or a diphenylamino group
  • X 1 is —NH— or a combination of single bonds.
  • m1 and m2 each independently represent an integer of 0 or more and satisfy 1 ⁇ m1 + m2 ⁇ 20, but considering the balance between the charge transportability of the resulting thin film and the solubility of the aniline derivative Then, it is preferable to satisfy 2 ⁇ m1 + m2 ⁇ 8, more preferably satisfy 2 ⁇ m1 + m2 ⁇ 6, and even more preferably satisfy 2 ⁇ m1 + m2 ⁇ 4.
  • the substituent Z 1 is preferably a halogen atom or an aryl group having 6 to 20 carbon atoms which may be substituted with Z 3.
  • a phenyl group which may be substituted with 3 is more preferred, and optimally absent (ie, unsubstituted).
  • the substituent Z 2 is a halogen atom or preferably an alkyl group which may having 1 to 20 carbon atoms optionally substituted by Z 3, halogen atoms or carbon atoms and optionally substituted by Z 3 1 ⁇ 4,, It is more preferable that the alkyl group is not present (that is, unsubstituted).
  • Z 3 is preferably a halogen atom, more preferably a fluorine atom, and most preferably not present (that is, unsubstituted).
  • the alkyl group, alkenyl group, and alkynyl group preferably have 10 or less carbon atoms, more preferably 6 or less, and even more preferably 4 or less.
  • the carbon number of the aryl group and heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.
  • the method for synthesizing the aniline derivative is not particularly limited, but Bulletin of Chemical Society of Japan, 67, pp.1749-1752, (1994), Synthetic Metals, 84, pp.119-120, (1997), Thin Solid Films, 520 (24), pp. 7157-7163, (2012), International Publication No. 2008/032617, International Publication No. 2008/032616, International Publication No. 2008/129947, etc. A method is mentioned.
  • aniline derivative represented by the formula (1) examples include phenyldianiline, phenyltrianiline, phenyltetraaniline, phenylpentaaniline, tetraaniline (aniline tetramer), octaaniline (aniline octamer), Although hexadecaaniline (aniline 16-mer) and what is represented by a following formula are mentioned, it is not limited to these.
  • Examples of the organic silane compound having a chlorine-containing monovalent hydrocarbon group as a substituent on a silicon atom used in the charge transport varnish of the present invention include, for example, dialkoxysilane having a chlorine-containing monovalent hydrocarbon group as a substituent, Although trialkoxysilane is mentioned, trialkoxysilane having a chlorine-containing monovalent hydrocarbon group as a substituent is preferable.
  • Examples of the chlorine-containing monovalent hydrocarbon group include alkyl chloride groups having 1 to 20 carbon atoms, alkenyl chloride groups having 2 to 20 carbon atoms, alkynyl chloride groups having 2 to 20 carbon atoms, and aryl chlorides having 6 to 20 carbon atoms.
  • alkyl chloride groups having 1 to 20 carbon atoms and aryl chloride groups having 6 to 20 carbon atoms are preferable, alkyl chloride groups having 1 to 10 carbon atoms and aryl chloride groups having 6 to 10 carbon atoms are more preferable. preferable.
  • alkyl chloride group having 1 to 20 carbon atoms include groups in which at least one hydrogen atom of the above-described alkyl group having 1 to 20 carbon atoms is substituted with a chlorine atom. More specifically, chloromethyl group, dichloromethyl group, trichloromethyl group, 1-chloroethyl group, 1,1-dichloroethyl group, 2-chloroethyl group, 2,2-dichloroethyl group, 2,2,2- Trichloroethyl group, 1,1,2,2,2-pentachloroethyl group, 3-chloropropyl group, 3,3-dichloropropyl group, 3,3,3-trichloropropyl group, 2,2,3,3 , 3-pentachloropropyl group, 1,1,2,2,3,3,3-heptachloropropyl group and the like.
  • alkenyl chloride group having 2 to 20 carbon atoms include groups obtained by substituting at least one hydrogen atom of the alkenyl group having 2 to 20 carbon atoms with a chlorine atom. More specifically, a 1-chloroethenyl group, a 3-chloro-1-propenyl group and the like can be mentioned.
  • alkynyl chloride group having 2 to 20 carbon atoms include a group in which at least one hydrogen atom of the alkynyl group having 2 to 20 carbon atoms is replaced with a chlorine atom. More specifically, 1-chloroethynyl group, 3-chloro-1-propynyl group and the like can be mentioned.
  • aryl chloride group having 6 to 20 carbon atoms include a group obtained by substituting at least one hydrogen atom of the above aryl group having 6 to 20 carbon atoms with a chlorine atom. More specifically, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4,6-trichlorophenyl group, perchlorophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2- A naphthyl group etc. are mentioned.
  • Examples of the organic silane compounds that can be suitably used in the present invention include chloroalkyltrialkoxysilanes such as chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane, and 2-chlorophenyltrimethoxysilane.
  • Chlorophenyltrialkoxysilane such as 3-chlorophenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 2-chlorophenyltriethoxysilane, 3-chlorophenyltriethoxysilane, 4-chlorophenyltriethoxysilane, and the like.
  • Alkoxysilane is preferred, 4-chlorophenyltrialkoxysilane is more preferred, and 4-chlorophenyltrimethoxysilane is most preferred.
  • the amount of the organic silane compound having a chlorine-containing monovalent hydrocarbon group as a substituent is not particularly limited as long as it does not adversely affect the contact angle and organic EL device characteristics of the obtained thin film. And usually about 0.1 to 50% by mass, preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and still more preferably 1% with respect to the total mass of the dopant substance. About 20% by mass.
  • the dopant substance used in the charge transporting varnish of the present invention is not particularly limited as long as it is soluble in at least one solvent used in the varnish, and both inorganic dopant substances and organic dopant substances are used. it can.
  • inorganic dopant materials include inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminum chloride (III) (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), and boron tribromide (BBr 3).
  • inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid
  • BBr 3 boron tribromide
  • Organic dopant materials include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl -1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalen
  • Non-aryl sulfone compounds such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) .
  • TCNQ 7,7,8,8-tetracyanoquinodimethane
  • DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
  • heteropolyacids are suitable.
  • high hole acceptance from transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO) is achieved.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • Heteropolyacids typically have a structure in which a heteroatom is located at the center of the molecule, represented by a Keggin type represented by formula (B1) or a Dawson type chemical structure represented by formula (B2), and vanadium ( V), molybdenum (Mo), tungsten (W), and other polyacids such as isopolyacids that are oxygen acids and oxygenates of different elements are condensed.
  • a heteroatom represented by formula (B1) or a Dawson type chemical structure represented by formula (B2)
  • V vanadium
  • Mo molybdenum
  • W tungsten
  • other polyacids such as isopolyacids that are oxygen acids and oxygenates of different elements are condensed.
  • oxygen acid of such a different element mainly include silicon (Si), phosphorus (P), and arsenic (As) oxygen acids.
  • heteropolyacid examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and lintongue molybdic acid. These may be used alone or in combination of two or more. Good.
  • the heteropolyacid used by this invention is available as a commercial item, and can also be synthesize
  • the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable.
  • one of the two or more types of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
  • Heteropolyacids are those obtained as commercially available products or known syntheses even if the number of elements in the quantitative analysis such as elemental analysis is large or small from the structure represented by the general formula As long as it is appropriately synthesized according to the method, it can be used in the present invention.
  • phosphotungstic acid is represented by the chemical formula H 3 (PW 12 O 40 ) ⁇ nH 2 O
  • phosphomolybdic acid is represented by the chemical formula H 3 (PMo 12 O 40 ) ⁇ nH 2 O, respectively.
  • P (phosphorus), O (oxygen), W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product.
  • W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product.
  • it can be used in the present invention.
  • the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthesized product or commercially available product, but a commercially available form and a known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydration water and other impurities.
  • aryl sulfonic acid compounds can be suitably used as the dopant substance.
  • an aryl sulfonic acid compound represented by the formula (2) or (3) is preferable.
  • a 1 represents O or S, and O is preferable.
  • a 2 represents a naphthalene ring or an anthracene ring, and a naphthalene ring is preferable.
  • a 3 represents a divalent to tetravalent perfluorobiphenyl group, p is showed binding speed between A 1 and A 3, is an integer that satisfies 2 ⁇ p ⁇ 4,
  • a 3 is a divalent par It is preferably a fluorobiphenyl group and p is 2.
  • q represents the number of sulfonic acid groups bonded to A 2 and is an integer satisfying 1 ⁇ q ⁇ 4, but 2 is optimal.
  • a 4 to A 8 are independently of each other a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated group having 2 to 20 carbon atoms.
  • An alkenyl group is represented, and at least three of A 4 to A 8 are halogen atoms.
  • halogenated alkyl group having 1 to 20 carbon atoms examples include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3- Trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4, Examples include 4-nonafluorobutyl group.
  • alkenyl halide having 2 to 20 carbon atoms examples include a perfluorovinyl group, a perfluoropropenyl group (allyl group), a perfluorobutenyl group, and the like.
  • Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms are the same as those described above, and the halogen atom is preferably a fluorine atom.
  • a 4 to A 8 are a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkenyl halide having 2 to 10 carbon atoms.
  • at least three of A 4 to A 8 are preferably fluorine atoms, hydrogen atom, fluorine atom, cyano group, alkyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms.
  • the perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms
  • the perfluoroalkenyl group is a group in which all hydrogen atoms of the alkenyl group are substituted with fluorine atoms.
  • R represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1 ⁇ r ⁇ 4, preferably 2 to 4, and 2 is optimal.
  • the molecular weight of the aryl sulfonic acid compound used as the dopant substance is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less in consideration of solubility in an organic solvent when used with a charge transporting oligomer. It is.
  • the amount of the dopant substance used is appropriately determined in consideration of the type of the dopant substance, the desired degree of charge transportability, etc. In general, the mass ratio is in the range of 0.01 to 50 with respect to the charge transporting substance 1.
  • a highly soluble solvent that can dissolve the charge transporting material, the dopant material, and the organosilane compound satisfactorily can be used.
  • highly soluble solvents include cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol monomethyl ether, N
  • An organic solvent such as, but not limited to, N-dimethylisobutyric acid amide. These solvents can be used alone or in combination of two or more, and the amount used can be 5 to 100% by mass with respect to the total solvent used in the varnish.
  • the charge transporting substance, the dopant substance, and the organosilane compound are all preferably completely dissolved or uniformly dispersed in the above-mentioned solvent. More preferred.
  • the varnish has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure).
  • a viscosity 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure).
  • the 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. These solvents may be used alone or in combination of two or more.
  • the addition ratio of the high-viscosity organic solvent to the entire solvent used in the varnish of the present invention is preferably within a range where no solid precipitates, and the addition ratio is preferably 5 to 90% by mass as long as no solid precipitates.
  • solvents are used in an amount of 1 to 90% by mass, preferably It is also possible to mix at a ratio of 1 to 50% by mass.
  • solvents include propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol.
  • Examples include, but are not limited to, monoethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, and n-hexyl acetate. These solvents can be used alone or in combination of two or more.
  • the viscosity of the varnish of the present invention is appropriately set according to the thickness of the thin film to be produced, the solid content concentration, etc., but is usually 1 to 50 mPa ⁇ s at 25 ° C.
  • the surface tension of the varnish of the present invention is appropriately set according to the coating method used, but is usually 20 to 50 mN / m.
  • the solid content concentration of the charge transporting varnish in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc. In consideration of improving the coatability of the varnish, it is preferably about 0.5 to 5.0% by mass, more preferably about 1.0 to 3.0% by mass.
  • the solid content means a charge transporting substance and a dopant substance.
  • a charge transporting thin film can be formed on a base material by applying the charge transporting varnish described above onto the base material and baking it.
  • the coating method of the varnish is not particularly limited, and examples thereof include a dipping 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. Accordingly, it is preferable to adjust the viscosity and surface tension of the varnish.
  • the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and a high charge transport property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum. Obtainable.
  • the firing temperature is appropriately set within a range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability imparted to the obtained thin film, the type and boiling point of the solvent, and the like.
  • the obtained thin film is used as a hole injection layer of an organic EL device, it is preferably about 140 to 250 ° C., more preferably about 145 to 240 ° C.
  • a temperature change of two or more steps may be applied for the purpose of developing a higher uniform film forming property or causing the reaction to proceed on the substrate. What is necessary is just to perform using suitable apparatuses, such as oven.
  • the thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 200 nm when used as a hole injection layer in an organic EL device.
  • Methods for changing the film thickness include methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate during coating.
  • the charge transporting thin film of the present invention described above is excellent in charge transporting property and flatness. Further, on the thin film, an organic solvent such as toluene, xylene, chloroform, 3-phenoxytoluene, tetralin and the like contained in a varnish used when forming a hole transport layer or a light emitting layer of an organic EL element by a wet process. Can form a suitable coating film. Therefore, the thin film obtained from the charge transporting varnish of the present invention can be suitably used for an electronic device such as an organic EL element having a multilayer structure formed by a wet process.
  • an organic solvent such as toluene, xylene, chloroform, 3-phenoxytoluene, tetralin and the like contained in a varnish used when forming a hole transport layer or a light emitting layer of an organic EL element by a wet process.
  • the example of the manufacturing method of the OLED element which has a positive hole injection layer which consists of a thin film obtained from the charge transportable varnish of this invention is as follows.
  • the electrode substrate to be used is preferably cleaned in advance by liquid cleaning with a detergent, alcohol, pure water or the like.
  • the anode substrate is subjected to surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use. It is preferable.
  • the surface treatment may not be performed.
  • the charge transporting varnish of the present invention is applied onto the anode substrate and baked to produce a hole injection layer on the electrode.
  • This is introduced into a vacuum deposition 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 to form an OLED element.
  • an electron blocking layer may be provided between the light emitting layer and the hole transport layer.
  • the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), metal anodes typified by aluminum, alloys thereof, and the like. What performed the chemical conversion process is preferable.
  • Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
  • Other metals constituting the metal anode include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium.
  • Materials for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spirodimer, N, N′-bis (naphthalen-1-yl) -N, N′-bis (Phenyl) -benzidine ( ⁇ -NPD), N, N′-bis (naphthalen-2-yl) -N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl)- N, N′-bis (phenyl) -benzidine, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis ( Naphthalen-1-yl) -N, N′-bis (phenyl) -9,9-spirobifluorene, N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-spir
  • Materials for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq 3 ), bis (8-quinolinolato) zinc (II) (Znq 2 ), bis (2-methyl-8-quinolinolato)- 4- (p-phenylphenolate) aluminum (III) (BAlq), 4,4′-bis (2,2-diphenylvinyl) biphenyl, 9,10-di (naphthalen-2-yl) anthracene, 2-t -Butyl-9,10-di (naphthalen-2-yl) anthracene, 2,7-bis [9,9-di (4-methylphenyl) -fluoren-2-yl] -9,9-di (4- Methylphenyl) fluorene, 2-methyl-9,10-bis (naphthalen-2-yl) anthracene, 2- (9,9-spirobifluoren-2-yl) -9,9-spir
  • luminescent dopants examples include 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-10-.
  • Materials for forming the electron transport layer / hole block layer include 8-hydroxyquinolinolate-lithium, 2,2 ′, 2 ′′-(1,3,5-benztolyl) -tris (1-phenyl-1- H-benzimidazole), 2- (4-biphenyl) 5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10- Phenanthroline, 4,7-diphenyl-1,10-phenanthroline, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum, 1,3-bis [2- (2,2′-bipyridine- 6-yl) -1,3,4-oxadiazo-5-yl] benzene, 6,6′-bis [5- (biphenyl-4-yl) -1,3,4-oxadiazo-2-yl] -2 , 2'- Pyridine, 3- (4-bi
  • Materials for forming the electron injection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride ( MgF 2 ), cesium fluoride (CsF), strontium fluoride (SrF 2 ), molybdenum trioxide (MoO 3 ), aluminum, Li (acac), lithium acetate, lithium benzoate and the like.
  • Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
  • Examples of the material for forming the electron blocking layer include tris (phenylpyrazole) iridium.
  • the manufacturing method of the PLED element using the charge transportable varnish of this invention is not specifically limited, The following methods are mentioned.
  • the hole transport polymer layer and the light emitting polymer layer are sequentially formed.
  • a PLED element having a charge transporting thin film formed by the charge transporting varnish of the invention can be produced.
  • the charge transporting varnish of the present invention is applied on the anode substrate to prepare a hole injection layer by the above method, and a hole transporting polymer layer and a light emitting polymer layer are sequentially formed thereon. Then, a cathode is vapor-deposited to obtain a PLED element.
  • the hole transporting polymer layer and the light emitting polymer layer can be formed by adding a solvent to a hole transporting polymer material or a light emitting polymer material, or a material obtained by adding a dopant substance to the hole transporting polymer material. And a method of forming a film by uniformly dispersing and coating the film on a hole injection layer or a hole transporting polymer layer and then firing the respective layers.
  • Examples of the light-emitting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH). And polyphenylene vinylene derivatives such as -PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (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)
  • PVCz polyvinylcarbazole
  • Examples of the solvent include toluene, xylene, chloroform, 3-phenoxytoluene, and tetralin.
  • Examples of the dissolution or uniform dispersion method include methods such as stirring, heating and stirring, and ultrasonic dispersion.
  • the application method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dipping method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating method.
  • the application is preferably performed under an inert gas such as nitrogen or argon.
  • Examples of the firing method include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.
  • Example 1-2 A charge transporting varnish was prepared in the same manner as in Example 1 except that 0.011 g of 4-chlorophenyltrimethoxysilane was replaced with 0.011 g of ethyltrimethoxysilane (solid content: 3.0% by mass).
  • Example 1-3 A charge transport varnish was prepared in the same manner as in Example 1 except that 0.011 g of 4-chlorophenyltrimethoxysilane was replaced with 0.011 g of trimethoxy (3,3,3-trifluoropropyl) silane (solid content) 3.0 mass%).
  • Example 1-4 A charge transport varnish was prepared in the same manner as in Example 1 except that 0.011 g of 4-chlorophenyltrimethoxysilane was replaced with 0.011 g of trimethoxy (phenyl) silane (solid content: 3.0% by mass).
  • Example 1-5 A charge transporting varnish was prepared in the same manner as in Example 1 except that 0.011 g of 4-chlorophenyltrimethoxysilane was replaced with 0.011 g of triethoxy (perfluorophenyl) silane (solid content: 3.0% by mass) .
  • the contact angle of the charge transport varnish produced in Example 1 and Comparative Examples 1-1 to 1-5 was measured by the following method. Each charge transporting varnish is formed on an indium tin oxide (ITO) substrate by spin coating, dried in air at 80 ° C. for 1 minute, and then fired at 230 ° C. for 15 minutes to form a thin film. Produced. With respect to the obtained thin film, contact angles of 3-phenoxytoluene and tetralin were measured. The results are shown in Table 1.
  • the contact angle of the solvent used for the upper layer material is 10 ° or more, the upper layer material may repel during lamination, and a uniform film may not be obtained.
  • Table 1 the contact angle of the solvent on the thin film prepared from the charge transporting varnish of Example 1 to which 4-chlorophenyltrimethoxysilane, which is an organosilane compound having a chlorine-containing monovalent hydrocarbon group, was added was The contact angle of the solvent on the thin film prepared from the charge transporting varnish of Comparative Example 1-1 to which no organosilane compound was added was not changed, and the added chlorine-containing organosilane compound did not affect the wettability of the upper layer. Further, since the contact angle is 3 ° or less, no repelling occurs at the time of lamination, the upper layer coating property is good, and the upper layer material is expected to be formed uniformly.
  • Two-layer device A substrate for evaluating electrical characteristics is a 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate (hereinafter abbreviated as an ITO substrate) in which indium tin oxide is patterned with a film thickness of 150 nm on the surface.
  • ITO substrate 25 mm ⁇ 25 mm ⁇ 0.7 t glass substrate
  • the ITO substrate was used after removing impurities on the surface using an O 2 plasma cleaning device (150 W, 30 seconds).
  • Example 2 The varnish obtained in Example 1 was applied to an ITO substrate using a spin coater, then dried at 80 ° C. for 1 minute, and further baked at 230 ° C. for 15 minutes in an air atmosphere to be uniformly 30 nm on the ITO substrate. A thin film (hole injection layer) was formed. On top of that, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) and an aluminum thin film were deposited using a vapor deposition apparatus (vacuum degree 1.0 ⁇ 10 ⁇ 5 Pa). A two-layer element was obtained by sequentially laminating.
  • the film thickness was 30 nm and 100 nm, respectively, and the vapor deposition rate was 0.2 nm / sec.
  • the characteristics of the two-layer element were evaluated after sealing with a sealing substrate. Sealing was performed according to the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of ⁇ 85 ° C. or less, the device is placed between the sealing substrates, and the sealing substrate is attached with an adhesive (MORESCO Corp., Mores Moisture Cut WB90US (P)). Combined.
  • a water-absorbing agent manufactured by Dynic Co., Ltd., HD-071010W-40 was placed in the sealing substrate together with the element.
  • 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 produced from the varnish of Example 1 is a varnish containing no organosilane compound (Comparative Example 1-1) or a varnish containing an organosilane compound containing no halogen atom (Comparative Example 1-1). It can be seen that the film has excellent charge transportability as compared with the thin film produced from Comparative Examples 1-2 and 1-4). In addition, it can be seen that the film has a charge transporting property comparable to that of a thin film made from a varnish (Comparative Examples 1-3, 1-5) to which a fluorine-containing organosilane compound is added.
  • Example 3 Manufacture and characteristic evaluation of organic EL element
  • a uniform thin film of 30 nm was formed on the ITO substrate in the same manner as in Example 2.
  • N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -) is applied to the ITO substrate on which the thin film has been formed using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa).
  • NPD 30 nm was laminated.
  • CBP and Ir (PPy) 3 were co-evaporated.
  • the deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and the layers were laminated to 40 nm.
  • an organic EL element was obtained by sequentially laminating thin films of BAlq, lithium fluoride, and aluminum.
  • the deposition rate was 0.2 nm / second for BAlq and aluminum and 0.02 nm / second for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 100 nm, respectively.
  • the organic EL element was sealed with a sealing substrate in the same manner as in Example 2.

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  • Optics & Photonics (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

Le vernis à transport de charge de l'invention contient une substance de transport de charge, une substance dopante, un composé silane organique possédant en tant que substituant un groupe hydrocarbure monovalent à teneur en chlore tel qu'un 4-chlorophényltriméthoxysilane, ou similaire, et un solvant organique. Ce vernis à transport de charge est excellent en termes de matité, de propriétés de transport de charge, de propriétés d'application d'un matériau de couche supérieure, et fournit une pellicule présentant d'excellentes caractéristiques de brillance dans le cas d'une mise en œuvre dans un élément électroluminescent organique.
PCT/JP2015/075541 2014-09-10 2015-09-09 Vernis à transport de charge WO2016039360A1 (fr)

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CN106688120A (zh) 2017-05-17
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CN106688120B (zh) 2018-09-11
TW201623216A (zh) 2016-07-01
KR102388046B1 (ko) 2022-04-19
KR20170052560A (ko) 2017-05-12

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