WO2020262419A1 - Charge-transporting varnish - Google Patents
Charge-transporting varnish Download PDFInfo
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- WO2020262419A1 WO2020262419A1 PCT/JP2020/024704 JP2020024704W WO2020262419A1 WO 2020262419 A1 WO2020262419 A1 WO 2020262419A1 JP 2020024704 W JP2020024704 W JP 2020024704W WO 2020262419 A1 WO2020262419 A1 WO 2020262419A1
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- WIPO (PCT)
- Prior art keywords
- group
- charge
- carbon atoms
- transporting
- transporting varnish
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- 239000002966 varnish Substances 0.000 title claims abstract description 173
- -1 aryl sulfonic acid ester compound Chemical class 0.000 claims abstract description 267
- 239000002019 doping agent Substances 0.000 claims abstract description 22
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical class N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims abstract description 17
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 189
- 125000003118 aryl group Chemical group 0.000 claims description 75
- 239000010409 thin film Substances 0.000 claims description 72
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 70
- 125000005843 halogen group Chemical group 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- 150000002430 hydrocarbons Chemical group 0.000 claims description 43
- 238000002347 injection Methods 0.000 claims description 40
- 239000007924 injection Substances 0.000 claims description 40
- 238000005401 electroluminescence Methods 0.000 claims description 39
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 38
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 21
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000002521 alkyl halide group Chemical group 0.000 claims description 7
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 125000005264 aryl amine group Chemical group 0.000 claims description 6
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 112
- 239000000758 substrate Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 42
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 30
- 239000002904 solvent Substances 0.000 description 29
- 239000010408 film Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000005192 partition Methods 0.000 description 25
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 24
- 125000001153 fluoro group Chemical group F* 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 229910052731 fluorine Inorganic materials 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 18
- 125000001072 heteroaryl group Chemical group 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 150000001448 anilines Chemical class 0.000 description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 14
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 description 12
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 12
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 12
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 12
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 12
- 229960001826 dimethylphthalate Drugs 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000002356 single layer Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- CIBQKYNGEIFTDM-UHFFFAOYSA-N 2,2-di(propan-2-yl)propanedioic acid Chemical compound CC(C)C(C(C)C)(C(O)=O)C(O)=O CIBQKYNGEIFTDM-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000002346 layers by function Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 230000002140 halogenating effect Effects 0.000 description 8
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
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- 125000006038 hexenyl group Chemical group 0.000 description 6
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- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 5
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- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 5
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
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- AQOSPGCCTHGZFL-UHFFFAOYSA-N 1-(3a-hydroxy-7-methoxy-1,2,4,8b-tetrahydropyrrolo[2,3-b]indol-3-yl)ethanone Chemical compound COC1=CC=C2NC3(O)N(C(C)=O)CCC3C2=C1 AQOSPGCCTHGZFL-UHFFFAOYSA-N 0.000 description 3
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
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- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
Definitions
- the present invention relates to a charge transporting varnish.
- the method for forming an organic functional layer such as a hole injection layer used in an organic electroluminescence (EL) device is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing each of these processes, the wet process can efficiently produce a thin film having a large area and high flatness. Therefore, at present, the area of organic EL displays is being increased, and a hole injection layer that can be formed by a wet process is desired.
- the applicant has applied a charge transporting material that can be applied to various wet processes and provides a thin film capable of realizing excellent EL device characteristics when applied to a hole injection layer of an organic EL device.
- we have been developing compounds with good solubility in organic solvents used for them see, for example, Patent Documents 1 to 3).
- a partition wall (bank) is generally provided so as to surround the layer formation region, and a partition wall (bank) is provided in the opening of the partition wall.
- Organic functional ink is applied.
- the ink applied in the opening may crawl up on the side surface of the partition wall, and the thickness of the peripheral portion of the coating film in contact with the side surface of the partition wall may be thicker than that of the central portion of the coating film, so-called crawling phenomenon may occur. ..
- crawling phenomenon occurs, the plurality of organic functional layers formed between the electrodes do not function in the order of stacking, causing a situation in which a leak current path is formed.
- Patent Documents 4 and 5 propose means for suppressing the crawling phenomenon, but in response to the recent situation in which the development of organic EL displays using a wet process is further accelerated, the suppression of such a crawling phenomenon is suppressed.
- the demand for technology related to is increasing.
- the present invention has been made in view of the above circumstances, and is a charge-transporting varnish that does not cause a creep-up phenomenon, and has excellent characteristics when a thin film obtained from the varnish is applied to a hole injection layer or the like. It is an object of the present invention to provide a charge transporting varnish capable of realizing an organic EL device.
- the present inventor has obtained (A) a monodisperse charge-transporting organic compound, (B) a dopant containing two predetermined compounds, and (C) an organic solvent.
- the present invention has been completed by finding that when the charge-transporting varnish containing the varnish is applied into the partition wall by a wet process, the creeping up of the varnish is extremely suppressed.
- the present invention provides the following charge transporting varnish.
- a charge-transporting varnish containing (A) a monodisperse charge-transporting organic compound, (B) a dopant, and (C) an organic solvent.
- a 1 may have a substituent and is represented by an m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings or the following formula (B1a) or (B1b). Is an m-valent group derived from the compound to be (In the formula, W 1 and W 2 may independently have -O-, -S-, -S (O)-or -S (O 2 )-, or -N.
- a 2 is -O-, -S- or -NH-;
- a 3 is, or an (n + 1) -valent aromatic group with 6 to 20 carbon atoms;
- X 1 is an alkylene group having 2 to 5 carbon atoms, and an —O—, —S— or carbonyl group may be interposed between the carbon atoms of the alkylene group, and one of the hydrogen atoms of the alkylene group.
- X 2 is a single bond, -O-, -S- or -NR-, and R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms
- X 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
- m is an integer that satisfies 1 ⁇ m ⁇ 4.
- n is an integer that satisfies 1 ⁇ n ⁇ 4.
- R s1 to R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R s5 may have a substituent. It is a monovalent hydrocarbon group having 2 to 20 carbon atoms; A 11 is an m-valent group derived from perfluorobiphenyl, A 12 is an -O- or -S-, and A 13 is a (n + 1) -valent group derived from naphthalene or anthracene. Yes; m and n are the same as described above.
- R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 is a linear or branched monovalent fat. Although it is a group hydrocarbon group, the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more;
- a 14 is an m-valent hydrocarbon group containing one or more aromatic rings, which may have a substituent, A 15 is —O— or —S—, and A 16 is ( It is an n + 1) valent aromatic group; m and n are the same as described above.
- R s9 to R s13 are independently hydrogen atom, nitro group, cyano group, halogen atom, alkyl group having 1 to 10 carbon atoms, alkyl halide group having 1 to 10 carbon atoms, or carbon number of carbon atoms. 2-10 halogenated alkenyl groups; R s14 to R s17 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms; R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or ⁇ OR s19 , and R s19 has 2 to 20 carbon atoms which may have a substituent.
- R q1 to R q4 are independently hydrogen atoms or halogen atoms, but at least one is a halogen atom.
- B3 A charge-transporting varnish according to any one of 1 to 8, wherein the halogenated or cyanated benzoquinone is represented by the following formula (B3).
- R q5 to R q8 are independently hydrogen atoms, halogen atoms or cyano groups, but at least one is a halogen atom or cyano group.
- the content of the (B1) aryl sulfonic acid ester compound is 0.01 to 50 in molar ratio with respect to the (B2) halogenated tetracyanoquinodimethane or the (B3) halogenated or cyanated benzoquinone.
- the charge-transporting varnish of the present invention By using the charge-transporting varnish of the present invention, it is possible to produce a charge-transporting thin film in which the varnish creeps up (so-called pile-up) is extremely suppressed even when it is applied into the partition wall by a wet process. Further, the charge-transporting thin film obtained from the charge-transporting varnish of the present invention is excellent in flatness and charge-transporting property. Therefore, the charge transporting varnish of the present invention can be suitably used for producing a thin film for an electronic device including an organic EL device, particularly a thin film for an organic EL display.
- the charge transport varnish of the present invention is a charge transport varnish containing (A) a monodisperse charge transport organic compound, (B) a dopant and (C) an organic solvent, and (B) the dopant is (B1). It contains an aryl sulfonic acid ester compound and (B2) halogenated tetracyanoquinodimethane or (B3) halogenated or cyanated benzoquinone.
- charge transporting organic compound for example, those conventionally used in the field of organic EL can be used.
- arylamine derivatives aniline derivatives
- oligoaniline derivatives N, N'-diarylbenzidine derivatives, N, N, N', N'-tetraarylbenzidine derivatives, oligothiophene derivatives, and thienothiophene derivatives.
- Thionophen derivatives such as thienobenzothiophene derivatives
- various charge-transporting organic compounds such as pyrrole derivatives such as oligopyrrole.
- arylamine derivatives and thiophene derivatives are preferable.
- the charge-transporting organic compound needs to be monodisperse (that is, the molecular weight distribution is 1).
- the molecular weight of the charge-transporting organic compound is usually about 200 to 9,000 from the viewpoint of preparing a uniform varnish that gives a thin film having high flatness, but 300 from the viewpoint of obtaining a thin film having more excellent charge-transporting property.
- the above is preferable, 400 or more is more preferable, and from the viewpoint of preparing a uniform varnish that gives a thin film having high flatness with better reproducibility, 8,000 or less is preferable, 7,000 or less is more preferable, and 6,000 or less is preferable. Even more preferably, 5,000 or less is even more preferable.
- Examples of the charge-transporting organic compound include JP-A-2002-151272, International Publication No. 2004/105446, International Publication No. 2005/043962, International Publication No. 2008/032617, and International Publication No. 2008/032616. , International Publication No. 2013/0426223, International Publication No. 2014/141998, International Publication No. 2014/185208, International Publication No. 2015/050253, International Publication No. 2015/137391, International Publication No. 2015/137395, International Publication No. Examples thereof are those disclosed in Publication No. 2015/146912, International Publication No. 2015/146965, International Publication No. 2016/190326, International Publication No. 2016/136544, International Publication No. 2016/204079, and the like.
- a tertiary arylamine compound having at least one nitrogen atom and all nitrogen atoms having a tertiary arylamine structure is also preferable. That is, the tertiary arylamine compound has at least one nitrogen atom and has a structure in which three aromatic groups are bonded to all the nitrogen atoms.
- the tertiary arylamine compound preferably has two or more nitrogen atoms.
- tertiary arylamine compound examples include a compound represented by the following formula (A1) or (A2).
- R 1 and R 2 are independently substituted with a hydrogen atom, a halogen atom, a nitro group or a cyano group, or a halogen atom, respectively, an alkyl group having 1 to 20 carbon atoms, and carbon. It is an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl.
- 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 , Bicyclooctyl group, bicyclononyl group, bicyclodecyl group and other cyclic alkyl groups having 3 to 20 carbon atoms.
- the alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include a vinyl group, an n-1-propenyl group, an n-2-propenyl group and 1-methyl.
- Examples thereof include a -1-propenyl group, a 1-methyl-2-propenyl group, an n-1-pentenyl group, an n-1-decenyl group, an n-1-eicosenyl 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.
- 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, Examples thereof include an n-1-decynyl group, an n-1-pentadecynyl group, and an n-1-eicosynyl group.
- Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group and a 2-phenanthryl group. Examples thereof include a 3-phenanthryl group, a 4-phenanthryl group and a 9-phenanthryl group.
- 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 and 3-.
- Isooxazolyl group 4-isoxazolyl group, 5-isooxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4- Examples thereof include an imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
- R 1 and R 2 include an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a fluorine atom, a cyano group and a halogen atom, and a carbon number which may be substituted with a halogen atom.
- An aryl group of 6 to 20 or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom is preferable, and a heteroaryl group having 1 carbon atom which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom is preferable.
- a phenyl group which may be substituted with an alkyl group of to 10 or a halogen atom is more preferable, a hydrogen atom or a fluorine atom is more preferable, and a hydrogen atom is the most suitable.
- Ph 1 is a group represented by the formula (P1).
- R 3 to R 6 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group or a cyano group, or a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms.
- R 3 to R 6 include an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, a fluorine atom, a cyano group and a halogen atom, and 6 to 6 carbon atoms which may be substituted with a halogen atom.
- a heteroaryl group having 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom is preferable, and a heteroaryl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom is preferable.
- the alkyl group or the phenyl group which may be substituted with the halogen atom is more preferable, the hydrogen atom or the fluorine atom is more preferable, and the hydrogen atom is the most suitable.
- Suitable groups for Ph 1 include, but are not limited to, 1,4-phenylene groups.
- Ar 1 is a group independently represented by any of the following formulas (Ar1-1) to (Ar1-11), and in particular, the following formulas (Ar1-1') to (Ar1-1') to ( A group represented by any one of Ar1-11') is preferable.
- R 7 to R 27 , R 30 to R 51 and R 53 to R 154 may be independently substituted with a hydrogen atom, a halogen atom, a nitro group or a cyano group, or a halogen atom, a diphenylamino group, respectively.
- R 28 and R 29 are aryl groups having 6 to 20 carbon atoms or heteroaryl groups having 2 to 20 carbon atoms, which may be independently substituted with Z 1 .
- R 52 is 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 1 .
- Z 1 is 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 a halogen atom, a nitro group or a cyano group, or Z 2.
- Z 2 is an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group or a cyano group, or Z 3 .
- Z 3 is a halogen atom, a nitro group or a cyano group.
- R 7 to R 27 , R 30 to R 51 and R 53 to R 154 are substituted with a diphenylamino group or a halogen atom which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom.
- An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom may be used.
- an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a fluorine atom, a cyano group or a halogen atom, or a phenyl group which may be substituted with a halogen atom is more preferable, and a hydrogen atom or a fluorine atom is preferable. Is even more preferred, and a hydrogen atom is optimal.
- an aryl group having 6 to 14 carbon atoms which may be substituted with a halogen atom or a heteroaryl group having 2 to 14 carbon atoms which may be substituted with a halogen atom is preferable, and a halogen atom.
- a phenyl group optionally substituted with, or a naphthyl group optionally substituted with a halogen atom is more preferred, a phenyl group optionally substituted with a halogen atom is even more preferred, and a phenyl group is even more preferred.
- a hydrogen atom is preferably an aryl group of Z 1 is carbon atoms 6 also be ⁇ 20 substituted by a hydrogen atom, an optionally substituted phenyl group Z 1, or substituted with Z 1
- a good naphthyl group is more preferred, a phenyl group which may be substituted with Z 1 is even more preferred, and a phenyl group is even more preferred.
- Ar 4 is independently composed of an aryl group having 6 to 20 carbon atoms. It is an aryl group having 6 to 20 carbon atoms which may be substituted with a certain diallylamino group. Specific examples of the aryl group having 6 to 20 carbon atoms include those similar to those described in R 1 and R 2 above.
- diarylamino group examples include a diphenylamino group, a 1-naphthylphenylamino group, a di (1-naphthyl) amino group, a 1-naphthyl-2-naphthylamino group, a di (2-naphthyl) amino group and the like. Can be mentioned.
- Ar 4 includes phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthril group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4- Phenantryl group, 9-phenanthryl group, p- (diphenylamino) phenyl group, p- (1-naphthylphenylamino) phenyl group, p- (di (1-naphthyl) amino) phenyl group, p- (1-naphthyl-) 2-Phenylamino) phenyl group, p- [di (2-naphthyl) amino] phenyl group and the like are preferable, and p- (diphenylamino) phenyl group is more preferable.
- Ar 2 is a group independently represented by any of the formulas (Ar2-1) to (Ar2-18), and in particular, the formulas (Ar2-1'-1) to (Ar2-1'-1) to ( The group represented by any one of Ar2-18'-2) is preferable.
- Ar 4 is the same as described above, DPA is a diphenylamino group, and the broken line is a bond.
- R 155 is a hydrogen atom, an aryl group having 6 to 14 carbon atoms which may be substituted with Z 1. , Or a heteroaryl group having 2 to 14 carbon atoms which may be substituted with Z 1 .
- Examples of the aryl group and the heteroaryl group include those similar to those described in the description of R 1 and R 2 .
- R 155 a hydrogen atom, Z 1 optionally substituted by a phenyl group, Z 1 in optionally substituted 1-naphthyl group, which may have been or 2-naphthyl substituted with Z 1 group, may be substituted with Z 1 in optionally substituted 2-pyridyl group, optionally substituted 3-pyridyl group by a phenyl group which may be substituted with Z 1, or Z 1 4
- a pyridyl group is preferred, a phenyl group which may be substituted with Z 1 is even more preferred, and a phenyl group or a (2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl) group is even more preferred. ..
- R 156 and R 157 may be substituted with a phenyl group which may be substituted with Z 1.
- Examples of the aryl group and the heteroaryl group include those similar to those described in the description of R 1 and R 2 .
- an aryl group optionally having 6 to 14 carbon atoms is preferably substituted by a phenyl group which may be substituted with Z 1, which may be substituted with Z 1
- Ar 3 is a group represented by any of the formulas (Ar3-1) to (Ar3-8), and in particular, in the formulas (Ar3-1') to (Ar3-8').
- the group represented by either is preferable.
- DPA is the same as described above, and the broken line is the bond.
- p is an integer of 1 to 10, but from the viewpoint of increasing the solubility of the compound in an organic solvent, 1 to 5 is preferable, 1 to 3 is more preferable, and 1 or 2 is even more preferable. 1 is optimal.
- q is 1 or 2.
- the aniline derivative represented by the formula (A1) and the aniline derivative represented by the formula (A2) can be produced, for example, according to the method described in International Publication No. 2015/050253.
- tertiary arylamine compound examples include, for example, a compound represented by the following formula (A3).
- r is an integer of 2-4.
- Ar 11 is an r-valent aromatic group having 6 to 20 carbon atoms which may be substituted.
- the aromatic group is a group obtained by removing r hydrogen atoms from the aromatic ring of an aromatic compound having 6 to 20 carbon atoms.
- a group derived from a compound represented by any of the following formulas (A3-1) to (A3-8) is particularly preferable.
- L 1 ⁇ L 3 are each independently a single bond, - (CR 201 R 202) s -, - C (O) -, - O -, - S -, - S (O) -, - S (O 2) - or -NR 203 - a.
- s is an integer from 1 to 6.
- L 4 ⁇ L 13 each independently represent a single bond, -CR 201 R 202 -, - C (O) -, - O -, - S-, -S (O) -, - S (O 2) - or -NR 203 - a.
- R 201 and R 202 are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 201 and R 202 are bonded to each other to form a ring together with the carbon atom to which they are bonded. You may be doing it.
- ⁇ (CR 201 R 202 ) s ⁇ when s is 2 or more, each R 201 and R 202 may be the same or different from each other.
- R 203 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
- the aromatic group may have a part or all of its hydrogen atom further substituted with a substituent.
- substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxy group, an amino group, a silanol group, a thiol group, a carboxy group, a sulfonic acid ester group, a phosphoric acid group and a phosphoric acid.
- Examples thereof include an ester group, an ester group, a thioester group, an amide group, a monovalent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group and a sulfo group.
- a cyano group or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable.
- 1,4-phenylene group, fluorene-2,7-diyl group, 9,9-dimethylfluorene-2,7-diyl group and the like which may be substituted are preferable, and even if they are substituted. Good, 1,4-phenylene group or biphenyl-4,4'-diyl group is more preferable.
- Ar 12 and Ar 13 are monovalent aromatic groups having 6 to 20 carbon atoms which may be independently substituted with Z 11 , and Ar 12 and Ar 13 are bonded to each other. Then, they may form a ring together with the nitrogen atom to which they are bonded. Further, each of Ar 12 and Ar 13 may be the same as or different from each other.
- Z 11 is a monovalent aliphatic hydrocarbon group or monovalent aromatic group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group or a cyano group, or a halogen atom, or a polymerizable group. ..
- Examples of the monovalent aromatic group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, and a 3-phenanthryl group.
- Examples thereof include an aryl group such as a group, a 4-phenylyl group, a 9-phenanthryl group, a 2-biphenylyl group, a 3-biphenylyl group and a 4-biphenylyl group.
- the monovalent aliphatic hydrocarbon 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.
- Examples of the polymerizable group include, but are not limited to, those represented by the following formulas.
- Ra is a hydrogen atom or a methyl group.
- R b and R d are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, but methyl groups and ethyl groups are preferable.
- R c , R e, and R f are alkylene groups having 1 to 8 carbon atoms, which may independently contain a single bond or an oxygen atom, a sulfur atom, or a nitrogen atom.
- R g , R h and R i are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group and n-propyl.
- Y a and Y b are independently single bonds or divalent aromatic groups having 6 to 20 carbon atoms.
- the divalent aromatic group includes a 1,3-phenylene group, a 1,4-phenylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, and a 2,6-naphthylene group. Examples thereof include a 4,4'-biphenylylene group. Of these, a 1,3-phenylene group or a 1,4-phenylene group is preferable.
- Ar a is a monovalent aromatic group having 6 to 20 carbon atoms which may have a substituent.
- Examples of the monovalent aromatic group include those similar to those described above.
- a methyl group, an ethyl group, a polymerizable group represented by the following formula and the like are preferable. (In the formula, the broken line is the bond.)
- Ar 12 and Ar 13 examples include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group and 2-vinyl.
- a phenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, a 1-naphthyl group, a 2-naphthyl group and the like are preferable.
- the compound represented by the formula (A3) can be synthesized by a known method, or a commercially available product can also be used.
- tertiary arylamine compound examples include those represented by the following formula (A4), for example.
- Ar 21 to Ar 23 are independently divalent aromatic groups having 6 to 20 carbon atoms.
- a divalent group derived from the compound represented by the above-mentioned formula (A3-1), (A3-3) or (A3-4) is preferable.
- a 1,4-phenylene group a biphenyl-4,4'-diyl group, a terphenyl-4,4''-diyl group and the like are preferable, and a 1,4-phenylene group.
- a biphenyl-4,4'-diyl group is more preferable.
- Ar 24 to Ar 29 are monovalent aromatic groups having 6 to 20 carbon atoms which may be independently substituted with Z 21 .
- the monovalent aromatic group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, and a 3-phenanthryl group.
- Examples thereof include an aryl group such as a group, a 4-phenylyl group, a 9-phenanthryl group, a 2-biphenylyl group, a 3-biphenylyl group and a 4-biphenylyl group.
- Z 21 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, a nitro group or a cyano group, or a halogen atom, a nitro group or a cyano group, ⁇ N (Ar 30 ) ( Ar 31 ), or a polymerizable group.
- the monovalent aliphatic hydrocarbon 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 and n.
- -Butyl group isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- Alkyl group having 1 to 20 carbon atoms such as decyl group, n-undecyl group, n-dodecyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a butenyl group, a 2-butenyl group, a 3-butenyl group and a hexenyl group.
- Examples of the polymerizable group include those similar to those described above.
- Ar 30 and Ar 31 are each independently an aryl group having 6 to 20 carbon atoms which may be substituted with Z 22 , and they may be bonded to each other to form a ring with the nitrogen atom to which they are bonded.
- Z 22 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a nitro group or a cyano group, or a halogen atom, a nitro group or a cyano group.
- aryl group having 6 to 20 carbon atoms and the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms are the same as those described above.
- phenyl group, 1-naphthyl group, 2-naphthyl group, 1-biphenylyl group are preferable, and phenyl group, 1-biphenylyl group and the like are more preferable.
- -N (Ar 30 ) (Ar 31 ) a diphenylamino group, a phenyl (4-biphenylyl) amino group, a bis (4-biphenylyl) amino group, an N-carbazolyl group and the like are preferable.
- an alkyl group having 1 to 10 carbon atoms, ⁇ N (Ar 30 ) (Ar 31 ) and the like are preferable.
- Ar 24 to Ar 29 examples include phenyl group, 4-biphenylyl group, 4-diphenylaminophenyl group, 4-phenyl (4-biphenylyl) aminophenyl group, bis (4-biphenylyl) aminophenyl group, and 4'-diphenylamino.
- -4-biphenylyl group, 4-phenyl (4-biphenylyl) amino-4-biphenylyl group, 4'-bis (4-biphenylyl) amino-4-biphenylyl group, N-carbazolylphenyl group, 4'-N- Carbazolyl-4-biphenylyl groups and the like are preferred.
- the compound represented by the formula (A4) can be synthesized by a known method, or a commercially available product can also be used.
- tertiary arylamine compound examples include those represented by the following formula (A5), for example.
- Ar 41 and Ar 42 are independently phenyl groups, 1-naphthyl groups or 2-naphthyl groups, respectively.
- R 301 and R 302 are independently hydrogen atoms, diarylaminophenyl groups in which each aryl group is an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group include those similar to those described in the description of R 1 and R 2 in the formula (A2).
- L 21 is a divalent linking group containing a propane-2,2-diyl group or a 1,1,1,1,3,3,3-hexafluoropropane-2,2-diyl group.
- x is an integer from 1 to 10.
- the compound represented by the formula (A5) can be synthesized by a known method, or a commercially available product can also be used.
- the tertiary arylamine compound is not limited to the above-mentioned compound as long as it has at least one nitrogen atom and all nitrogen atoms have a tertiary arylamine structure.
- Other tertiary arylamine compounds that can be used in the present invention include, for example, the arylamine compound described in International Publication No. 2005/094133, and the triarylamine partial structure and polymerizable property described in Japanese Patent No. 5287455. Examples thereof include a polymerizable compound having a group, a triarylamine compound described in Japanese Patent No. 5602191, a compound described in paragraph [0054] of Japanese Patent No. 6177771, and the like.
- Preferred examples of the tertiary arylamine compound include, but are not limited to, those shown below.
- the charge-transporting varnish of the present invention contains (B1) aryl sulfonic acid ester compound and (B2) halogenated tetracyanoquinodimethane or (B3) halogenated or cyanated benzoquinone as the dopant of the component (B).
- the aryl sulfonic acid ester compound is not particularly limited as long as it has a sulfonic acid ester group bonded to the aromatic ring.
- the molecular weight of the aryl sulfonic acid ester compound is preferably 100 or more, more preferably 200 or more, preferably 5,000 or less, more preferably 4,000 or less, still more preferably. It is 3,000 or less, more preferably 2,000 or less.
- the number of sulfonic acid ester groups contained in the aryl sulfonic acid ester compound is preferably 2 or more, more preferably 3 or more, preferably 6 or less, and more preferably 5 or less.
- the aryl sulfonic acid ester compound preferably comprises a fluorine-substituted aromatic ring.
- aryl sulfonic acid ester compound those represented by the following formula (B1) or (B1') are preferable.
- a 1 may have a substituent and is an m-valent hydrocarbon group having 6 to 20 carbon atoms including one or more aromatic rings, or the following formula ( Obtained by removing the m-valent group derived from the compound represented by B1a) or (B1b) (that is, m hydrogen atoms on the aromatic ring of the compound represented by the following formula (B1a) or (B1b). The group to be used).
- W 1 and W 2 may independently have -O-, -S-, -S (O)-or -S (O 2 )-, or -N. -, -Si-, -P- or -P (O)-)
- the m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings is obtained by removing m hydrogen atoms from the hydrocarbon having 6 to 20 carbon atoms containing one or more aromatic rings. It is a group.
- the hydrocarbon containing one or more aromatic rings include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Of these, as the m-valent hydrocarbon group, a group derived from benzene, biphenyl, or the like is preferable.
- a part or all of the hydrogen atom of the hydrocarbon group may be further substituted with a substituent.
- substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxy group, an amino group, a silanol group, a thiol group, a carboxy group, a sulfonic acid ester group, a phosphoric acid group and a phosphoric acid.
- an ester group an ester group, a thioester group, an amide group, a monovalent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfo group and the like.
- the monovalent hydrocarbon group 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.
- Carbons such as groups, sec-butyl groups, tert-butyl groups, n-pentyl groups, cyclopentyl groups, n-hexyl groups, cyclohexyl groups, n-heptyl groups, n-octyl groups, n-nonyl groups and n-decyl groups.
- An alkenyl group having 2 to 10 carbon atoms such as a group; an aryl group having 6 to 20 carbon atoms such as a phenyl group, a xsilyl group, a trill group, a 1-naphthyl group and a 2-naphthyl group; a carbon such as a benzyl group and a phenylethyl group.
- the number 7 to 20 aralkyl groups and the like can be mentioned.
- organooxy group examples include an alkoxy group, an alkenyloxy group, and an aryloxy group.
- alkyl group, alkenyl group and aryl group contained therein examples include those similar to those described above.
- organoamino group examples include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group and dodecyl.
- Alkylamino group having 1 to 12 carbon atoms such as amino group; dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, dicyclohexylamino group, diheptylamino group, dioctylamino group , Dialkylamino group in which each alkyl group such as dinonylamino group and didecylamino group is an alkyl group having 1 to 12 carbon atoms; morpholino group and the like can be mentioned.
- organosilyl group examples include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, an octyldimethylsilyl group and a decyldimethyl group.
- examples thereof include a trialkylsilyl group in which each alkyl group such as a silyl group is an alkyl group having 1 to 10 carbon atoms.
- organothio group examples include alkylthio groups having 1 to 12 carbon atoms such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group and dodecylthio group. Be done.
- acyl group examples include acyl groups having 1 to 10 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group and benzoyl group.
- the carbon number of the monovalent hydrocarbon group, organooxy group, organoamino group, organosilyl group, organothio group and acyl group is preferably 1 to 8.
- a fluorine atom, a sulfonic acid group, an alkyl group, an organooxy group, and an organosilyl group are more preferable.
- a 2 is -O-, -S- or -NH-. Of these, —O— is preferable because it is easy to synthesize.
- a 3 is a (n + 1) -valent aromatic group having 6 to 20 carbon atoms.
- the aromatic group is a group obtained by removing (n + 1) hydrogen atoms on an aromatic ring from an aromatic compound having 6 to 20 carbon atoms.
- the aromatic compound means an aromatic hydrocarbon and an aromatic heterocyclic compound. Examples of the aromatic compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like.
- the aromatic group represented by A 3 is a group derived from naphthalene or anthracene. Is preferable.
- X 1 is an alkylene group having 2 to 5 carbon atoms, and the alkylene group is formed between the carbon atoms (carbon-carbon bond) of ⁇ O—, ⁇ .
- An S- or a carbonyl group may be interposed, and a part or all of the hydrogen atom may be further substituted with an alkyl group having 1 to 20 carbon atoms.
- X 1 an ethylene group, a trimethylene group, a methyleneoxymethylene group, a methylenethiomethylene group and the like are preferable, and a part or all of the hydrogen atoms of these groups are further substituted with an alkyl group having 1 to 20 carbon atoms. You may.
- alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group and n-hexyl group. , Cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, bicyclohexyl group and the like.
- X 2 is a single bond, -O-, -S- or -NR-.
- R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- the monovalent hydrocarbon group an alkyl group such as a methyl group, an ethyl group or an n-propyl group is preferable.
- X 2 a single bond, —O— or —S— is preferable, and a single bond or —O— is more preferable.
- X 3 is a monovalent hydrocarbon group substituted by 1 carbon atoms which may be 1-20.
- the monovalent hydrocarbon group 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, an isobutyl group and sec.
- a part or all of the hydrogen atoms of the monovalent hydrocarbon group may be further substituted with a substituent.
- substituents include those similar to those described in the description of A 1 .
- X 3 an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable.
- m is an integer satisfying 1 ⁇ m ⁇ 4, but 2 is preferable.
- n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
- the aryl sulfonic acid ester compounds represented by the formulas (B1) and (B1') are highly soluble in a wide range of solvents including low protic solvents, the physical properties of the solution are prepared using a wide variety of solvents. It is possible to do so and the coating characteristics are high. Therefore, it is preferable to apply in the state of a sulfonic acid ester and generate sulfonic acid when the coating film is dried or fired.
- the temperature at which sulfonic acid is generated from the sulfonic acid ester is preferably 40 to 260 ° C. because it is stable at room temperature and preferably equal to or lower than the firing temperature. Further, considering the high stability in the varnish and the ease of desorption during firing, 80 to 230 ° C. is preferable, and 120 to 180 ° C. is more preferable.
- aryl sulfonic acid ester compound represented by the formula (B1) those represented by any of the following formulas (B1-1) to (B1-3) are preferable.
- a 11 is an m-valent group derived from perfluorobiphenyl (that is, a group obtained by removing m fluorine atoms from perfluorobiphenyl).
- a 12 is —O— or —S—, but —O— is preferred.
- a 13 is a (n + 1) -valent group derived from naphthalene or anthracene (that is, a group obtained by removing (n + 1) hydrogen atoms from naphthalene or anthracene), but a group derived from naphthalene is preferable. ..
- R s1 to R s4 are independently hydrogen atoms or linear or branched alkyl groups having 1 to 6 carbon atoms, and R s5 may be substituted. It is a good monovalent hydrocarbon group having 2 to 20 carbon atoms.
- Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. , N-Hexyl group and the like. Of these, an alkyl group having 1 to 3 carbon atoms is preferable.
- the monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl.
- Examples include an alkyl group such as a group, a sec-butyl group and a tert-butyl group; and an aryl group such as a phenyl group, a naphthyl group and a phenanthryl group.
- R s1 to R s4 it is preferable that R s1 or R s3 is a linear alkyl group having 1 to 3 carbon atoms and the rest are hydrogen atoms. Further, it is preferable that R s1 is a linear alkyl group having 1 to 3 carbon atoms and R s2 to R s4 are hydrogen atoms. As the linear alkyl group having 1 to 3 carbon atoms, a methyl group is preferable. Further, as R s5 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.
- n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
- a 14 is an m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings which may be substituted.
- the hydrocarbon group is a group obtained by removing m hydrogen atoms from a hydrocarbon having one or more aromatic rings and having 6 to 20 carbon atoms.
- Examples of the hydrocarbon include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
- a part or all of the hydrogen atom of the hydrocarbon group may be further substituted with a substituent, and such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a nitro.
- Group cyano group, hydroxy group, amino group, silanol group, thiol group, carboxy group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, ester group, thioester group, amide group, monovalent hydrocarbon group, organo Examples thereof include an oxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group and a sulfo group. Of these, as A 14 , a group derived from benzene, biphenyl, or the like is preferable.
- a 15 is —O— or —S—, but —O— is preferred.
- a 16 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms.
- the aromatic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
- the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Of these, as A 16 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
- R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group.
- R s8 is a linear or branched monovalent aliphatic hydrocarbon group.
- the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more.
- the upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
- linear or branched monovalent aliphatic hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-.
- Alkyl group having 1 to 20 carbon atoms such as butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1- Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and a hexenyl group.
- R s6 A hydrogen atom is preferable as R s6
- R s7 and R s8 an alkyl group having 1 to 6 carbon atoms is preferable as R s7 and R s8 .
- R s7 and R s8 may be the same or different.
- n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
- R s9 to R s13 are independently hydrogen atom, nitro group, cyano group, halogen atom, alkyl group having 1 to 10 carbon atoms, and alkyl halide group having 1 to 10 carbon atoms, respectively. , Or a halogenated alkenyl group having 2 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl.
- the alkyl halide group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms.
- the alkyl halide group may be linear, branched or cyclic, and specific examples thereof include a trifluoromethyl group, a 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 , 2,2,3,3,4,4,4-nonafluorobutyl group and the like.
- the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms.
- Specific examples thereof include a perfluorovinyl group, a perfluoro-1-propenyl group, a perfluoro-2-propenyl group, a perfluoro-1-butenyl group, a perfluoro-2-butenyl group, and a perfluoro-3-butenyl group. And so on.
- R s9 a nitro group, a cyano group, an alkyl halide group having 1 to 10 carbon atoms, an alkenyl halide group having 2 to 10 carbon atoms and the like are preferable, and a nitro group, a cyano group and 1 to 10 carbon atoms are preferable.
- the alkyl halide group of 4 and the alkenyl halide group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group, the perfluoropropenyl group and the like are even more preferable.
- R s10 to R s13 a halogen atom is preferable, and a fluorine atom is more preferable.
- a 17 is -O-, -S- or -NH-, but -O- is preferable.
- a 18 is an (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms.
- the aromatic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
- the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Of these, as A 18 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
- R s14 to R s17 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
- the monovalent aliphatic hydrocarbon group 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.
- R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or ⁇ OR s19 .
- R s19 is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.
- Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R s18 include those similar to those described in the description of R s14 to R s17 .
- R s18 is a monovalent aliphatic hydrocarbon group
- R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Is even more preferable.
- the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by R s19 includes an aryl group such as a phenyl group, a naphthyl group and a phenanthryl group in addition to the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group. And so on. Of these, as R s19 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable. Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.
- n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
- aryl sulfonic acid ester compound represented by the formula (B1-3) those represented by the following formula (B1-3-1) or (B1-3-2) are particularly preferable.
- R s20 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include those described in the description of R s18 .
- R s14 to R s17 is a linear alkyl group having 1 to 3 carbon atoms, and the rest is hydrogen. It is preferably an atom. Further, it is preferable that R s14 is a linear alkyl group having 1 to 3 carbon atoms and R s15 to R s17 are hydrogen atoms. As the linear alkyl group having 1 to 3 carbon atoms, a methyl group is preferable. Further, as R s19 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.
- the total number of carbon atoms of R s14 , R s16 and R s20 is preferably 6 or more.
- the upper limit of the total number of carbon atoms of R s14 , R s16 and R s20 is preferably 20 or less, and more preferably 10 or less.
- R s14 is preferably a hydrogen atom
- R s16 and R s20 are preferably an alkyl group having 1 to 6 carbon atoms.
- R s16 and R s20 may be the same as or different from each other.
- the aryl sulfonic acid ester compound represented by the formula (B1) may be used alone or in combination of two or more.
- Suitable aryl sulfonic acid ester compounds include, but are not limited to, those shown below.
- the aryl sulfonic acid ester compound represented by the formula (B1) is obtained by reacting the sulfonate compound represented by the formula (B1A) with a halogenating agent, for example, as shown in the following scheme A, to form the following formula (B1).
- the sulfonyl halide compound represented by B1B) is synthesized (hereinafter, also referred to as step 1), and the sulfonyl halide compound is reacted with the compound represented by the formula (B1C) (hereinafter, also referred to as step 2).
- step 1 In the formula, A 1 to A 3 , X 1 to X 3 , m and n are the same as described above.
- M + is a monovalent cation such as sodium ion, potassium ion, pyridinium ion, quaternary ammonium ion and the like.
- .Hal is a halogen atom such as a chlorine atom and a bromine atom.
- the sulfonate compound represented by the formula (B1A) can be synthesized according to a known method.
- halogenating agent used in step 1 examples include halogenating agents such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, and phosphorus (V) chloride, but thionyl chloride is preferable.
- the amount of the halogenating agent used is not limited as long as it is 1 times or more the molar amount of the sulfonate compound, but it is preferably used in an amount of 2 to 10 times the mass ratio of the sulfonate compound.
- the reaction solvent used in step 1 is preferably a solvent that does not react with the halogenating agent, and examples thereof include chloroform, dichloroethane, carbon tetrachloride, hexane, and heptane. Further, the reaction can be carried out without a solvent, and in this case, it is preferable to use a halogenating agent in an amount equal to or more than a uniform solution at the end of the reaction. Further, in order to promote the reaction, a catalyst such as N, N-dimethylformamide may be used.
- the reaction temperature can be about 0 to 150 ° C., but is preferably 20 to 100 ° C. and below the boiling point of the halogenating agent used. After completion of the reaction, the crude product obtained by concentration under reduced pressure or the like is generally used in the next step.
- Examples of the compound represented by the formula (B1C) include glycols such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, and ethylene glycol monohexyl ether.
- Ethers; alcohols such as 2-ethyl-1-hexanol, 2-butyl-1-octanol, 1-octanol, 3-nonanol and the like can be mentioned.
- a base may be used in combination.
- the base that can be used include sodium hydride, pyridine, triethylamine, diisopropylethylamine and the like, but sodium hydride, pyridine and triethylamine are preferable.
- the amount of the base used is preferably 1 times the molar amount to the amount of the solvent with respect to the sulfonyl halide compound.
- reaction solvent used in step 2 various organic solvents can be used, but tetrahydrofuran, dichloroethane, chloroform and pyridine are preferable.
- the reaction temperature is not particularly limited, but 0 to 80 ° C. is preferable.
- a pure aryl sulfonic acid ester compound can be obtained by post-treatment and purification using conventional methods such as concentration under reduced pressure, liquid separation extraction, washing with water, reprecipitation, recrystallization, and chromatography. It is also possible to obtain a high-purity sulfonic acid compound by subjecting the obtained pure aryl sulfonic acid ester compound to heat treatment or the like.
- the aryl sulfonic acid ester compound represented by the formula (B1) can also be synthesized from the sulfonic acid compound represented by the formula (B1D) as shown in the following scheme B.
- the halogenating agent used in the first and second stage reactions, the compound represented by the formula (B1C), the reaction solvent and other components are the same as in steps 1 and 2 in the scheme A. Can be used.
- a 1 to A 3 , X 1 to X 3 , Hal, m and n are the same as above.
- the sulfonic acid compound represented by the formula (B1D) can be synthesized according to a known method.
- the aryl sulfonic acid ester compound represented by the formula (B1') can be synthesized according to a conventionally known method, for example, the method described in Japanese Patent No. 5136795.
- R q1 to R q4 are independently hydrogen atoms or halogen atoms, but at least one is a halogen atom.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
- at least two of R q1 to R q4 are preferably halogen atoms, at least three are more preferably halogen atoms, and most preferably all are halogen atoms.
- tetracyanoquinodimethane derivative examples include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro.
- F4TCNQ Tetrafluoro-7,7,8,8-Tetracyanoquinodimethane
- F4TCNQ Tetrafluoro-7,7,8,8-Tetracyanoquinodimethane
- Tetrachloro-7,7,8,8-Tetracyanoquinodimethane Methane 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8, Examples thereof include 8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane.
- F4TCNQ is preferable.
- R q5 to R q8 are independently hydrogen atoms, halogen atoms or cyano groups, but at least one is a halogen atom or cyano group.
- the halogen atom include the same as those described above, and a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
- halogenated or cyanated benzoquinone 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (chloranil), trifluoro-1
- DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
- chloranil tetrachloro-1,4-benzoquinone
- trifluoro-1 examples thereof include 4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, tetracyano-1,4-benzoquinone and the like.
- 2,3-dichloro-5,6-dicyano-p-benzoquinone, trifluorobenzoquinone, tetrafluorobenzoquinone, and tetracyanobenzoquinone are preferable, and DDQ, chloranil, tetrafluoro-1,4-benzoquinone, and tetracyano-1 are preferable.
- 4-Benzoquinone is more preferred, and DDQ is even more preferred.
- the content of the (B1) aryl sulfonic acid ester compound is usually 0 in molar ratio with respect to (B2) tetracyanoquinodimethane halogenated or (B3) halogenated or benzoquinone cyanated.
- the amount is about .01 to 50, preferably about 0.1 to 20, and more preferably about 1.0 to 10.
- the total content of the dopant of the component (B) is such that the ratio (D / H) of the content of the dopant to the charge-transporting organic compound is usually about 0.01 to 50 in terms of molar ratio. It is preferably an amount of about 0.1 to 10, and more preferably an amount of about 1.0 to 5.0.
- (B2) halogenated tetracyanoquinodimethane can be used alone or in combination of two or more, and (B3) halogenated or cyanated benzoquinone can be used alone or in combination of two or more. be able to. Further, (B2) halogenated tetracyanoquinodimethane and (B3) halogenated or cyanated benzoquinone can be used in combination.
- the organic solvent (C) is not particularly limited as long as it can dissolve or disperse each of the above-mentioned components and each of the optional components described below, but a low-polarity solvent may be used because of its excellent process compatibility. preferable.
- a low-polarity solvent is defined as a solvent having a relative permittivity of less than 7 at a frequency of 100 kHz
- a high-polarity solvent is defined as a solvent having a relative permittivity of 7 or more at a frequency of 100 kHz.
- low polar solvent examples include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetraline, cyclohexylbenzene and decylbenzene; 1-octanol, 1-nonanol, 1-decanol and the like.
- Alibo alcohol solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc.
- Solvents Methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis (2-ethylhexyl) phthalate, dimethyl phthalate, diisopropyl malate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether
- ester solvents such as acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
- Examples of the highly polar solvent include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
- Ketone solvent such as ethyl methyl ketone, isophorone, cyclohexanone; Cyano solvent such as acetonitrile and 3-methoxypropionitrile; Ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, Polyhydric alcohol solvents such as 2,3-butanediol; diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyl Monohydric alcohol solvents other than aliphatic alcohols such as oxyethanol, 3-phenoxybenzyl alcohol and tetrahydrofurfuryl alcohol; sulfoxide solvents such as dimethyl sulfoxide and the like can be mentioned.
- Ketone solvent such as ethyl methyl ketone, isophor
- the amount of the organic solvent used is such that the solid content concentration in the varnish of the present invention is usually 0.1 to 20% by mass from the viewpoint of ensuring a sufficient film thickness while suppressing the precipitation of the charge-transporting organic compound.
- the amount is preferably 0.5 to 10% by mass.
- the solid content means a component other than the solvent among the components contained in the varnish.
- the solvent may be used alone or in combination of two or more.
- the charge-transporting varnish of the present invention may further contain an organic silane compound for the purpose of adjusting the film physical characteristics of the obtained charge-transporting thin film.
- organic silane compound examples include a dialkoxysilane compound, a trialkoxysilane compound, and a tetraalkoxysilane compound.
- a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
- the organic silane compound may be used alone or in combination of two or more.
- the content thereof is usually about 0.1 to 50% by mass in the solid content, but the flatness of the obtained thin film is improved and the decrease in charge transportability is suppressed. In consideration of such a balance, it is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and even more preferably about 1 to 20% by mass.
- the charge-transporting varnish of the present invention may contain an amine compound from the viewpoint of dissolving a charge-transporting organic compound or a dopant in a solvent to obtain a highly uniform varnish, and the content thereof is usually 0 in the solid content. It is about 1 to 50% by mass.
- the method for preparing the charge-transporting varnish is not particularly limited, and examples thereof include a method of adding a charge-transporting organic compound and a dopant and, if necessary, other components to the organic solvent in any order or at the same time.
- each component may be dissolved in one solvent sequentially or simultaneously, and another solvent may be added thereto.
- Each component may be sequentially or simultaneously dissolved in a mixed solvent of a plurality of organic solvents. It may be dissolved.
- the charge transporting varnish of the present invention is filtered using a submicrometer order filter or the like after dissolving each component in an organic solvent.
- the viscosity of the charge-transporting varnish of the present invention is usually 1 to 50 mPa ⁇ s at 25 ° C.
- the surface tension of the charge-transporting varnish of the present invention is usually 20 to 50 mN / m at 25 ° C.
- the viscosity is a value measured by a TVE-25 type viscometer manufactured by Toki Sangyo Co., Ltd.
- the surface tension is a value measured by an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
- the viscosity and surface tension of the varnish can be adjusted by changing the types of solvents described above, their ratios, the solid content concentration, and the like in consideration of various factors such as a desired film thickness.
- the charge-transporting thin film of the present invention can be formed by applying the charge-transporting varnish of the present invention on a substrate and firing it.
- varnish coating method examples include, but are not limited to, the dip method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spray method, slit coating method, and the like. It is preferable to adjust the viscosity and surface tension of the varnish according to the coating method.
- the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and a thin film having a uniform film-forming surface and charge-transporting property can be obtained not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum.
- an inert gas such as nitrogen or in a vacuum.
- a thin film having higher charge transportability can be obtained with good reproducibility.
- the firing temperature is usually set appropriately within the range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability applied to the obtained thin film, the type of solvent, the boiling point, and the like.
- a temperature change of two or more steps may be applied for the purpose of exhibiting higher uniform film forming property or allowing the reaction to proceed on the substrate, and heating may be performed by, for example, a hot plate or the like. It may be carried out using an appropriate device such as an oven.
- the film thickness of the charge transporting thin film is not particularly limited, but when it is used as a functional layer between the anode and the light emitting layer such as a hole injection layer, a hole transport layer or a hole injection transport layer of an organic EL element, 5 It is preferably about 300 nm.
- a method of changing the film thickness there are methods such as changing the solid content concentration in the varnish and changing the amount of liquid on the substrate at the time of coating.
- the charge-transporting thin film of the present invention can be formed by the method described above, but by using the charge-transporting varnish of the present invention, the charge-transporting thin film can be suitably formed in the partition wall of the substrate with a partition wall.
- the substrate with a partition wall is not particularly limited as long as it is a substrate on which a predetermined pattern is formed by a known photolithography method or the like. Normally, there are a plurality of openings defined by the partition wall on the substrate. Usually, the size of the opening is 100 to 210 ⁇ m on the long side, 40 ⁇ m ⁇ 100 ⁇ m on the short side, and the bank taper angle is 20 to 80 °.
- the material of the substrate is not particularly limited, but is a transparent electrode material typified by indium tin oxide (ITO) and indium zinc oxide (IZO) used as an anode material of an electronic element; aluminum, gold, Metal anode materials composed of metals typified by silver, copper, indium, etc. or alloys thereof; polymer anode materials such as polythiophene derivatives and polyaniline derivatives having high charge transport properties, etc., are subjected to flattening treatment. Is preferable.
- the charge transporting varnish of the present invention is applied to the inside of the partition wall of the substrate with a partition wall by an inkjet method, then depressurized, and further heated if necessary to remove the solvent from the charge transporting varnish coated inside the partition wall.
- a charge-transporting thin film can be produced to produce a substrate with a charge-transporting thin film, and further, by laminating other functional films on the charge-transporting thin film, an electronic element such as an organic EL element can be formed. Can be manufactured.
- the atmosphere at the time of coating with the inkjet is not particularly limited, and may be any of an air atmosphere, an atmosphere of an inert gas such as nitrogen, and a reduced pressure.
- the degree of decompression (vacuum degree) at the time of depressurization is not particularly limited as long as the solvent of the varnish evaporates, but is usually 1,000 Pa or less, preferably 100 Pa or less, more preferably 50 Pa or less, still more preferably 25 Pa or less, and further. It is preferably 10 Pa or less.
- the depressurization time is also not particularly limited as long as the solvent evaporates, but is usually about 0.1 to 60 minutes, preferably about 1 to 30 minutes.
- the conditions for firing (heating) are the same as the above-mentioned conditions.
- the pile-up index described later is usually a high value of 83% or more, preferably 86% or more, more preferably 89% or more, even more preferably 92% or more, still more preferably 95% or more. Up can be suppressed.
- the pile-up index is when the partition wall (bank) width is A ( ⁇ m) and the film thickness range of + 10% from the film thickness of the charge-transporting thin film at the center of the partition wall (bank) is B ( ⁇ m). It can be calculated by the formula (B / A) ⁇ 100 (%).
- the organic EL device of the present invention has a pair of electrodes, and has a functional layer made of the charge-transporting thin film of the present invention between these electrodes.
- Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f).
- an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole block layer or the like may be provided between the light emitting layer and the cathode.
- the hole injection layer, the hole transport layer or the hole injection transport layer may have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may serve as a hole block layer or the like. It may also have the functions of.
- an arbitrary functional layer can be provided between the layers.
- Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode (c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode (f) Electron / hole injection transport layer / light emitting layer / cathode
- the "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 hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and a layer of hole transporting material between the light emitting layer and the anode. When two or more layers are provided, the layer close to the anode is the “hole injection layer”, and the other layers are the “hole transport layers”.
- the hole injection (transport) layer a thin film having excellent not only hole acceptability from the anode but also hole injection property into the hole transport (emission) layer is used.
- the "electron injection layer”, “electron transport layer” and “electron transport layer” are 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. Is. When only one layer of electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injection transporting layer”, and two layers of electron transporting material are provided between the light emitting layer and the cathode. When the above is provided, the layer close to the cathode is the “electron injection layer”, and the other layers are the “electron transport layer”.
- the "light emitting layer” is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is adopted.
- the host material mainly has a function of promoting the recombination of electrons and holes and confining the excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by the recombination. Has a function.
- the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
- the charge transporting thin film of the present invention can be suitably used as a functional layer provided between the anode and the light emitting layer in an organic EL device, and can be used as a hole injection layer, a hole transport layer, or a hole injection transport layer. It can be used more preferably, and can be used even more preferably as a hole injection layer.
- the materials and manufacturing methods used when manufacturing an organic EL device using the charge transporting varnish of the present invention include, but are not limited to, the following.
- An example of a method for producing an organic EL device having a hole injection layer made of a charge transporting thin film obtained from the charge transporting varnish of the present invention is as follows. It is preferable that the electrode is preliminarily subjected to surface treatment such as cleaning with alcohol, pure water or the like, UV ozone treatment, oxygen-plasma treatment or the like within a range that does not adversely affect the electrode.
- a hole injection layer is formed on the anode substrate by the above method using the charge transporting varnish of the present invention. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited.
- a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light emitting layer containing a light emitting polymer are used instead of forming the hole transport layer and the light emitting layer by vapor deposition in the method. These layers are formed by a wet process using. If necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
- anode material examples include transparent electrodes typified by ITO and IZO, metals typified by aluminum, and metal anodes composed of alloys thereof, and those subjected to flattening treatment are preferable.
- Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
- other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
- Examples of the material for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spirodimer, and N, N'-bis (naphthalen-1-yl) -N, N'-.
- Examples of the material forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyryl arylene derivative, and (2-hydroxyphenyl).
- a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyryl arylene derivative, and (2-hydroxyphenyl).
- Low molecular weight luminescent materials such as benzothiazole metal complexes and silol derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3- Alkylthiophene), a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as polyvinylcarbazole, and the like, but are not limited thereto.
- the light emitting layer When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant may be a metal such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ). Examples thereof include, but are not limited to, a complex, a naphthacene derivative such as rubrene, a quinacridone derivative, and a condensed polycyclic aromatic ring such as perylene.
- Examples of the material for forming the electron transport layer / whole block layer include, but are not limited to, an oxydiazole derivative, a triazole derivative, a phenanthroline derivative, a phenylquinoxaline derivative, a benzimidazole derivative, and a pyrimidine derivative.
- Examples of the material forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (Mg O), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). ), But is not limited to these.
- cathode material examples include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
- Examples of the material for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.
- hole-transporting polymer examples include poly [(9,9-dihexylfluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,4-diamino).
- Phenylene poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,1'-biphenylene-4,4- Diamine)], poly [(9,9-bis ⁇ 1'-penten-5'-yl ⁇ fluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1, 4-Diaminophenylene)], poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) -benzidine] -endcapped with polysilsesquioxane, poly [(9,, 9-didioctylfluorenyl-2,7-diyl) -co- (4,4'-(N- (p-butylphenyl)) diphenylamine)] and the like
- luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF) and poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene) (MEH).
- PDAF poly (9,9-dialkylfluorene)
- MEH poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene)
- -PPV polyphenylene vinylene derivatives
- PAT poly (3-alkylthiophene)
- PVCz polyvinylcarbazole
- the materials forming the anode and cathode and the layer formed between them differ depending on whether the element having the bottom emission structure or the top emission structure is manufactured. Therefore, the material is appropriately selected in consideration of this point. ..
- a transparent anode is used on the substrate side to extract light from the substrate side
- a reflective anode made of metal is used and the direction is opposite to that of the substrate.
- Light is extracted from a certain transparent electrode (cathode) side. Therefore, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing an element having a bottom emission structure, and a reflective anode such as Al / Nd is used when manufacturing an element having a top emission structure.
- the organic EL device of the present invention may be sealed together with a water catching agent or the like, if necessary, in accordance with a conventional method in order to prevent deterioration of characteristics.
- the charge transporting thin film of the present invention can be used as a functional layer of an organic EL element, but in addition, an organic photoelectric conversion element, an organic thin film solar cell, an organic perovskite photoelectric conversion element, an organic integrated circuit, and an organic Electric field effect transistors, organic thin films, organic light emitting transistors, organic optical testers, organic photoreceivers, organic electric field extinguishing devices, light emitting electronic chemical batteries, quantum dot light emitting diodes, quantum lasers, organic laser diodes, organic Plasmon light emitting devices, etc. It can also be used as a functional layer of an electronic device.
- the equipment used is as follows. (1) MALDI-TOF-MS: Bruker's autoflex III smart beam (2) 1 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd. (3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Sangyo Co., Ltd. (decompression plasma method) (4) Varnish application: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (5) Film thickness measurement and surface shape measurement: Fine shape measuring machine surf coder ET-4000A manufactured by Kosaka Laboratory Co., Ltd. (6) Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
- Measurement of element current density Multi-channel IVL measuring device manufactured by EHC Co., Ltd.
- Inkjet device Dedicated driver WAVE BUILDER (model number: PIJD-1) manufactured by Cluster Technology Co., Ltd., observation device with camera inkjetlado, automatic stage Inkjet Designer and inkjet head PIJ-25NSET
- MMA Methyl methacrylate
- HEMA 2-Hydroxyethyl methacrylate
- HPMA 4-Hydroxyphenyl methacrylate
- HPMA-QD Condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
- Compound CHMI N-cyclohexylmaleimide
- PFHMA 2- (perfluorohexyl) ethyl methacrylate
- MAA AIBN methacrylate: ⁇ , ⁇ '-azobisisobutyronitrile
- QD1 ⁇ , ⁇ , ⁇ '-tris (4) -Hydroxyphenyl
- GT-401 Tetrabutanetetracarboxylate (Tetrabutantetracarboxylate) 3,4-Epoxycyclohexylmethyl) modified ⁇ -caprolactone (trade name: Epolide GT-401, manufactured by Daicel Co., Ltd.)
- PGME Propylene Glycol Monomethyl Ether
- PGMEA Propylene Glycol Monomethyl Ether Acetate
- CHN Cyclohexanone
- TMAH Tetramethylammonium Hydroxide
- the number average molecular weight (Mn) and weight average molecular weight (Mw) of the acrylic polymers P1 and P2 were measured by gel permeation chromatography (GPC) under the following conditions.
- GPC gel permeation chromatography
- ⁇ Chromatograph GPC device LC-20AD manufactured by Shimadzu Corporation -Column: Shodex KF-804L and 803L (manufactured by Showa Denko KK) and TSK-GEL (manufactured by Tosoh Corporation) are connected in series.
- the thin film was immersed in a 1.0 mass% TMAH aqueous solution for 120 seconds for development, and then the thin film was washed with running water for 20 seconds using ultrapure water. Next, the thin film on which this rectangular pattern was formed was post-baked (230 ° C., 30 minutes) and cured to prepare a substrate with a partition wall.
- the reaction mixture was cooled to room temperature, and the cooled reaction mixture, toluene, and ion-exchanged water were mixed and subjected to liquid separation treatment.
- the obtained organic layer was dried over sodium sulfate and concentrated.
- the concentrated solution was filtered through silica gel, 0.2 g of activated carbon was added to the obtained filtrate, and the mixture was stirred at room temperature for 30 minutes. Then, the activated carbon was removed by filtration, and the filtrate was concentrated.
- the concentrate was added dropwise to a mixed solvent of methanol and ethyl acetate (500 mL / 500 mL), the obtained slurry was stirred at room temperature overnight, and then the slurry was filtered to recover the filtrate.
- Example 1-2 To 0.057 g of the aniline derivative A, 0.245 g of the aryl sulfonic acid ester and 0.025 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish B.
- Example 1-3 To 0.184 g of the aniline derivative A, 0.327 g of the aryl sulfonic acid ester and 0.015 g of DDQ, 5.00 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish C.
- Example 1-4 To 0.003 g of aniline derivative B, 0.325 g of aryl sulfonic acid ester and 0.018 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish D.
- Example 1-5 To aniline derivative B 0.257 g, aryl sulfonic acid ester D 0.245 g and F4TCNQ 0.025 g, triethylene glycol butyl methyl ether 5.0 g, diisopropyl malonic acid 3.00 g and dimethyl phthalate 2.00 g were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish E.
- Example 1-6 To aniline derivative B 0.184 g, aryl sulfonic acid ester C 0.327 g and DDQ 0.015 g, triethylene glycol butyl methyl ether 5.0 g, diisopropyl malonic acid 3.0 g and dimethyl phthalate 2.0 g were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish F.
- Polymer H1 (TFB polymer, LT-N148 manufactured by Luminescence Technology Co., Ltd.) represented by the following formula (H1) is 0.180 g, aryl sulfonic acid ester C 0.120 g and F4TCNQ 0.002 g, and triethylene glycol butyl methyl ether 5.00 g. 3.00 g of diisopropyl malonate and 2.00 g of dimethyl phthalate were added and stirred at room temperature to dissolve. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 ⁇ m to prepare a charge-transporting varnish K.
- the single-layer element A was formed by forming aluminum on the ITO substrate on which the thin film was formed at a vacuum level of 1.0 ⁇ 10 -5 Pa at 0.2 nm / sec to 80 nm. Made.
- the elements were sealed with a sealing substrate and then their characteristics were evaluated. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C or less, the elements are placed between the sealing substrates, and the sealing substrate is attached with an adhesive (Morresco Moisture Cut WB90US (P) manufactured by MORESCO Corporation).
- a water trapping agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed 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 annealing treatment at 80 ° C. for 1 hour to cure the adhesive.
- Example 2-2 A single-layer device B was produced in the same manner as in Example 2-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
- Example 2-3 A single-layer device C was produced in the same manner as in Example 2-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
- Example 2-4 A single-layer element D was produced in the same manner as in Example 2-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 2-5 A single-layer element E was produced in the same manner as in Example 2-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 2-6 A single-layer device F was produced in the same manner as in Example 2-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 2-1 A single-layer device G was produced in the same manner as in Example 2-1 except that the charge-transporting varnish G was used instead of the charge-transporting varnish A.
- Example 2-2 A single-layer device H was produced in the same manner as in Example 2-1 except that the charge-transporting varnish H was used instead of the charge-transporting varnish A.
- Example 2-3 A single-layer device I was produced in the same manner as in Example 2-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 2-4 A single-layer element J was produced in the same manner as in Example 2-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- the vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm / sec.
- the film thicknesses of the ⁇ -NPD and aluminum thin films were 30 nm and 80 nm, respectively.
- the element was sealed in the same manner as in Example 2-1 and then its characteristics were evaluated.
- Example 3-2 A hole-only element B was produced in the same manner as in Example 3-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
- Example 3-3 A hole-only element C was produced in the same manner as in Example 3-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
- Example 3-4 A hole-only element D was produced in the same manner as in Example 3-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 3-5 A hole-only element E was produced in the same manner as in Example 3-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 3-6 A hole-only element F was produced in the same manner as in Example 3-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 3-3 A hole-only element I was produced in the same manner as in Example 3-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 3-4 A hole-only element J was produced in the same manner as in Example 3-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- the thin film prepared from the charge transporting varnish of the present invention exhibits good hole injectability into ⁇ -NPD, which is often used as a hole transporting layer.
- Example 4-1 The charge-transporting varnish A is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a uniform thin film of 50 nm on the ITO substrate. did. On it, ⁇ -NPD was deposited at 0.2 nm / sec at 30 nm using a thin film deposition apparatus (vacuum degree 1.0 ⁇ 10 -5 Pa). Next, CBP and Ir (PPy) 3 were co-deposited.
- the vapor deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and 40 nm was laminated.
- a thin film of tris (8-quinolinolate) aluminum (III) (Alq 3 ), lithium fluoride, and aluminum was sequentially laminated to obtain an organic EL element A.
- the vapor deposition rate was 0.2 nm / sec for Alq 3 and aluminum, and 0.02 nm / sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
- the element was sealed in the same manner as in Example 2-1 and then its characteristics were evaluated.
- Example 4-2 An organic EL element B was produced in the same manner as in Example 4-1 except that the charge transporting varnish B was used instead of the charge transporting varnish A.
- Example 4-3 The organic EL element C was produced in the same manner as in Example 4-1 except that the charge transporting varnish C was used instead of the charge transporting varnish A.
- Example 4-4 An organic EL element D was produced in the same manner as in Example 4-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 4-5 An organic EL element E was produced in the same manner as in Example 4-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 4-6 An organic EL element F was produced in the same manner as in Example 4-1 except that a charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 4-3 An organic EL element I was produced in the same manner as in Example 4-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- Example 4-4 An organic EL element J was produced in the same manner as in Example 4-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
- the thin film prepared from the charge-transporting varnish of the present invention showed high organic EL characteristics.
- Example 5-2 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
- Example 5-3 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
- Example 5-4 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A.
- Example 5-5 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A.
- Example 5-6 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A.
- Example 5-1 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish G was used instead of the charge-transporting varnish A.
- Example 5-2 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish H was used instead of the charge-transporting varnish A.
- Example 5-3 A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A.
- Example 5-4 A substrate K with a charge-transporting thin film was produced in the same manner as in Example 5-1 except that the charge-transporting varnish K was used instead of the charge-transporting varnish A, but an uneven structure was generated on the film surface. No flat film was obtained.
- Example 5-5 A substrate L with a charge-transporting thin film was produced in the same manner as in Example 5-1 except that the charge-transporting varnish L was used instead of the charge-transporting varnish A, but an uneven structure was generated on the film surface. No flat film was obtained.
- the pile-up index was calculated for the prepared charge-transporting thin film.
- the pile-up index is (B) when the partition wall (bank) width is A ( ⁇ m) and the film thickness range of + 10% from the film thickness of the charge-transporting thin film at the center of the partition wall (bank) is B ( ⁇ m). It was calculated as / A) ⁇ 100 (%).
- Tables 4-5 In addition, Examples 5-1 to 5-3 and 5-6 and Comparative Examples 5-1 and 5-2 have a short side, and Examples 5-4 and 5-5 and Comparative Example 5-3 have a long side.
- the pile-up index was calculated as the partition wall width for each.
- the charge-transporting thin film formed by using the charge-transporting varnish of the present invention had good flatness and showed a high pile-up index of 95% or more.
- the charge-transporting thin film formed by using the charge-transporting varnish of the comparative example showed a lower pile-up index as compared with the example.
- the polymer H1 was used (Comparative Examples 5-4 and 5-5), an uneven structure was generated on the film surface, and a flat film could not be obtained.
Abstract
Description
1.(A)単分散の電荷輸送性有機化合物、(B)ドーパント及び(C)有機溶媒を含む電荷輸送性ワニスであって、
(B)ドーパントが、(B1)アリールスルホン酸エステル化合物と、(B2)ハロゲン化テトラシアノキノジメタン又は(B3)ハロゲン化若しくはシアノ化ベンゾキノンとを含む電荷輸送性ワニス。
2.前記単分散の電荷輸送性有機化合物が、アリールアミン誘導体である1の電荷輸送性ワニス。
3.前記アリールアミン誘導体が、3級アリールアミン化合物である2の輸送性ワニス。
4.前記3級アリールアミン化合物が、少なくとも1つの窒素原子を有し、かつ全ての窒素原子が3級アリールアミン構造を有するものである3の電荷輸送性ワニス。
5.前記3級アリールアミン化合物が、少なくとも2つの窒素原子を有し、かつ全ての窒素原子が3級アリールアミン構造を有するものである4の電荷輸送性ワニス。
6.前記アリールスルホン酸エステル化合物が、下記式(B1)又は(B1')で表されるものである1~5のいずれかの電荷輸送性ワニス。
A2は、-O-、-S-又は-NH-であり;
A3は、又は炭素数6~20の(n+1)価の芳香族基であり;
X1は、炭素数2~5のアルキレン基であり、該アルキレン基の炭素原子間に、-O-、-S-又はカルボニル基が介在していてもよく、該アルキレン基の水素原子の一部又は全部が、更に炭素数1~20のアルキル基で置換されていてもよく;
X2は、単結合、-O-、-S-又は-NR-であり、Rは、水素原子又は炭素数1~10の1価炭化水素基であり;
X3は、置換基を有していてもよい炭素数1~20の1価炭化水素基であり;
mは、1≦m≦4を満たす整数であり;
nは、1≦n≦4を満たす整数である。]
7.前記アリールスルホン酸エステル化合物が、下記式(B1-1)~(B1-3)のいずれかで表されるものである6の電荷輸送性ワニス。
A11は、パーフルオロビフェニルから誘導されるm価の基であり、A12は、-O-又は-S-であり、A13は、ナフタレン又はアントラセンから誘導される(n+1)価の基であり;
m及びnは、前記と同じである。)
A14は、置換基を有していてもよい、1つ以上の芳香環を含むm価の炭化水素基であり、A15は、-O-又は-S-であり、A16は、(n+1)価の芳香族基であり;
m及びnは、前記と同じである。)
Rs14~Rs17は、それぞれ独立に、水素原子、又は直鎖状若しくは分岐状の炭素数1~20の1価脂肪族炭化水素基であり;
Rs18は、直鎖状若しくは分岐状の炭素数1~20の1価脂肪族炭化水素基、又は-ORs19であり、Rs19は、置換基を有していてもよい炭素数2~20の1価炭化水素基であり;
A17は、-O-、-S-又は-NH-であり;
A18は、(n+1)価の芳香族基であり;
nは、前記と同じである。)
8.(B2)ハロゲン化テトラシアノキノジメタンが、下記式(B2)で表されるものである1~7のいずれかの電荷輸送性ワニス。
9.(B3)ハロゲン化又はシアノ化ベンゾキノンが、下記式(B3)で表されるものである1~8のいずれかの電荷輸送性ワニス。
10.前記(B1)アリールスルホン酸エステル化合物の含有量が、前記(B2)ハロゲン化テトラシアノキノジメタン又は前記(B3)ハロゲン化若しくはシアノ化ベンゾキノンに対し、モル比で、0.01~50である1~9のいずれかの電荷輸送性ワニス。
11.前記単分散の電荷輸送性有機化合物の分子量が、200~9,000である1~10のいずれかの電荷輸送性ワニス。
12.前記有機溶媒が、低極性有機溶媒を含む1~11のいずれかの電荷輸送性ワニス。
13.1~12のいずれかの電荷輸送性ワニスから得られる電荷輸送性薄膜。
14.13の電荷輸送性薄膜を備える有機EL素子。
15.前記電荷輸送性薄膜が、正孔注入層又は正孔輸送層である14の有機EL素子。 That is, the present invention provides the following charge transporting varnish.
1. 1. A charge-transporting varnish containing (A) a monodisperse charge-transporting organic compound, (B) a dopant, and (C) an organic solvent.
A charge-transporting varnish in which the dopant (B) comprises (B1) an aryl sulfonic acid ester compound and (B2) a halogenated tetracyanoquinodimethane or (B3) a halogenated or cyanated benzoquinone.
2. 2. The charge-transporting varnish of 1 in which the monodisperse charge-transporting organic compound is an arylamine derivative.
3. 3. 2. Transport varnish of 2 in which the arylamine derivative is a tertiary arylamine compound.
4. 3. A charge-transporting varnish of 3, wherein the tertiary arylamine compound has at least one nitrogen atom and all nitrogen atoms have a tertiary arylamine structure.
5. 4. The charge-transporting varnish of 4, wherein the tertiary arylamine compound has at least two nitrogen atoms and all nitrogen atoms have a tertiary arylamine structure.
6. A charge-transporting varnish according to any one of 1 to 5, wherein the aryl sulfonic acid ester compound is represented by the following formula (B1) or (B1').
A 2 is -O-, -S- or -NH-;
A 3 is, or an (n + 1) -valent aromatic group with 6 to 20 carbon atoms;
X 1 is an alkylene group having 2 to 5 carbon atoms, and an —O—, —S— or carbonyl group may be interposed between the carbon atoms of the alkylene group, and one of the hydrogen atoms of the alkylene group. Part or all may be further substituted with an alkyl group having 1 to 20 carbon atoms;
X 2 is a single bond, -O-, -S- or -NR-, and R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms;
X 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
m is an integer that satisfies 1 ≦ m ≦ 4.
n is an integer that satisfies 1 ≦ n ≦ 4. ]
7. The charge transporting varnish of 6 in which the aryl sulfonic acid ester compound is represented by any of the following formulas (B1-1) to (B1-3).
A 11 is an m-valent group derived from perfluorobiphenyl, A 12 is an -O- or -S-, and A 13 is a (n + 1) -valent group derived from naphthalene or anthracene. Yes;
m and n are the same as described above. )
A 14 is an m-valent hydrocarbon group containing one or more aromatic rings, which may have a substituent, A 15 is —O— or —S—, and A 16 is ( It is an n + 1) valent aromatic group;
m and n are the same as described above. )
R s14 to R s17 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms;
R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or −OR s19 , and R s19 has 2 to 20 carbon atoms which may have a substituent. Is a monovalent hydrocarbon group of
A 17 is -O-, -S- or -NH-;
A 18 is an (n + 1) -valent aromatic group;
n is the same as described above. )
8. (B2) A charge-transporting varnish according to any one of 1 to 7, wherein the halogenated tetracyanoquinodimethane is represented by the following formula (B2).
9. (B3) A charge-transporting varnish according to any one of 1 to 8, wherein the halogenated or cyanated benzoquinone is represented by the following formula (B3).
10. The content of the (B1) aryl sulfonic acid ester compound is 0.01 to 50 in molar ratio with respect to the (B2) halogenated tetracyanoquinodimethane or the (B3) halogenated or cyanated benzoquinone. A charge transporting varnish of any one of 1-9.
11. A charge-transporting varnish according to any one of 1 to 10, wherein the monodisperse charge-transporting organic compound has a molecular weight of 200 to 9,000.
12. The charge transporting varnish according to any one of 1 to 11, wherein the organic solvent contains a low-polarity organic solvent.
A charge-transporting thin film obtained from any of the charge-transporting varnishes of 13.1-12.
An organic EL device including a charge transporting thin film of 14.13.
15. 14 organic EL devices in which the charge transporting thin film is a hole injection layer or a hole transport layer.
本発明の電荷輸送性ワニスは、(A)単分散の電荷輸送性有機化合物、(B)ドーパント及び(C)有機溶媒を含む電荷輸送性ワニスであって、(B)ドーパントが、(B1)アリールスルホン酸エステル化合物と、(B2)ハロゲン化テトラシアノキノジメタン又は(B3)ハロゲン化若しくはシアノ化ベンゾキノンとを含むものである。 [Charge transport varnish]
The charge transport varnish of the present invention is a charge transport varnish containing (A) a monodisperse charge transport organic compound, (B) a dopant and (C) an organic solvent, and (B) the dopant is (B1). It contains an aryl sulfonic acid ester compound and (B2) halogenated tetracyanoquinodimethane or (B3) halogenated or cyanated benzoquinone.
本発明において、電荷輸送性有機化合物としては、例えば従来有機ELの分野等で用いられるものを用いることができる。その具体例としては、オリゴアニリン誘導体、N,N'-ジアリールベンジジン誘導体、N,N,N',N'-テトラアリールベンジジン誘導体等のアリールアミン誘導体(アニリン誘導体)、オリゴチオフェン誘導体、チエノチオフェン誘導体、チエノベンゾチオフェン誘導体等のチオフェン誘導体、オリゴピロール等のピロール誘導体等の各種電荷輸送性有機化合物が挙げられる。これらのうち、アリールアミン誘導体、チオフェン誘導体が好ましい。 [(A) Charge-transporting organic compound]
In the present invention, as the charge transporting organic compound, for example, those conventionally used in the field of organic EL can be used. Specific examples thereof include arylamine derivatives (aniline derivatives) such as oligoaniline derivatives, N, N'-diarylbenzidine derivatives, N, N, N', N'-tetraarylbenzidine derivatives, oligothiophene derivatives, and thienothiophene derivatives. , Thionophen derivatives such as thienobenzothiophene derivatives, and various charge-transporting organic compounds such as pyrrole derivatives such as oligopyrrole. Of these, arylamine derivatives and thiophene derivatives are preferable.
本発明の電荷輸送性ワニスは、(B)成分のドーパントとして、(B1)アリールスルホン酸エステル化合物及び(B2)ハロゲン化テトラシアノキノジメタン又は(B3)ハロゲン化若しくはシアノ化ベンゾキノンを含む。 [(B) Dopant]
The charge-transporting varnish of the present invention contains (B1) aryl sulfonic acid ester compound and (B2) halogenated tetracyanoquinodimethane or (B3) halogenated or cyanated benzoquinone as the dopant of the component (B).
前記アリールスルホン酸エステル化合物は、芳香環上にスルホン酸エステル基が結合したものであれば特に限定されない。本発明の好ましい一態様において、前記アリールスルホン酸エステル化合物の分子量は、好ましくは100以上、より好ましくは200以上であり、好ましくは5,000以下、より好ましくは4,000以下、より一層好ましくは3,000以下、更に好ましくは2,000以下である。本発明の好ましい一態様において、前記アリールスルホン酸エステル化合物が有するスルホン酸エステル基の数は、好ましくは2以上、より好ましくは3以上であり、好ましくは6以下、より好ましくは5以下である。本発明の好ましい一態様において、前記アリールスルホン酸エステル化合物は、好ましくはフッ素で置換された芳香環を含む。 [(B1) Aryl sulfonic acid ester compound]
The aryl sulfonic acid ester compound is not particularly limited as long as it has a sulfonic acid ester group bonded to the aromatic ring. In a preferred embodiment of the present invention, the molecular weight of the aryl sulfonic acid ester compound is preferably 100 or more, more preferably 200 or more, preferably 5,000 or less, more preferably 4,000 or less, still more preferably. It is 3,000 or less, more preferably 2,000 or less. In a preferred embodiment of the present invention, the number of sulfonic acid ester groups contained in the aryl sulfonic acid ester compound is preferably 2 or more, more preferably 3 or more, preferably 6 or less, and more preferably 5 or less. In a preferred embodiment of the invention, the aryl sulfonic acid ester compound preferably comprises a fluorine-substituted aromatic ring.
前記ハロゲン化テトラシアノキノジメタンとしては、下記式(B2)で表されるものが好ましい。
As the halogenated tetracyanoquinodimethane, those represented by the following formula (B2) are preferable.
前記ハロゲン化又はシアノ化ベンゾキノンとしては、式(B3)で表されるものが好ましい。
As the halogenated or cyanated benzoquinone, those represented by the formula (B3) are preferable.
(C)有機溶媒としては、前述した各成分や後述する各任意成分を溶解又は分散可能なものであれば、特に限定されないが、プロセス適合性に優れている点で低極性溶媒を用いることが好ましい。本発明において、低極性溶媒とは周波数100kHzでの比誘電率が7未満のものを、高極性溶媒とは周波数100kHzでの比誘電率が7以上のものと定義する。 [(C) Organic solvent]
The organic solvent (C) is not particularly limited as long as it can dissolve or disperse each of the above-mentioned components and each of the optional components described below, but a low-polarity solvent may be used because of its excellent process compatibility. preferable. In the present invention, a low-polarity solvent is defined as a solvent having a relative permittivity of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as a solvent having a relative permittivity of 7 or more at a frequency of 100 kHz.
本発明の電荷輸送性ワニスは、得られる電荷輸送性薄膜の膜物性の調整等の目的で、更に有機シラン化合物を含んでもよい。前記有機シラン化合物としては、ジアルコキシシラン化合物、トリアルコキシシラン化合物又はテトラアルコキシシラン化合物が挙げられる。とりわけ、有機シラン化合物としては、ジアルコキシシラン化合物又はトリアルコキシシラン化合物が好ましく、トリアルコキシシラン化合物がより好ましい。有機シラン化合物は、1種単独で又は2種以上を組み合わせて用いてもよい。 [Other ingredients]
The charge-transporting varnish of the present invention may further contain an organic silane compound for the purpose of adjusting the film physical characteristics of the obtained charge-transporting thin film. Examples of the organic silane compound include a dialkoxysilane compound, a trialkoxysilane compound, and a tetraalkoxysilane compound. In particular, as the organic silane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The organic silane compound may be used alone or in combination of two or more.
本発明の電荷輸送性薄膜は、本発明の電荷輸送性ワニスを基材上に塗布し、焼成することで形成することができる。 [Charge transport thin film]
The charge-transporting thin film of the present invention can be formed by applying the charge-transporting varnish of the present invention on a substrate and firing it.
本発明の有機EL素子は、一対の電極を有し、これら電極の間に、本発明の電荷輸送性薄膜からなる機能層を有するものである。 [Organic EL element]
The organic EL device of the present invention has a pair of electrodes, and has a functional layer made of the charge-transporting thin film of the present invention between these electrodes.
(a)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(b)陽極/正孔注入層/正孔輸送層/発光層/電子注入輸送層/陰極
(c)陽極/正孔注入輸送層/発光層/電子輸送層/電子注入層/陰極
(d)陽極/正孔注入輸送層/発光層/電子注入輸送層/陰極
(e)陽極/正孔注入層/正孔輸送層/発光層/陰極
(f)陽極/正孔注入輸送層/発光層/陰極 Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f). In the following configuration, if necessary, an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole block layer or the like may be provided between the light emitting layer and the cathode. Further, the hole injection layer, the hole transport layer or the hole injection transport layer may have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may serve as a hole block layer or the like. It may also have the functions of. Further, if necessary, an arbitrary functional layer can be provided between the layers.
(A) Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode (c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode (f) Electron / hole injection transport layer / light emitting layer / cathode
(1)MALDI-TOF-MS:ブルカー社製autoflex III smartbeam
(2)1H-NMR:日本電子(株)製JNM-ECP300 FT NMR SYSTEM
(3)基板洗浄:長州産業(株)製基板洗浄装置(減圧プラズマ方式)
(4)ワニスの塗布:ミカサ(株)製スピンコーターMS-A100
(5)膜厚測定及び表面形状測定:(株)小坂研究所製微細形状測定機サーフコーダET-4000A
(6)素子の作製:長州産業(株)製多機能蒸着装置システムC-E2L1G1-N
(7)素子の電流密度の測定:(株)イーエッチシー製多チャンネルIVL測定装置
(8)インクジェット装置:クラスターテクノロジー(株)製専用ドライバWAVE BUILDER(型番:PIJD-1)、カメラ付き観測装置inkjetlado、自動ステージInkjet Designer及びインクジェットヘッドPIJ-25NSET The equipment used is as follows.
(1) MALDI-TOF-MS: Bruker's autoflex III smart beam
(2) 1 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd.
(3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Sangyo Co., Ltd. (decompression plasma method)
(4) Varnish application: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(5) Film thickness measurement and surface shape measurement: Fine shape measuring machine surf coder ET-4000A manufactured by Kosaka Laboratory Co., Ltd.
(6) Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
(7) Measurement of element current density: Multi-channel IVL measuring device manufactured by EHC Co., Ltd. (8) Inkjet device: Dedicated driver WAVE BUILDER (model number: PIJD-1) manufactured by Cluster Technology Co., Ltd., observation device with camera inkjetlado, automatic stage Inkjet Designer and inkjet head PIJ-25NSET
MMA:メチルメタクリレート
HEMA:2-ヒドロキシエチルメタクリレート
HPMA:4-ヒドロキシフェニルメタクリレート
HPMA-QD:4-ヒドロキシフェニルメタクリレート1molと1,2-ナフトキノン-2-ジアジド-5-スルホニルクロリド1.1molとの縮合反応によって合成した化合物
CHMI:N-シクロヘキシルマレイミド
PFHMA:2-(パーフルオロヘキシル)エチルメタクリレート
MAA:メタクリル酸
AIBN:α,α'-アゾビスイソブチロニトリル
QD1:α,α,α'-トリス(4-ヒドロキシフェニル)-1-エチル-4-イソプロピルベンゼン1molと1,2-ナフトキノン-2-ジアジド-5-スルホニルクロリド1.5molとの縮合反応によって合成した化合物
GT-401:ブタンテトラカルボン酸テトラ(3,4-エポキシシクロヘキシルメチル)修飾ε-カプロラクトン(商品名:エポリードGT-401、(株)ダイセル製)
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
CHN:シクロヘキサノン
TMAH:テトラメチルアンモニウムヒドロキシド The reagents used are as follows.
MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate HPMA: 4-Hydroxyphenyl methacrylate HPMA-QD: Condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compound CHMI: N-cyclohexylmaleimide PFHMA: 2- (perfluorohexyl) ethyl methacrylate MAA: AIBN methacrylate: α, α'-azobisisobutyronitrile QD1: α, α, α'-tris (4) -Hydroxyphenyl) A compound synthesized by a condensation reaction of 1 mol of -1-ethyl-4-isopropylbenzene and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. GT-401: Tetrabutanetetracarboxylate (Tetrabutantetracarboxylate) 3,4-Epoxycyclohexylmethyl) modified ε-caprolactone (trade name: Epolide GT-401, manufactured by Daicel Co., Ltd.)
PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate CHN: Cyclohexanone TMAH: Tetramethylammonium Hydroxide
(1)アクリル重合体の合成
[合成例1-1]
MMA(10.0g)、HEMA(12.5g)、CHMI(20.0g)、HPMA(2.50g)、MAA(5.00g)及びAIBN(3.20g)をPGME(79.8g)に溶解し、60~100℃にて20時間反応させることにより、アクリル重合体P1溶液(固形分濃度40質量%)を得た。アクリル重合体P1のMnは3,700、Mwは6,100であった。 [1] Preparation of substrate with partition wall (bank) (1) Synthesis of acrylic polymer [Synthesis Example 1-1]
MMA (10.0 g), HEMA (12.5 g), CHMI (20.0 g), HPMA (2.50 g), MAA (5.00 g) and AIBN (3.20 g) are dissolved in PGME (79.8 g). Then, the reaction was carried out at 60 to 100 ° C. for 20 hours to obtain an acrylic polymer P1 solution (solid content concentration: 40% by mass). The Mn of the acrylic polymer P1 was 3,700 and the Mw was 6,100.
HPMA-QD(2.50g)、PFHMA(7.84g)、MAA(0.70g)、CHMI(1.46g)及びAIBN(0.33g)をCHN(51.3g)に溶解し、110℃にて20時間攪拌して反応させることにより、アクリル重合体P2溶液(固形分濃度20質量%)を得た。アクリル重合体P2のMnは4,300、Mwは6,300であった。 [Synthesis Example 1-2]
HPMA-QD (2.50 g), PFHMA (7.84 g), MAA (0.70 g), CHMI (1.46 g) and AIBN (0.33 g) were dissolved in CHN (51.3 g) and heated to 110 ° C. By stirring and reacting for 20 hours, an acrylic polymer P2 solution (solid content concentration: 20% by mass) was obtained. The Mn of the acrylic polymer P2 was 4,300 and the Mw was 6,300.
・クロマトグラフ:(株)島津製作所製GPC装置LC-20AD
・カラム:Shodex KF-804L及び803L(昭和電工(株)製)並びにTSK-GEL(東ソー(株)製)を直列接続
・カラム温度:40℃
・検出器:UV検出器(254nm)及びRI検出器
・溶離液:テトラヒドロフラン
・カラム流速:1mL/分 The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acrylic polymers P1 and P2 were measured by gel permeation chromatography (GPC) under the following conditions.
・ Chromatograph: GPC device LC-20AD manufactured by Shimadzu Corporation
-Column: Shodex KF-804L and 803L (manufactured by Showa Denko KK) and TSK-GEL (manufactured by Tosoh Corporation) are connected in series.-Column temperature: 40 ° C
-Detector: UV detector (254 nm) and RI detector-Eluent: tetrahydrofuran-Column flow rate: 1 mL / min
[製造例1]
アクリル重合体P1溶液(5.04g)、アクリル重合体P2溶液(0.05g)、QD1(0.40g)、GT-401(0.09g)及びPGMEA(6.42g)を混合し、室温で3時間攪拌して均一な溶液とし、ポジ型感光性樹脂組成物を得た。 (2) Production of Positive Photosensitive Resin Composition [Production Example 1]
Acrylic polymer P1 solution (5.04 g), acrylic polymer P2 solution (0.05 g), QD1 (0.40 g), GT-401 (0.09 g) and PGMEA (6.42 g) are mixed and at room temperature. The mixture was stirred for 3 hours to obtain a uniform solution to obtain a positive photosensitive resin composition.
[製造例2]
(株)テクノビジョン製UV-312を用いて10分間オゾン洗浄したITO-ガラス基板上に、スピンコーターを用いて、製造例1で得られたポジ型感光性樹脂組成物を塗布した後、基板をホットプレート上でプリベーク(100℃、120秒間)し、膜厚1.2μmの薄膜を形成した。この薄膜に、長辺200μm、短辺100μmの長方形が多数描かれたパターンのマスクを介して、キヤノン(株)製紫外線照射装置PLA-600FAにより、波長365nmの紫外線を用いて175mJ/cm2で露光した。その後、薄膜を1.0質量%TMAH水溶液に120秒間浸漬して現像を行った後、超純水を用いて薄膜の流水洗浄を20秒間行った。次いで、この長方形パターンが形成された薄膜をポストベーク(230℃、30分間)して硬化させ、隔壁付基板を作製した。 (3) Fabrication of Substrate with Partition (Bank) [Manufacturing Example 2]
The positive photosensitive resin composition obtained in Production Example 1 was applied to an ITO-glass substrate that had been ozone-cleaned for 10 minutes using UV-312 manufactured by Technovision Co., Ltd. using a spin coater, and then the substrate. Was prebaked (100 ° C., 120 seconds) on a hot plate to form a thin film having a film thickness of 1.2 μm. At 175 mJ / cm 2 using ultraviolet rays with a wavelength of 365 nm by the ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask with a pattern in which a large number of rectangles with a long side of 200 μm and a short side of 100 μm are drawn on this thin film. Exposed. Then, the thin film was immersed in a 1.0 mass% TMAH aqueous solution for 120 seconds for development, and then the thin film was washed with running water for 20 seconds using ultrapure water. Next, the thin film on which this rectangular pattern was formed was post-baked (230 ° C., 30 minutes) and cured to prepare a substrate with a partition wall.
[合成例2-1]アニリン誘導体Aの合成
攪拌終了後、反応混合物を室温まで冷却し、冷却した反応混合物と、トルエンと、イオン交換水とを混合して分液処理をした。得られた有機層を硫酸ナトリウムで乾燥し、濃縮した。濃縮液をシリカゲルにてろ過を行い、得られたろ液に活性炭0.2gを加え、室温で30分攪拌した。
その後、ろ過にて活性炭を取り除き、ろ液を濃縮した。濃縮液をメタノール及び酢酸エチルの混合溶媒(500mL/500mL)に滴下し、得られたスラリーを室温で一晩攪拌し、次いでスラリーをろ過してろ物を回収した。得られたろ物を乾燥し、目的とするアニリン誘導体Aを得た(収量5.88g、収率83%)。
1H-NMR(500MHz, THF-d8) δ[ppm]: 8.02-8.10(m, 10H), 7.48-7.63(m, 22H), 7.28-7.39(m, 14H), 7.19-7.24(m, 10H), 7.02-7.09(m, 12H).
MALDI-TOF-MS m/Z found: 1404.88 ([M]+calcd:1404.56). 1.00 g of N1- (4-aminophenyl) benzene-1,4-diamine, 8.89 g of 2-bromo-9-phenyl-9H-carbazole, 112 mg of palladium acetate and 3.47 g of tert-butoxysodium were placed in a flask. After that, the inside of the flask was replaced with nitrogen. Toluene (30 mL) and a previously prepared toluene solution of di-tert-butyl (phenyl) phosphine (2.75 mL (concentration: 81.0 g / L)) were added thereto, and the mixture was stirred at 90 ° C. for 6 hours.
After the stirring was completed, the reaction mixture was cooled to room temperature, and the cooled reaction mixture, toluene, and ion-exchanged water were mixed and subjected to liquid separation treatment. The obtained organic layer was dried over sodium sulfate and concentrated. The concentrated solution was filtered through silica gel, 0.2 g of activated carbon was added to the obtained filtrate, and the mixture was stirred at room temperature for 30 minutes.
Then, the activated carbon was removed by filtration, and the filtrate was concentrated. The concentrate was added dropwise to a mixed solvent of methanol and ethyl acetate (500 mL / 500 mL), the obtained slurry was stirred at room temperature overnight, and then the slurry was filtered to recover the filtrate. The obtained filtrate was dried to obtain the desired aniline derivative A (yield 5.88 g, yield 83%).
1 H-NMR (500MHz, THF-d 8 ) δ [ppm]: 8.02-8.10 (m, 10H), 7.48-7.63 (m, 22H), 7.28-7.39 (m, 14H), 7.19-7.24 (m, 10H), 7.02-7.09 (m, 12H).
MALDI-TOF-MS m / Z found: 1404.88 ([M] + calcd: 1404.56).
国際公開第2015/050253号に記載された方法に従って、下記式で表されるアニリン誘導体Bを合成した。
[合成例3-1]アリールスルホン酸エステルCの合成
国際公開第2017/217455号に記載された方法に従って、下記式で表されるアリールスルホン酸エステルCを合成した。
まず、国際公開第2015/111654号に記載の方法に従って、下記式で表されるアリールスルホン酸D'を合成した。
アリールスルホン酸D'(4.97g、10mmol)に、塩化チオニル(25g)及び触媒としてN,N-ジメチルホルムアミド(0.4mL)を加え、1時間加熱還流した後、塩化チオニルを留去し、アリールスルホン酸D'の酸クロリドを含む固体を得た。本化合物はこれ以上精製することなく次工程に使用した。
前記固体にクロロホルム(30mL)及びピリジン(20mL)を加え、0℃にてプロピレングリコールモノエチルエーテル6.24g(60mmol)を加えた。室温まで昇温し、その後1.5時間攪拌した。溶媒を留去した後、水を加え、酢酸エチルにて抽出し、有機層を硫酸ナトリウムにて乾燥させた。ろ過、濃縮後、得られた粗生成物をシリカゲルカラムクロマトグラフィー(ヘキサン/酢酸エチル)で精製することにより、アリールスルホン酸エステルD1.32gを白色固体として得た(収率20%(アリールスルホン酸D'からの2段階収率))。1H-NMR及びLC/MSの測定結果を以下に示す。
1H-NMR(500MHz, CDCl3): δ 0.89-0.95(m, 6H), 1.34 and 1.39(a pair of d, J=6.5Hz, 6H), 3.28-3.50(m, 8H), 4.81-4.87(m, 2H), 7.26(s, 1H), 8.22(d, J=9.0Hz, 1H), 8.47(s, 1H), 8.54(d, J=9.0Hz, 1H) , 8.68(s, 1H).
LC/MS (ESI+) m/z; 687 [M+NH4]+
Thionyl chloride (25 g) and N, N-dimethylformamide (0.4 mL) as a catalyst were added to aryl sulfonic acid D'(4.97 g, 10 mmol), heated and refluxed for 1 hour, and then thionyl chloride was distilled off. A solid containing the acid chloride of aryl sulfonic acid D'was obtained. This compound was used in the next step without further purification.
Chloroform (30 mL) and pyridine (20 mL) were added to the solid, and 6.24 g (60 mmol) of propylene glycol monoethyl ether was added at 0 ° C. The temperature was raised to room temperature, and then the mixture was stirred for 1.5 hours. After distilling off the solvent, water was added, the mixture was extracted with ethyl acetate, and the organic layer was dried over sodium sulfate. After filtration and concentration, the obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 1.32 g of aryl sulfonic acid ester D as a white solid (yield 20% (aryl sulfonic acid). Two-step yield from D')). 1 The measurement results of 1 H-NMR and LC / MS are shown below.
1 1 H-NMR (500MHz, CDCl 3 ): δ 0.89-0.95 (m, 6H), 1.34 and 1.39 (a pair of d, J = 6.5Hz, 6H), 3.28-3.50 (m, 8H), 4.81-4.87 (m, 2H), 7.26 (s, 1H), 8.22 (d, J = 9.0Hz, 1H), 8.47 (s, 1H), 8.54 (d, J = 9.0Hz, 1H), 8.68 (s, 1H) ..
LC / MS (ESI + ) m / z; 687 [M + NH 4 ] +
[実施例1-1]
アニリン誘導体A0.183g、アリールスルホン酸エステルC0.325g及びF4TCNQ0.018gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスAを調製した。 [4] Preparation of charge-transporting varnish [Example 1-1]
To 0.003 g of aniline derivative A, 0.325 g of aryl sulfonic acid ester and 0.018 g of F4TCNQ, 5.00 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added and stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish A.
アニリン誘導体A0.257g、アリールスルホン酸エステルD0.245g及びF4TCNQ0.025gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスBを調製した。 [Example 1-2]
To 0.057 g of the aniline derivative A, 0.245 g of the aryl sulfonic acid ester and 0.025 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish B.
アニリン誘導体A0.184g、アリールスルホン酸エステルC0.327g及びDDQ0.015gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスCを調製した。 [Example 1-3]
To 0.184 g of the aniline derivative A, 0.327 g of the aryl sulfonic acid ester and 0.015 g of DDQ, 5.00 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish C.
アニリン誘導体B0.183g、アリールスルホン酸エステルC0.325g及びF4TCNQ0.018gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスDを調製した。 [Example 1-4]
To 0.003 g of aniline derivative B, 0.325 g of aryl sulfonic acid ester and 0.018 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish D.
アニリン誘導体B0.257g、アリールスルホン酸エステルD0.245g及びF4TCNQ0.025gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスEを調製した。 [Example 1-5]
To aniline derivative B 0.257 g, aryl sulfonic acid ester D 0.245 g and F4TCNQ 0.025 g, triethylene glycol butyl methyl ether 5.0 g, diisopropyl malonic acid 3.00 g and dimethyl phthalate 2.00 g were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish E.
アニリン誘導体B0.184g、アリールスルホン酸エステルC0.327g及びDDQ0.015gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスFを調製した。 [Example 1-6]
To aniline derivative B 0.184 g, aryl sulfonic acid ester C 0.327 g and DDQ 0.015 g, triethylene glycol butyl methyl ether 5.0 g, diisopropyl malonic acid 3.0 g and dimethyl phthalate 2.0 g were added, and the mixture was stirred at room temperature. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish F.
アニリン誘導体A0.479g及びF4TCNQ0.047gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスGを調製した。 [Comparative Example 1-1]
To 0.009 g of aniline derivative A and 0.047 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was dissolved by stirring at room temperature. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish G.
アニリン誘導体A0.487g及びDDQ0.039gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスHを調製した。 [Comparative Example 1-2]
To 0.487 g of aniline derivative A and 0.039 g of DDQ, 5.00 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was dissolved by stirring at room temperature. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish H.
アニリン誘導体B0.479g及びF4TCNQ0.047gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスIを調製した。 [Comparative Example 1-3]
To 0.007 g of aniline derivative B and 0.047 g of F4TCNQ, 5.0 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was dissolved by stirring at room temperature. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish I.
アニリン誘導体B0.487g及びDDQ0.039gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスJを調製した。 [Comparative Example 1-4]
To 0.487 g of aniline derivative B and 0.039 g of DDQ, 5.00 g of triethylene glycol butyl methyl ether, 3.00 g of diisopropyl malonic acid and 2.00 g of dimethyl phthalate were added, and the mixture was dissolved by stirring at room temperature. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish J.
下記式(H1)で表されるポリマーH1(TFBポリマー、Luminescence Technology社製LT-N148)0.180g、アリールスルホン酸エステルC0.120g及びF4TCNQ0.002gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスKを調製した。
Polymer H1 (TFB polymer, LT-N148 manufactured by Luminescence Technology Co., Ltd.) represented by the following formula (H1) is 0.180 g, aryl sulfonic acid ester C 0.120 g and F4TCNQ 0.002 g, and triethylene glycol butyl methyl ether 5.00 g. 3.00 g of diisopropyl malonate and 2.00 g of dimethyl phthalate were added and stirred at room temperature to dissolve. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish K.
ポリマーH1 0.180g、アリールスルホン酸エステルD0.120g及びF4TCNQ0.002gに、トリエチレングリコールブチルメチルエーテル5.00g、マロン酸ジイソプロピル3.00g及びフタル酸ジメチル2.00gを加え、室温で攪拌して溶解させた。得られた溶液を孔径0.2μmのPTFEシリンジフィルターでろ過し、電荷輸送性ワニスLを調製した。 [Comparative Example 1-6]
To 0.180 g of polymer H1. It was dissolved. The obtained solution was filtered through a PTFE syringe filter having a pore size of 0.2 μm to prepare a charge-transporting varnish L.
[実施例2-1]
電荷輸送性ワニスAを、スピンコーターを用いてITO基板に塗布した後、大気下、120℃で1分間乾燥し、次いで200℃で15分間焼成し、ITO基板上に厚さ50nmの均一な薄膜を形成した。ITO基板としては、パターニングされた厚さ150nmのITO膜が表面に形成された、25mm×25mm×0.7tのガラス基板を用い、使用前にO2プラズマ洗浄装置(150W、30秒間)によって表面上の不純物を除去した。次いで、薄膜を形成したITO基板に対し、蒸着装置(真空度1.0×10-5Pa)を用いて、アルミニウムを0.2nm/秒にて80nm成膜することで、単層素子Aを作製した。
なお、空気中の酸素、水等の影響による特性劣化を防止するため、素子は封止基板により封止した後、その特性を評価した。封止は、以下の手順で行った。酸素濃度2ppm以下、露点-76℃以下の窒素雰囲気中で、素子を封止基板の間に収め、封止基板を接着剤(((株)MORESCO製モレスコモイスチャーカットWB90US(P))により貼り合わせた。この際、捕水剤(ダイニック(株)製HD-071010W-40)を素子と共に封止基板内に収めた。貼り合わせた封止基板に対し、UV光を照射(波長:365nm、照射量:6,000mJ/cm2)した後、80℃で1時間、アニーリング処理して接着剤を硬化させた。 [5] Fabrication and characterization of single-layer device (SLD) [Example 2-1]
The charge-transporting varnish A is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a uniform thin film having a thickness of 50 nm on the ITO substrate. Was formed. As the ITO substrate, a 25 mm × 25 mm × 0.7 t glass substrate having a patterned ITO film having a thickness of 150 nm formed on the surface was used, and the surface was subjected to an O 2 plasma cleaning device (150 W, 30 seconds) before use. The above impurities were removed. Next, the single-layer element A was formed by forming aluminum on the ITO substrate on which the thin film was formed at a vacuum level of 1.0 × 10 -5 Pa at 0.2 nm / sec to 80 nm. Made.
In order to prevent deterioration of characteristics due to the influence of oxygen, water, etc. in the air, the elements were sealed with a sealing substrate and then their characteristics were evaluated. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C or less, the elements are placed between the sealing substrates, and the sealing substrate is attached with an adhesive (Morresco Moisture Cut WB90US (P) manufactured by MORESCO Corporation). At this time, a water trapping agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed 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 annealing treatment at 80 ° C. for 1 hour to cure the adhesive.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスBを用いた以外は、実施例2-1と同様の方法で単層素子Bを作製した。 [Example 2-2]
A single-layer device B was produced in the same manner as in Example 2-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスCを用いた以外は、実施例2-1と同様の方法で単層素子Cを作製した。 [Example 2-3]
A single-layer device C was produced in the same manner as in Example 2-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスDを用い、230℃で15分間焼成した以外は、実施例2-1と同様の方法で単層素子Dを作製した。 [Example 2-4]
A single-layer element D was produced in the same manner as in Example 2-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスEを用い、230℃で15分間焼成した以外は、実施例2-1と同様の方法で単層素子Eを作製した。 [Example 2-5]
A single-layer element E was produced in the same manner as in Example 2-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスFを用い、230℃で15分間焼成した以外は、実施例2-1と同様の方法で単層素子Fを作製した。 [Example 2-6]
A single-layer device F was produced in the same manner as in Example 2-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスGを用いた以外は、実施例2-1と同様の方法で単層素子Gを作製した。 [Comparative Example 2-1]
A single-layer device G was produced in the same manner as in Example 2-1 except that the charge-transporting varnish G was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスHを用いた以外は、実施例2-1と同様の方法で単層素子Hを作製した。 [Comparative Example 2-2]
A single-layer device H was produced in the same manner as in Example 2-1 except that the charge-transporting varnish H was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスIを用い、230℃で15分間焼成した以外は、実施例2-1と同様の方法で単層素子Iを作製した。 [Comparative Example 2-3]
A single-layer device I was produced in the same manner as in Example 2-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスJを用い、230℃で15分間焼成した以外は、実施例2-1と同様の方法で単層素子Jを作製した。 [Comparative Example 2-4]
A single-layer element J was produced in the same manner as in Example 2-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
以下の実施例及び比較例において、ITO基板は、前記と同様のものを使用した。
[実施例3-1]
電荷輸送性ワニスAを、スピンコーターを用いてITO基板に塗布した後、大気下、120℃で1分間乾燥し、次いで200℃で15分間焼成し、ITO基板上に50nmの均一な薄膜を形成した。
その上に、蒸着装置(真空度1.0×10-5Pa)を用いてα-NPD及びアルミニウムの薄膜を順次積層し、ホールオンリー素子Aを得た。蒸着は、蒸着レート0.2nm/秒の条件で行った。α-NPD及びアルミニウムの薄膜の膜厚は、それぞれ30nm及び80nmとした。
なお、素子は、実施例2-1と同様の方法で封止した後、その特性を評価した。 [6] Fabrication and Characteristic Evaluation of Hole-Only Device (HOD) In the following Examples and Comparative Examples, the same ITO substrate as described above was used.
[Example 3-1]
The charge-transporting varnish A is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a uniform thin film of 50 nm on the ITO substrate. did.
A thin film of α-NPD and aluminum was sequentially laminated on it using a thin film deposition apparatus (vacuum degree 1.0 × 10 -5 Pa) to obtain a hole-only element A. The vapor deposition was carried out under the condition of a vapor deposition rate of 0.2 nm / sec. The film thicknesses of the α-NPD and aluminum thin films were 30 nm and 80 nm, respectively.
The element was sealed in the same manner as in Example 2-1 and then its characteristics were evaluated.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスBを用いた以外は、実施例3-1と同様の方法でホールオンリー素子Bを作製した。 [Example 3-2]
A hole-only element B was produced in the same manner as in Example 3-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスCを用いた以外は、実施例3-1と同様の方法でホールオンリー素子Cを作製した。 [Example 3-3]
A hole-only element C was produced in the same manner as in Example 3-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスDを用い、230℃で15分間焼成した以外は、実施例3-1と同様の方法でホールオンリー素子Dを作製した。 [Example 3-4]
A hole-only element D was produced in the same manner as in Example 3-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスEを用い、230℃で15分間焼成した以外は、実施例3-1と同様の方法でホールオンリー素子Eを作製した。 [Example 3-5]
A hole-only element E was produced in the same manner as in Example 3-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスFを用い、230℃で15分間焼成した以外は、実施例3-1と同様の方法でホールオンリー素子Fを作製した。 [Example 3-6]
A hole-only element F was produced in the same manner as in Example 3-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスGを用いた以外は、実施例3-1と同様の方法でホールオンリー素子Gを作製した。 [Comparative Example 3-1]
A hole-only element G was produced in the same manner as in Example 3-1 except that the charge-transporting varnish G was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスHを用いた以外は、実施例3-1と同様の方法でホールオンリー素子Hを作製した。 [Comparative Example 3-2]
A hole-only element H was produced in the same manner as in Example 3-1 except that the charge-transporting varnish H was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスIを用い、230℃で15分間焼成した以外は、実施例3-1と同様の方法でホールオンリー素子Iを作製した。 [Comparative Example 3-3]
A hole-only element I was produced in the same manner as in Example 3-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスJを用い、230℃で15分間焼成した以外は、実施例3-1と同様の方法でホールオンリー素子Jを作製した。 [Comparative Example 3-4]
A hole-only element J was produced in the same manner as in Example 3-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
以下の実施例及び比較例において、ITO基板は、前記と同様のものを使用した。
[実施例4-1]
電荷輸送性ワニスAを、スピンコーターを用いてITO基板に塗布した後、大気下、120℃で1分間乾燥し、次いで200℃で15分間焼成し、ITO基板上に50nmの均一な薄膜を形成した。
その上に、蒸着装置(真空度1.0×10-5Pa)を用いてα-NPDを0.2nm/秒にて30nm成膜した。次に、CBPとIr(PPy)3を共蒸着した。共蒸着はIr(PPy)3の濃度が6%になるように蒸着レートをコントロールし、40nm積層させた。次いで、トリス(8-キノリノラート)アルミニウム(III)(Alq3)、フッ化リチウム及びアルミニウムの薄膜を順次積層して有機EL素子Aを得た。この際、蒸着レートは、Alq3及びアルミニウムについては0.2nm/秒、フッ化リチウムについては0.02nm/秒の条件でそれぞれ行い、膜厚は、それぞれ20nm、0.5nm及び80nmとした。
なお、素子は、実施例2-1と同様の方法で封止した後、その特性を評価した。 [7] Fabrication and Characteristic Evaluation of Organic EL Element In the following Examples and Comparative Examples, the same ITO substrate as described above was used.
[Example 4-1]
The charge-transporting varnish A is applied to an ITO substrate using a spin coater, dried in the air at 120 ° C. for 1 minute, and then fired at 200 ° C. for 15 minutes to form a uniform thin film of 50 nm on the ITO substrate. did.
On it, α-NPD was deposited at 0.2 nm / sec at 30 nm using a thin film deposition apparatus (vacuum degree 1.0 × 10 -5 Pa). Next, CBP and Ir (PPy) 3 were co-deposited. For co-evaporation, the vapor deposition rate was controlled so that the concentration of Ir (PPy) 3 was 6%, and 40 nm was laminated. Next, a thin film of tris (8-quinolinolate) aluminum (III) (Alq 3 ), lithium fluoride, and aluminum was sequentially laminated to obtain an organic EL element A. At this time, the vapor deposition rate was 0.2 nm / sec for Alq 3 and aluminum, and 0.02 nm / sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.
The element was sealed in the same manner as in Example 2-1 and then its characteristics were evaluated.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスBを用いた以外は、実施例4-1と同様の方法で有機EL素子Bを作製した。 [Example 4-2]
An organic EL element B was produced in the same manner as in Example 4-1 except that the charge transporting varnish B was used instead of the charge transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスCを用いた以外は、実施例4-1と同様の方法で有機EL素子Cを作製した。 [Example 4-3]
The organic EL element C was produced in the same manner as in Example 4-1 except that the charge transporting varnish C was used instead of the charge transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスDを用い、230℃で15分間焼成した以外は、実施例4-1と同様の方法で有機EL素子Dを作製した。 [Example 4-4]
An organic EL element D was produced in the same manner as in Example 4-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスEを用い、230℃で15分間焼成した以外は、実施例4-1と同様の方法で有機EL素子Eを作製した。 [Example 4-5]
An organic EL element E was produced in the same manner as in Example 4-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスFを用い、230℃で15分間焼成した以外は、実施例4-1と同様の方法で有機EL素子Fを作製した。 [Example 4-6]
An organic EL element F was produced in the same manner as in Example 4-1 except that a charge-transporting varnish F was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスGを用いた以外は、実施例4-1と同様の方法で有機EL素子Gを作製した。 [Comparative Example 4-1]
An organic EL device G was produced in the same manner as in Example 4-1 except that the charge transporting varnish G was used instead of the charge transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスHを用いた以外は、実施例4-1と同様の方法で有機EL素子Hを作製した。 [Comparative Example 4-2]
The organic EL element H was produced in the same manner as in Example 4-1 except that the charge transporting varnish H was used instead of the charge transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスIを用い、230℃で15分間焼成した以外は、実施例4-1と同様の方法で有機EL素子Iを作製した。 [Comparative Example 4-3]
An organic EL element I was produced in the same manner as in Example 4-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスJを用い、230℃で15分間焼成した以外は、実施例4-1と同様の方法で有機EL素子Jを作製した。 [Comparative Example 4-4]
An organic EL element J was produced in the same manner as in Example 4-1 except that the charge-transporting varnish J was used instead of the charge-transporting varnish A and was fired at 230 ° C. for 15 minutes.
[実施例5-1]
電荷輸送性ワニスAを、固形分濃度が2.3質量%となるように溶媒で希釈し、製造例2で作製した隔壁付基板上の長方形の開口部(膜形成領域)に、インクジェット装置を用いて吐出した。なお、電荷輸送性ワニスを希釈する際に、ワニス中の混合溶媒の組成比率が変化しないように希釈した。得られた塗膜を、その後すぐに、常温で10Pa以下の減圧度(真空度)で15分間減圧乾燥し、次いで常圧で、200℃15分間乾燥して隔壁内に電荷輸送性薄膜を形成し、電荷輸送性薄膜付き基板Aを得た。なお、電荷輸送性薄膜の開口部中央付近の膜厚が90~110nmとなるように吐出した。 [7] Fabrication of a substrate with a charge-transporting thin film by coating with an inkjet [Example 5-1]
The charge-transporting varnish A is diluted with a solvent so that the solid content concentration is 2.3% by mass, and an inkjet device is placed in a rectangular opening (film forming region) on the partition substrate prepared in Production Example 2. Discharged using. When the charge transporting varnish was diluted, it was diluted so that the composition ratio of the mixed solvent in the varnish did not change. Immediately thereafter, the obtained coating film was dried under reduced pressure (vacuum degree) of 10 Pa or less at room temperature for 15 minutes, and then dried at 200 ° C. for 15 minutes at normal pressure to form a charge-transporting thin film in the partition wall. A substrate A with a charge-transporting thin film was obtained. The charge-transporting thin film was discharged so that the film thickness near the center of the opening was 90 to 110 nm.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスBを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Example 5-2]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish B was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスCを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Example 5-3]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish C was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスDを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Example 5-4]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish D was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスEを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Example 5-5]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish E was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスFを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Example 5-6]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish F was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスGを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Comparative Example 5-1]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish G was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスHを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Comparative Example 5-2]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish H was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスIを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板を作製した。 [Comparative Example 5-3]
A substrate with a charge-transporting thin film was prepared in the same manner as in Example 5-1 except that the charge-transporting varnish I was used instead of the charge-transporting varnish A.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスKを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板Kを作製したが、膜表面に凹凸構造が発生し、平坦な膜は得られなかった。 [Comparative Example 5-4]
A substrate K with a charge-transporting thin film was produced in the same manner as in Example 5-1 except that the charge-transporting varnish K was used instead of the charge-transporting varnish A, but an uneven structure was generated on the film surface. No flat film was obtained.
電荷輸送性ワニスAのかわりに電荷輸送性ワニスLを用いた以外は、実施例5-1と同様の方法で電荷輸送性薄膜付き基板Lを作製したが、膜表面に凹凸構造が発生し、平坦な膜は得られなかった。 [Comparative Example 5-5]
A substrate L with a charge-transporting thin film was produced in the same manner as in Example 5-1 except that the charge-transporting varnish L was used instead of the charge-transporting varnish A, but an uneven structure was generated on the film surface. No flat film was obtained.
Claims (15)
- (A)単分散の電荷輸送性有機化合物、(B)ドーパント及び(C)有機溶媒を含む電荷輸送性ワニスであって、
(B)ドーパントが、(B1)アリールスルホン酸エステル化合物と、(B2)ハロゲン化テトラシアノキノジメタン又は(B3)ハロゲン化若しくはシアノ化ベンゾキノンとを含む電荷輸送性ワニス。 A charge-transporting varnish containing (A) a monodisperse charge-transporting organic compound, (B) a dopant, and (C) an organic solvent.
A charge-transporting varnish in which the dopant (B) comprises (B1) an aryl sulfonic acid ester compound and (B2) a halogenated tetracyanoquinodimethane or (B3) a halogenated or cyanated benzoquinone. - 前記単分散の電荷輸送性有機化合物が、アリールアミン誘導体である請求項1記載の電荷輸送性ワニス。 The charge-transporting varnish according to claim 1, wherein the monodisperse charge-transporting organic compound is an arylamine derivative.
- 前記アリールアミン誘導体が、3級アリールアミン化合物である請求項2記載の輸送性ワニス。 The transportable varnish according to claim 2, wherein the arylamine derivative is a tertiary arylamine compound.
- 前記3級アリールアミン化合物が、少なくとも1つの窒素原子を有し、かつ全ての窒素原子が3級アリールアミン構造を有するものである請求項3記載の電荷輸送性ワニス。 The charge transporting varnish according to claim 3, wherein the tertiary arylamine compound has at least one nitrogen atom and all nitrogen atoms have a tertiary arylamine structure.
- 前記3級アリールアミン化合物が、少なくとも2つの窒素原子を有し、かつ全ての窒素原子が3級アリールアミン構造を有するものである請求項4記載の電荷輸送性ワニス。 The charge transporting varnish according to claim 4, wherein the tertiary arylamine compound has at least two nitrogen atoms and all nitrogen atoms have a tertiary arylamine structure.
- 前記アリールスルホン酸エステル化合物が、下記式(B1)又は(B1')で表されるものである請求項1~5のいずれか1項記載の電荷輸送性ワニス。
A2は、-O-、-S-又は-NH-であり;
A3は、又は炭素数6~20の(n+1)価の芳香族基であり;
X1は、炭素数2~5のアルキレン基であり、該アルキレン基の炭素原子間に、-O-、-S-又はカルボニル基が介在していてもよく、該アルキレン基の水素原子の一部又は全部が、更に炭素数1~20のアルキル基で置換されていてもよく;
X2は、単結合、-O-、-S-又は-NR-であり、Rは、水素原子又は炭素数1~10の1価炭化水素基であり;
X3は、置換基を有していてもよい炭素数1~20の1価炭化水素基であり;
mは、1≦m≦4を満たす整数であり;
nは、1≦n≦4を満たす整数である。] The charge-transporting varnish according to any one of claims 1 to 5, wherein the aryl sulfonic acid ester compound is represented by the following formula (B1) or (B1').
A 2 is -O-, -S- or -NH-;
A 3 is, or an (n + 1) -valent aromatic group with 6 to 20 carbon atoms;
X 1 is an alkylene group having 2 to 5 carbon atoms, and an —O—, —S— or carbonyl group may be interposed between the carbon atoms of the alkylene group, and one of the hydrogen atoms of the alkylene group. Part or all may be further substituted with an alkyl group having 1 to 20 carbon atoms;
X 2 is a single bond, -O-, -S- or -NR-, and R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms;
X 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
m is an integer that satisfies 1 ≦ m ≦ 4.
n is an integer that satisfies 1 ≦ n ≦ 4. ] - 前記アリールスルホン酸エステル化合物が、下記式(B1-1)~(B1-3)のいずれかで表されるものである請求項6記載の電荷輸送性ワニス。
A11は、パーフルオロビフェニルから誘導されるm価の基であり、A12は、-O-又は-S-であり、A13は、ナフタレン又はアントラセンから誘導される(n+1)価の基であり;
m及びnは、前記と同じである。)
A14は、置換基を有していてもよい、1つ以上の芳香環を含むm価の炭化水素基であり、A15は、-O-又は-S-であり、A16は、(n+1)価の芳香族基であり;
m及びnは、前記と同じである。)
Rs14~Rs17は、それぞれ独立に、水素原子、又は直鎖状若しくは分岐状の炭素数1~20の1価脂肪族炭化水素基であり;
Rs18は、直鎖状若しくは分岐状の炭素数1~20の1価脂肪族炭化水素基、又は-ORs19であり、Rs19は、置換基を有していてもよい炭素数2~20の1価炭化水素基であり;
A17は、-O-、-S-又は-NH-であり;
A18は、(n+1)価の芳香族基であり;
nは、前記と同じである。) The charge transporting varnish according to claim 6, wherein the aryl sulfonic acid ester compound is represented by any of the following formulas (B1-1) to (B1-3).
A 11 is an m-valent group derived from perfluorobiphenyl, A 12 is an -O- or -S-, and A 13 is a (n + 1) -valent group derived from naphthalene or anthracene. Yes;
m and n are the same as described above. )
A 14 is an m-valent hydrocarbon group containing one or more aromatic rings, which may have a substituent, A 15 is —O— or —S—, and A 16 is ( It is an n + 1) valent aromatic group;
m and n are the same as described above. )
R s14 to R s17 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms;
R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or −OR s19 , and R s19 has 2 to 20 carbon atoms which may have a substituent. Is a monovalent hydrocarbon group of
A 17 is -O-, -S- or -NH-;
A 18 is an (n + 1) -valent aromatic group;
n is the same as described above. ) - (B2)ハロゲン化テトラシアノキノジメタンが、下記式(B2)で表されるものである請求項1~7のいずれか1項記載の電荷輸送性ワニス。
- (B3)ハロゲン化又はシアノ化ベンゾキノンが、下記式(B3)で表されるものである請求項1~8のいずれか1項記載の電荷輸送性ワニス。
- 前記(B1)アリールスルホン酸エステル化合物の含有量が、前記(B2)ハロゲン化テトラシアノキノジメタン又は前記(B3)ハロゲン化若しくはシアノ化ベンゾキノンに対し、モル比で、0.01~50である請求項1~9のいずれか1項記載の電荷輸送性ワニス。 The content of the (B1) aryl sulfonic acid ester compound is 0.01 to 50 in molar ratio with respect to the (B2) halogenated tetracyanoquinodimethane or the (B3) halogenated or cyanated benzoquinone. The charge-transporting varnish according to any one of claims 1 to 9.
- 前記単分散の電荷輸送性有機化合物の分子量が、200~9,000である請求項1~10のいずれか1項記載の電荷輸送性ワニス。 The charge-transporting varnish according to any one of claims 1 to 10, wherein the monodisperse charge-transporting organic compound has a molecular weight of 200 to 9,000.
- 前記有機溶媒が、低極性有機溶媒を含む請求項1~11のいずれか1項記載の電荷輸送性ワニス。 The charge-transporting varnish according to any one of claims 1 to 11, wherein the organic solvent contains a low-polarity organic solvent.
- 請求項1~12のいずれか1項記載の電荷輸送性ワニスから得られる電荷輸送性薄膜。 A charge-transporting thin film obtained from the charge-transporting varnish according to any one of claims 1 to 12.
- 請求項13記載の電荷輸送性薄膜を備える有機エレクトロルミネッセンス素子。 The organic electroluminescence device including the charge transporting thin film according to claim 13.
- 前記電荷輸送性薄膜が、正孔注入層又は正孔輸送層である請求項14記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 14, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.
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