Charge transport ink composition

Abstract

To provide a charge transport ink composition that provides a charge transport thin film with excellent charge transport properties.SOLUTION: A charge transport ink composition includes nickel oxide nanoparticles, a charge transport substance, and an organic solvent, and the charge transport substance is an arylamine derivative, or a polythiophene derivative or an amine adduct thereof.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a charge transport ink composition. [Background technology]

[0002] Organic electroluminescence (hereinafter referred to as organic EL) devices use various functional thin films, such as a light-emitting layer and a charge transport layer. In particular, the hole transport layer is responsible for transferring charges between the hole injection layer and the light-emitting layer, and plays an important role in achieving low-voltage operation and high brightness in organic EL devices.

[0003] Methods for forming hole transport layers are roughly divided into dry processes, such as vapor deposition, and wet processes, such as inkjet and spin coating. Comparing these processes, wet processes are more efficient at producing thin films with high flatness over large areas. Therefore, as organic EL displays are currently being made larger, there is a demand for hole transport layers that can be formed by wet processes, and technology related to hole transport materials that can be formed by wet processes has been reported (Patent Document 1).

[0004] Furthermore, in recent years, with the development of display technology, quantum dot electroluminescence (hereafter referred to as quantum dot EL) devices, which use quantum dot materials as their light-emitting layer, have appeared and are showing promise for a wide range of applications. These quantum dot EL devices can be manufactured at low cost using wet processes, and are attracting much attention in fields such as display technology and lighting due to their characteristics, such as control of emission wavelength, high color purity, high luminous efficiency, and flexibility.

[0005] In recent years, metal oxide nanoparticles have often been used to transport charges in such EL devices. Efficient charge transport to the light-emitting layer has been achieved by stacking a charge-transport layer made of metal oxide nanoparticles containing metals such as Ni, Zn, Ti, and Sn between the light-emitting layer and the anode or cathode. To improve this efficiency, studies have been conducted on controlling the type and dispersibility of metal oxide nanoparticles (Patent Documents 2 to 4). In particular, nickel oxide nanoparticles are p-type semiconductors, so charge-transporting thin films using them are expected to show little decrease in conductivity and improved charge transport. However, when nickel oxide nanoparticles are used alone, there is a problem of a decrease in the light-emitting intensity of the device, a phenomenon known as quenching (Non-Patent Document 1).

[0006] Currently, there is a demand for improved performance of organic EL devices and quantum dot EL devices, and improvements are constantly being sought for wet process materials for hole transport layers. In particular, there is an increasing demand for materials that can provide charge transport thin films with high hole transport properties, as these materials can contribute to improving the performance of organic EL devices and quantum dot EL devices, such as their luminance characteristics. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2008 / 032616 [Patent Document 2] International Publication No. 2023 / 079616 [Patent Document 3] International Publication No. 2023 / 195412 [Patent Document 4] International Publication No. 2016 / 128133 [Non-patent literature]

[0008] [Non-Patent Document 1] ACS Appl. Electron. Mater. 2019, 1, 2096-2102 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a charge transporting ink composition that is excellent in charge transporting properties, particularly hole transporting properties. [Means for solving the problem]

[0010] As a result of extensive research aimed at solving the above problems, the present inventors have found that a charge-transporting thin film with excellent charge transport properties can be obtained by using a charge-transporting ink composition that combines nickel oxide nanoparticles with a specific charge-transporting substance. They have also found that electronic devices fabricated using this charge-transporting thin film exhibit excellent properties by suppressing the quenching phenomenon caused by nickel oxide nanoparticles, thereby completing the present invention.

[0011] That is, the present invention provides the following charge transporting ink composition. 1. A method for producing a nickel oxide nanoparticle-containing electrocatalyst comprising the steps of: The charge transporting ink composition wherein the charge transporting substance is an arylamine derivative, or a polythiophene derivative or an amine adduct thereof. 2. A charge transporting ink composition according to claim 1, wherein the arylamine derivative is represented by the following formula (T1): [ka] [In the formula, Ph 1 represents a group represented by formula (P1), [ka] (In the formula, R 1 ~R 4each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom. Ar 1 each independently represents a group represented by any one of formulas [B1] to [B11], [ka] (In the formula, R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group, an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom; R 26 and R 27 are independent of each other, Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted by R 50 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Ar 3 each independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl group having 6 to 20 carbon atoms)amino group, Z 1 is a halogen atom, a nitro group, a cyano group, or Z 2represents 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, each of which may be substituted with Z 2 is a halogen atom, a nitro group, a cyano group, or Z 3 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 3 represents a halogen atom, a nitro group, or a cyano group; Z 4 is a halogen atom, a nitro group, a cyano group, Z 5 an aryl group having 6 to 20 carbon atoms which may be substituted with 5 represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted by, an organosilyl group, or an aryloxy group which may be substituted by, Z 5 is a halogen atom, a nitro group, a nitro group, or a Z 3 represents 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 Ar 2 each independently represents a group represented by any one of formulas [A1] to [A18], [ka] (In the formula, R 153 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with R 154 and R 155 are independent of each other, Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted by DPA represents a diphenylamino group; Ar 3 , Z 1and Z 3 ~Z 5 has the same meaning as above.) k represents an integer of 1 to 10. 3. The charge transporting ink composition of 1 or 2, wherein the polythiophene derivative or its amine adduct contains a repeating unit represented by the following formula (U1) or an amine adduct thereof: [ka] (In the formula, R u1 and R u2 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a fluoroalkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, -O-[ZO] p -R e or a sulfo group, or R u1 and R u2 are bonded to each other, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and which may be substituted with a sulfo group, Z is an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom, p is an integer of 1 or more, and R e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms. 4. R above u1 is a sulfo group, and the above R u2 is an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] p -R e or the above R u1 and R u2 The charge transport ink composition of 3, wherein -OYO- is formed by bonding. 5. The charge transporting ink composition according to any one of 1 to 4, further comprising a thiol compound represented by the following formula (X1): R x1 -SH (X1) (In the formula, R x1is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent. The substituents in the alkyl group, alkenyl group, and alkynyl group are each independently a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, an organooxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom. The substituents in the aryl group, aralkyl group, and heteroaryl group are, independently of one another, a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphate group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, an alkyl group having 1 to 20 carbon atoms, 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, an aralkyl group having 7 to 20 carbon atoms, an organoxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom. Above R x1 The alkyl group contained in may have at least one group selected from the group consisting of an oxygen atom, a carbonyl group, and an ester group between its carbon atoms. 6. R in the above formula (X1) x1 is an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms, and the substituents on the alkyl group and aryl group are each independently a hydroxy group, a carboxy group, an ester group, an organoxy group, or a halogen atom. 7. A charge-transporting thin film obtained from the charge-transporting ink composition of any one of 1 to 6. 8. An electronic device comprising the charge transport thin film of 7. 9. The electronic device of 8, wherein the charge transporting thin film is a hole injection layer, a hole transport layer, or a hole injection transport layer. 10. The electronic device of 9, wherein the electronic device is an organic EL device or a quantum dot EL device. [Effects of the Invention]

[0012] By using the charge transport ink composition of the present invention, a charge transport thin film with excellent charge transport properties (particularly hole transport properties) can be obtained. This charge transport thin film can be suitably used as a thin film for electronic devices such as organic EL devices and quantum dot EL devices. In particular, when the charge transport ink composition of the present invention is used to form a hole transport layer for an organic EL device or a quantum dot EL device, hole transport properties to the light-emitting layer formed thereon are improved, and the quenching phenomenon caused by nickel oxide nanoparticles is suppressed, which is expected to improve the brightness characteristics of the device. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in more detail below. The charge transporting ink composition according to the present invention is characterized by containing nickel oxide nanoparticles, a specific charge transporting substance, and an organic solvent. In the present invention, the term "charge transportability" is synonymous with "electrical conductivity" and "hole transportability." The charge transportable ink composition may itself have charge transportability, or the solid film obtained from the composition may have charge transportability.

[0014] [1] Nickel oxide nanoparticles The charge transport ink composition of the present invention contains nickel oxide nanoparticles. The term "nanoparticles" refers to fine particles whose primary particles have an average particle size on the order of nanometers (typically 500 nm or less). The term "nickel oxide nanoparticles" refers to NiO formed into nanoparticles.

[0015] In the present invention, the primary particle size of the nickel oxide nanoparticles is not particularly limited as long as it is nano-sized, but is usually 1 nm or more, and from the viewpoint of ensuring good particle dispersibility and ease of production, it is usually 200 nm or less, preferably 100 nm or less, and more preferably 30 nm or less.

[0016] The content of nickel oxide nanoparticles in the charge transport ink composition of the present invention is not particularly limited. However, from the viewpoint of improving the hole transport properties of the resulting thin film and enhancing the uniformity of the film, the lower limit of the solid content is preferably 10 mass %, more preferably 15 mass %, and even more preferably 20 mass %, and the upper limit is preferably 95 mass %, more preferably 85 mass %, and even more preferably 80 mass %.

[0017] The nickel oxide nanoparticles used in the present invention may also be used in the form of a sol dispersed in a dispersion medium. Examples of dispersion media include methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, ethyl acetate, toluene, propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol butyl methyl ether, and tripropylene glycol monomethyl ether.

[0018] The solid content concentration of the sol is not particularly limited, but is preferably 5 to 60 mass %, more preferably 5 to 50 mass %, and even more preferably 5 to 35 mass %.

[0019] The nickel oxide nanoparticles used in the present invention may contain Ni having at least two valences. The nickel oxide nanoparticles may also contain a metal dopant other than Ni. Examples of metal dopants include Cu, Li, K, Rb, Cs, Mg, Al, Co, Mn, Fe, Cr, Zr, V, Mo, and Zn. The metal dopants may be used alone or in combination of two or more.

[0020] [2] Charge transporting substance The charge transport material used in the present invention includes an arylamine derivative, a polythiophene derivative, or an amine adduct thereof, from the viewpoint of suppressing the quenching phenomenon of the device caused by nickel oxide nanoparticles. These can be appropriately selected from charge transport compounds, charge transport oligomers, charge transport polymers, etc. used in the field of organic electroluminescence (EL), etc. Specific examples thereof include arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, and N,N,N',N'-tetraarylbenzidine derivatives; and polythiophene derivatives such as poly(3-hexylthiophene-2,5-diyl) or their amine adducts. In the present invention, taking into consideration the effect of improving the charge transport properties of the resulting thin film and the effect of suppressing the quenching phenomenon of the device, arylamine derivatives represented by formula (T1) described below and polythiophene derivatives represented by formula (U1) or their amine adducts are preferred.

[0021] [Arylamine derivative represented by formula (T1)] [ka]

[0022] In formula (T1), Ph 1 represents a group represented by formula (P1).

[0023] [ka]

[0024] where R1 ~R 4 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom.

[0025] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0026] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups.

[0027] Specific examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.

[0028] Specific examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group, an n-3-butynyl group, a 1-methyl-2-propynyl group, an n-1-pentynyl group, an n-2-pentynyl group, an n-3-pentynyl group, an n-4-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, a 1,1-dimethyl-n-propynyl group, an n-1-hexynyl group, an n-1-decynyl group, an n-1-pentadecinyl group, and an n-1-eicosynyl group.

[0029] Specific 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, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0030] Specific examples of the heteroaryl group having 2 to 20 carbon atoms include oxygen-containing heteroaryl groups such as a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, and a 5-isoxazolyl group; sulfur-containing heteroaryl groups such as a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, and a 5-isothiazolyl group; Aryl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 3-pyrazyl group, 5-pyrazyl group, 6-pyrazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 6-pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 5-pyridazyl group, 6-pyridazyl group, 1,2,3-triazin-4-yl group, 1,2,3-triazin-5-yl group, 1,2,4-triazin-3-yl group a quinolinyl group, a 1,2,4-triazin-5-yl group, a 1,2,4-triazin-6-yl group, a 1,3,5-triazin-2-yl group, a 1,2,4,5-tetrazin-3-yl group, a 1,2,3,4-tetrazin-5-yl group, a 2-quinolinyl group, a 3-quinolinyl group, a 4-quinolinyl group, a 5-quinolinyl group, a 6-quinolinyl group, a 7-quinolinyl group, an 8-quinolinyl group, a 1-isoquinolinyl group, a 3-isoquinolinyl group, a 4-isoquinolinyl group, a 5-isoquinolinyl group, Examples of nitrogen-containing heteroaryl groups include a 6-isoquinolinyl group, a 7-isoquinolinyl group, an 8-isoquinolinyl group, a 2-quinoxanyl group, a 5-quinoxanyl group, a 6-quinoxanyl group, a 2-quinazolinyl group, a 4-quinazolinyl group, a 5-quinazolinyl group, a 6-quinazolinyl group, a 7-quinazolinyl group, an 8-quinazolinyl group, a 3-cinnolinyl group, a 4-cinnolinyl group, a 5-cinnolinyl group, a 6-cinnolinyl group, a 7-cinnolinyl group, and an 8-cinnolinyl group.

[0031] In particular, R 1 ~R 4is preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group of 1 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group of 6 to 20 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group of 2 to 20 carbon atoms which may be substituted with a halogen atom; more preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group of 1 to 10 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; still more preferably a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; and most preferably a hydrogen atom.

[0032] Below, Ph 1 Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0033] [ka]

[0034] Ar in the above formula (T1) 1 are each independently a group represented by any one of formulas [B1] to [B11], and are particularly preferably a group represented by any one of formulas [B1'] to [B11'].

[0035] [ka]

[0036] [ka]

[0037] where R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group, an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom; R 26 and R 27 are independent of each other, Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with 50 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted by 1 is a halogen atom, a nitro group, a cyano group, or Z 2 represents 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 2 is a halogen atom, a nitro group, a cyano group, or Z 3 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted by 3 represents a halogen atom, a nitro group, or a cyano group; Z 4 is a halogen atom, a nitro group, a cyano group, Z 5 an aryl group having 6 to 20 carbon atoms which may be substituted with 5 represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted by, an organosilyl group or an aryloxy group which may be substituted by, 5 is a halogen atom, a nitro group, a cyano group, or Z 3and R represents 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, each of which may be substituted with one of the following: 1 ~R 4 Examples include those similar to those described above.

[0038] Above Z 4 Examples of the organosilyl group include trialkylsilyl groups in which the alkyl group has 1 to 10 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, and decyldimethylsilyl group. Other examples include trialkoxysilyl groups in which the alkoxy group has 1 to 10 carbon atoms, such as trimethoxysilyl group, triethoxysilyl group, tri-n-propoxysilyl group, triisopropoxysilyl group, tri-n-butoxysilyl group, tri-s-butoxysilyl group, tri-t-butoxysilyl group, tri-n-pentoxysilyl group, tri-n-hexyloxysilyl group, tri-n-octyloxysilyl group, and tri-n-decyloxysilyl group.

[0039] Above Z 4 Examples of the aryloxy group include aryloxy groups having 6 to 20 carbon atoms, such as a phenoxy group, an anthracenoxy group, a naphthoxy group, a phenanthrenoxy group, and a fluorenoxy group.

[0040] The aryloxy group may have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. In the present invention, an alkenyl group having 2 to 20 carbon atoms is preferred. When the aryloxy group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0041] In particular, R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 is preferably a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a halogen atom, an alkyl group of 1 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group of 6 to 20 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group of 2 to 20 carbon atoms which may be substituted with a halogen atom; more preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group of 1 to 10 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; still more preferably a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; and most preferably a hydrogen atom. Also, R 26 and R 27 As for Z 1 an aryl group having 6 to 14 carbon atoms which may be substituted with 1 A heteroaryl group having 2 to 14 carbon atoms which may be substituted by is preferred, and Z 1 An aryl group having 6 to 14 carbon atoms which may be substituted with is more preferred, and Z 1 a phenyl group optionally substituted with Z 1 a 1-naphthyl group optionally substituted with Z 1 Even more preferred is a 2-naphthyl group optionally substituted with And R 50 As for the hydrogen atom, Z 1 an aryl group having 6 to 20 carbon atoms which may be substituted with 1 a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 4 A hydrogen atom, Z 1 an aryl group having 6 to 14 carbon atoms which may be substituted with 1 a heteroaryl group having 2 to 14 carbon atoms which may be substituted with 4 More preferred is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, Z 1an aryl group having 6 to 14 carbon atoms which may be substituted with 1 a nitrogen-containing heteroaryl group having 2 to 14 carbon atoms which may be substituted with 4 More preferred is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, Z 1 a phenyl group optionally substituted with Z 1 a 1-naphthyl group optionally substituted with Z 1 a 2-naphthyl group optionally substituted by Z 1 a 2-pyridyl group optionally substituted by Z 1 a 3-pyridyl group optionally substituted with Z 1 a 4-pyridyl group optionally substituted by Z 4 A methyl group optionally substituted with is more preferred.

[0042] Also, Ar 3 each independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl group having 6 to 20 carbon atoms)amino group. Specific examples of the aryl group having 6 to 20 carbon atoms include R 1 ~R 4 Specific examples of the di(aryl group having 6 to 20 carbon atoms)amino group include a diphenylamino group, a 1-naphthylphenylamino group, a di(1-naphthyl)amino group, a 1-naphthyl-2-naphthylamino group, and a di(2-naphthyl)amino group. Ar 3 As the alkyl group, 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, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a p-(diphenylamino)phenyl group, a p-(1-naphthylphenylamino)phenyl group, a p-(di(1-naphthyl)amino)phenyl group, a p-(1-naphthyl-2-naphthylamino)phenyl group, or a p-(di(2-naphthyl)amino)phenyl group is preferred, and a p-(diphenylamino)phenyl group is more preferred.

[0043] Below, Ar 1Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka] (In the formula, R 50 has the same meaning as above.)

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] Ar in the above formula (T1) 2 represent, independently of each other, a group represented by any one of formulas [A1] to [A18].

[0053] [ka]

[0054] where R 153 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with R 154 and R 155 are independent of each other, Z 1 DPA represents a diphenylamino group; Ar 3 , Z 1 and Z 4 has the same meaning as above. Specific examples of these halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 2 to 20 carbon atoms include the above-mentioned R 1 ~R 4 Examples include those similar to those described above.

[0055] In particular, R 153 As for the hydrogen atom, Z 1 an aryl group having 6 to 20 carbon atoms which may be substituted with 1 a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 4 A hydrogen atom, Z 1 an aryl group having 6 to 14 carbon atoms which may be substituted with 1 a heteroaryl group having 2 to 14 carbon atoms which may be substituted with 4 More preferred is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, Z 1 an aryl group having 6 to 14 carbon atoms which may be substituted with 1 a nitrogen-containing heteroaryl group having 2 to 14 carbon atoms which may be substituted with 4More preferred is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, Z 1 a phenyl group optionally substituted with Z 1 a 1-naphthyl group optionally substituted with Z 1 a 2-naphthyl group optionally substituted by Z 1 a 2-pyridyl group optionally substituted by Z 1 a 3-pyridyl group optionally substituted with Z 1 a 4-pyridyl group optionally substituted by Z 4 A methyl group optionally substituted with is more preferred. Also, R 154 and R 155 As for Z 1 an aryl group having 6 to 14 carbon atoms which may be substituted with 1 A heteroaryl group having 2 to 14 carbon atoms which may be substituted by is preferred, and Z 1 An aryl group having 6 to 14 carbon atoms which may be substituted with is more preferred, and Z 1 a phenyl group optionally substituted with Z 1 a 1-naphthyl group optionally substituted with Z 1 Even more preferred is a 2-naphthyl group optionally substituted with

[0056] Below, Ar 2 Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0057] [ka] (In the formula, DPA has the same meaning as above.)

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka] (In the formula, R 153 has the same meaning as above.)

[0063] [ka]

[0064] In the formula (T1), in consideration of the ease of synthesis of the resulting arylamine derivative, Ar 1 are all the same group, and Ar 2 are preferably all the same group, and Ar 1 and Ar 2 are all the same group. That is, the arylamine derivative represented by formula (T1) is more preferably an arylamine derivative represented by formula (T1-1). Furthermore, as will be described later, the arylamine derivative represented by formula (T1) is preferably an arylamine derivative represented by formula (T1-1), since it can be synthesized relatively easily using bis(4-aminophenyl)amine, which is a relatively inexpensive raw material compound, and has excellent solubility in organic solvents.

[0065] [ka]

[0066] In formula (T1-1), Ph 1 and k have the same meaning as above, and Ar 4represents a group represented by any one of the formulae [D1] to [D13], and is particularly preferably a group represented by any one of the formulae [D1'] to [D13']. In addition, Ar 4 Specific examples of 1 Specific examples of suitable groups for include the same as those mentioned above.

[0067] [ka] (In the formula, R 26 , R 27 , R 50 , Ar 3 and DPA have the same meanings as above.)

[0068] [ka] (In the formula, R 26 , R 27 , R 50 , Ar 3 and DPA have the same meanings as above.)

[0069] Furthermore, as will be described later, the arylamine derivative represented by formula (T1) is preferably an arylamine derivative represented by formula (T1-2), because it can be synthesized relatively easily using bis(4-aminophenyl)amine, which is a relatively inexpensive raw material compound, and the resulting arylamine derivative has excellent solubility in organic solvents.

[0070] [ka]

[0071] The above Ar 5 represents a group represented by any one of formulas [E1] to [E14].

[0072] [ka] (In the formula, R 50has the same meaning as above.)

[0073] In the above formula (T1), k represents an integer of 1 to 10, and from the viewpoint of increasing the solubility of the compound in organic solvents, k is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and optimally 1.

[0074] In addition, R 26 , R 27 , R 50 and R 153 ~R 155 In Z 1 is a halogen atom, a nitro group, a cyano group, Z 2 an alkyl group having 1 to 10 carbon atoms which may be substituted with 2 an alkenyl group having 2 to 10 carbon atoms which may be substituted with 2 and a halogen atom, a nitro group, a cyano group, a Z 2 an alkyl group having 1 to 3 carbon atoms which may be substituted with 2 an alkenyl group having 2 to 3 carbon atoms which may be substituted by 2 An alkynyl group having 2 to 3 carbon atoms which may be substituted with a fluorine atom, Z 2 an alkyl group having 1 to 3 carbon atoms which may be substituted with 2 an alkenyl group having 2 to 3 carbon atoms which may be substituted by 2 An alkynyl group having 2 to 3 carbon atoms which may be substituted with is even more preferred.

[0075] R 26 , R 27 , R 50 and R 153 ~R 155 In Z 4 is a halogen atom, a nitro group, a cyano group, Z 5 An aryl group having 6 to 14 carbon atoms which may be substituted by, an organosilyl group, or an aryloxy group which may be substituted by, is preferred, and a halogen atom, a nitro group, a cyano group, Z 5An aryl group having 6 to 10 carbon atoms which may be substituted by, a trialkoxysilyl group, or an aryloxy group having 6 to 20 carbon atoms which may be substituted by, is more preferred, and a fluorine atom, Z 5 an aryl group having 6 to 10 carbon atoms which may be substituted by, a trialkoxysilyl group in which each alkoxy group has 1 to 10 carbon atoms, or an aryloxy group having 6 to 14 carbon atoms which may have a substituent, is more preferred; a fluorine atom, Z 5 A phenyl group which may be substituted with one of the following, a trimethoxysilyl group, and a phenoxy group which may be substituted are more preferred.

[0076] R 26 , R 27 , R 50 and R 153 ~R 155 In Z 2 is a halogen atom, a nitro group, a cyano group, Z 3 An aryl group having 6 to 14 carbon atoms which may be substituted by a halogen atom, a nitro group, a cyano group, Z 3 An aryl group having 6 to 10 carbon atoms which may be substituted with a fluorine atom, Z 3 An aryl group having 6 to 10 carbon atoms which may be substituted with a fluorine atom, Z 3 A phenyl group optionally substituted with is more preferred.

[0077] R 26 , R 27 , R 50 and R 153 ~R 155 In Z 5 is a halogen atom, a nitro group, a cyano group, Z 3 an alkyl group having 1 to 10 carbon atoms which may be substituted with 3 an alkenyl group having 2 to 10 carbon atoms which may be substituted with 3 and a halogen atom, a nitro group, a cyano group, a Z 3 an alkyl group having 1 to 3 carbon atoms which may be substituted with 3 an alkenyl group having 2 to 3 carbon atoms which may be substituted by3 An alkynyl group having 2 to 3 carbon atoms which may be substituted with a fluorine atom, Z 3 an alkyl group having 1 to 3 carbon atoms which may be substituted with 3 an alkenyl group having 2 to 3 carbon atoms which may be substituted by 3 An alkynyl group having 2 to 3 carbon atoms which may be substituted with is even more preferred.

[0078] R 26 , R 27 , R 50 and R 153 ~R 155 In Z 3 is preferably a halogen atom, more preferably a fluorine atom.

[0079] On the other hand, R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 In Z 1 is a halogen atom, a nitro group, a cyano group, Z 2 an alkyl group having 1 to 3 carbon atoms which may be substituted with 2 an alkenyl group having 2 to 3 carbon atoms which may be substituted by 2 An alkynyl group having 2 to 3 carbon atoms which may be substituted with a halogen atom, Z 2 More preferred is an alkyl group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, Z 2 A methyl group optionally substituted with is even more preferred.

[0080] R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 In Z 4 is a halogen atom, a nitro group, a cyano group, Z 5 An aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom, Z 5 An aryl group having 6 to 10 carbon atoms which may be substituted with a fluorine atom, Z5 Even more preferred is a phenyl group optionally substituted with .

[0081] R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 In Z 2 is a halogen atom, a nitro group, a cyano group, Z 3 An aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom, Z 3 An aryl group having 6 to 10 carbon atoms which may be substituted with a fluorine atom, Z 3 Even more preferred is a phenyl group optionally substituted with .

[0082] R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 In Z 5 is a halogen atom, a nitro group, a cyano group, Z 3 an alkyl group having 1 to 3 carbon atoms which may be substituted with 3 an alkenyl group having 2 to 3 carbon atoms which may be substituted by 3 An alkynyl group having 2 to 3 carbon atoms which may be substituted with a halogen atom, Z 3 More preferred is an alkyl group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, Z 3 A methyl group optionally substituted with is even more preferred.

[0083] R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 In Z 3 is preferably a halogen atom, more preferably a fluorine atom.

[0084] In the present invention, R 50 and R 153Specific examples of groups suitable as include, but are not limited to, the following groups:

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] In the present invention, the alkyl group, alkenyl group, and alkynyl group each preferably have 10 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 4 or less carbon atoms. The aryl group and heteroaryl group preferably have 14 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably 6 or less carbon atoms.

[0093] Specific examples of the arylamine derivative represented by the above formula (T1) include, but are not limited to, those shown below.

[0094] [ka]

[0095] The arylamine derivative represented by formula (T1) of the present invention can be synthesized by a known method, for example, by the method described in WO 2015 / 050253.

[0096] [Polythiophene derivative represented by formula (U1) or its amine adduct] [ka]

[0097] In the formula, R u1 and R u2 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a fluoroalkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, -O-[ZO] p -R e or a sulfo group, or R u1 and R u2 are bonded to each other, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and which may be substituted with a sulfo group, Z is an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom, p is an integer of 1 or more, and R e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0098] The alkyl group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl, behenyl, triacontyl, and tetracontyl. In the present invention, alkyl groups having 1 to 18 carbon atoms are preferred, and alkyl groups having 1 to 8 carbon atoms are more preferred.

[0099] The fluoroalkyl group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 40 carbon atoms in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 1,2-difluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 1,1,2-trifluoroethyl group, a 1,2,2-trifluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 1,2,2,2-tetrafluoroethyl group, a perfluoroethyl group, a 1-fluoropropyl group, a 2-fluoropropyl group, a 3-fluoropropyl group, a 1,1-difluoropropyl group, a 1,2-difluoropropyl group, a 1,3-difluoropropyl group, a 2,2-difluoropropyl group, a 2,3-difluoropropyl group, a 3,3-difluoropropyl group, a 1,1,2-trifluoropropyl group, a 1,3-trifluoropropyl group, 1,2,3-trifluoropropyl group, 1,3,3-trifluoropropyl group, 2,2,3-trifluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,3-tetrafluoropropyl group, 1,2,2,3-tetrafluoropropyl group, 1,3,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2, Examples include a 3,3,3-tetrafluoropropyl group, a 1,1,2,2,3-pentafluoropropyl group, a 1,2,2,3,3-pentafluoropropyl group, a 1,1,3,3,3-pentafluoropropyl group, a 1,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group.

[0100] The alkoxy group having 1 to 40 carbon atoms may have a linear, branched, or cyclic alkyl group, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a c-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an n-undecyloxy group, an n-dodecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, an n-hexadecyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group, an n-nonadecyloxy group, and an n-eicosanyloxy group.

[0101] The fluoroalkoxy group having 1 to 40 carbon atoms is not particularly limited as long as it is an alkoxy group having 1 to 40 carbon atoms in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 1-fluoroethoxy group, a 2-fluoroethoxy group, a 1,2-difluoroethoxy group, a 1,1-difluoroethoxy group, a 2,2-difluoroethoxy group, a 1,1,2-trifluoroethoxy group, a 1,2, 2-trifluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,2,2,2-tetrafluoroethoxy group, perfluoroethoxy group, 1-fluoropropoxy group, 2-fluoropropoxy group, 3-fluoropropoxy group, 1,1-difluoropropoxy group, 1,2-difluoropropoxy group, 1,3-difluoropropoxy group, 2,2-difluoropropoxy group, 2,3-difluoropropoxy group, 3,3- Difluoropropoxy group, 1,1,2-trifluoropropoxy group, 1,1,3-trifluoropropoxy group, 1,2,3-trifluoropropoxy group, 1,3,3-trifluoropropoxy group, 2,2,3-trifluoropropoxy group, 2,3,3-trifluoropropoxy group, 3,3,3-trifluoropropoxy group, 1,1,2,2-tetrafluoropropoxy group, 1,1,2,3-tetrafluoropropoxy group, 1,2,2,3-tetrafluoropropoxy group groups, 1,3,3,3-tetrafluoropropoxy groups, 2,2,3,3-tetrafluoropropoxy groups, 2,3,3,3-tetrafluoropropoxy groups, 1,1,2,2,3-pentafluoropropoxy groups, 1,2,2,3,3-pentafluoropropoxy groups, 1,1,3,3,3-pentafluoropropoxy groups, 1,2,3,3,3-pentafluoropropoxy groups, 2,2,3,3,3-pentafluoropropoxy groups, and perfluoropropoxy groups.

[0102] The alkylene group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, and an eicosanylene group.

[0103] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl 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, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group, with a phenyl group, a tolyl group, and a naphthyl group being preferred.

[0104] Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, an anthracenoxy group, a naphthoxy group, a phenanthrenoxy group, and a fluorenoxy group.

[0105] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0106] In the above formula (U1), R u1 and R u2 are each independently a hydrogen atom, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or —O[C(R a R b )-C(R c R d )-O] p -R e , -OR f or a sulfo group, or R u1 and R u2 is preferably -OYO-, which is formed by bonding. R a ~R dare each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and specific examples of these groups are the same as those listed above. Among them, R a ~R d are preferably each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group. R e is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and is preferably a hydrogen atom, a methyl group, a propyl group, or a butyl group. Furthermore, p is preferably 1 to 5, and more preferably 1, 2 or 3.

[0107] R f represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms, but is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and more preferably -CHCF.

[0108] In the present invention, R u1 is preferably a hydrogen atom or a sulfo group, more preferably a sulfo group, and R u2 is preferably an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] p -R e , more preferably —O[C(R a R b )-C(R c R d )-O] p -R e -OR f , and even more preferably —O[C(R a R b )-C(R c R d )-O] p -R e , -O-CH2CH2-O-CH2CH2-O-CH3, -O-CH2CH2-O-CH2CH2-OH or -O-CH2CH2-OH, or Ru1 and R u2 are combined together to form -OYO-.

[0109] For example, the polythiophene derivative according to a preferred embodiment of the present invention is R u1 is a sulfo group, and R u2 contains a repeating unit other than a sulfo group, or R u1 and R u2 The repeating unit includes a repeating unit -OYO- formed by bonding of the following. Preferably, the polythiophene derivative is R u1 is a sulfo group, and R u2 is an alkoxy group having 1 to 40 carbon atoms or -O-[ZO] p -R e or R u1 and R u2 The repeating unit includes a repeating unit -OYO- formed by bonding of the following. More preferably, the polythiophene derivative is R u1 is a sulfo group, and R u2 But -O[C(R a R b )-C(R c R d )-O] p -R e -OR f The repeating unit is Even more preferably, the polythiophene derivative is R u1 is a sulfo group, and R u2 But -O[C(R a R b )-C(R c R d )-O] p -R e or R u1 and R u2 The repeating unit includes a repeating unit -OYO- formed by bonding of the following. More preferably, the polythiophene derivative is R u1 is a sulfo group, and R u2contains a repeating unit that is -O-CH2CH2-O-CH2CH2-O-CH3, -O-CH2CH2-O-CH2CH2-OH, or -O-CH2CH2-OH, or R u1 and R u2 are bonded to each other and contain a repeating unit that is a group represented by the following formulas (Y1) and (Y2).

[0110]

Chemical formula

[0111] Preferred specific examples of the above polythiophene derivative include, for example, polythiophene containing at least one repeating unit represented by the following formulas (U1-1) to (U1-5).

[0112]

Chemical formula

[0113] Further, preferred structures of the above polythiophene derivative include, for example, a polythiophene derivative having a structure represented by the following formula (U1a). In the following formula, each unit may be bonded randomly or as a block polymer.

[0114]

Chemical formula

[0115] In the formula, a to d represent the molar ratio of each unit and satisfy 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 < a + b ≦ 1, 0 ≦ c < 1, 0 ≦ d < 1, and a + b + c + d = 1.

[0116] Furthermore, the polythiophene derivatives may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers). As polymers containing monomers A and B, block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) m -including multi-block copolymers. Polythiophenes may also contain repeat units derived from other types of monomers, such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes (such as phenylene, phenylenevinylene, and fluorene).

[0117] In the present invention, the content of the repeating unit represented by formula (U1) in the polythiophene derivative is preferably more than 50 mol % of all repeating units contained in the polythiophene derivative, more preferably 80 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, and most preferably 100 mol %.

[0118] In the present invention, depending on the purity of the starting monomers used in the polymerization, the polymer formed may contain repeating units derived from impurities. In the present invention, the term "homopolymer" means a polymer containing repeating units derived from one type of monomer, but may also contain repeating units derived from impurities. In the present invention, the polythiophene derivative is preferably a polymer in which essentially all repeating units are repeating units represented by the above formula (U1), and more preferably a polymer containing at least one of the repeating units represented by the above formulas (U1-1) to (U1-5).

[0119] In the present invention, when the polythiophene derivative contains a repeating unit having a sulfo group, it is preferable to convert the polythiophene derivative into an amine adduct in which an amine compound is added to at least a portion of the sulfo groups contained in the polythiophene derivative, from the viewpoint of further improving solubility and dispersibility in organic solvents.

[0120] Amine compounds that can be used to form the amine adduct include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, and n-octylamine. monoalkylamine compounds such as n-octadecylamine, n-nonadecylamine, and n-eicosanylamine; primary amine compounds such as monoarylamine compounds such as aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1-anthrylamine, 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, and 9-phenanthrylamine; primary amine compounds such as N-ethylmethylamine, N-methyl-n-propylamine, N-methylisopropylamine, and N-methylisopropylamine; N-ethyl-n-butylamine, N-methyl-s-butylamine, N-methyl-t-butylamine, N-methylisobutylamine, diethylamine, N-ethyl-n-propylamine, N-ethylisopropylamine, N-ethyl-n-butylamine, N-ethyl-s-butylamine, N-ethyl-t-butylamine, dipropylamine, Nn-propylisopropylamine, Nn-propyl-n-butylamine, Nn-propyl-s-butylamine, diisopropylamine, Nn-butylisopropylamine, Nt-butylisopropylamine, di(n-butyl) dialkylamine compounds such as di(s-butyl)amine, di(s-butyl)amine, diisobutylamine, aziridine (ethyleneimine), 2-methylaziridine (propyleneimine), 2,2-dimethylaziridine, azetidine (trimethyleneimine), 2-methylazetidine, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, hexamethyleneimine, heptamethyleneimine, and octamethyleneimine;Diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1,1'-dinaphthylamine, 2,2'-dinaphthylamine, 1,2'-dinaphthylamine, carbazole, 7H-benzo[c]carbazole, 11H-benzo[a]carbazole, 7H-dibenzo[c,g]carbazole, 13H-dibenzo[a,i]carbazole and other diarylamine compounds; N-methylaniline, N-ethylaniline, Nn-propylaniline, N-iso ... secondary amine compounds such as alkylarylamine compounds, such as N,N-isopropylaniline, Nn-butylaniline, Ns-butylaniline, N-isobutylaniline, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, Nn-propyl-1-naphthylamine, indoline, isoindoline, 1,2,3,4-tetrahydroquinoline, and 1,2,3,4-tetrahydroisoquinoline; Trialkylamine compounds such as dimethylisopropylamine, N,N-dimethyl-n-butylamine, N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine, N,N-dimethylisobutylamine, N,N-diethylmethylamine, N-methyldi(n-propyl)amine, N-methyldiisopropylamine, N-methyldi(n-butyl)amine, N-methyldiisobutylamine, triethylamine, N,N-diethyl-n-butylamine, N,N-diisopropylethylamine, N,N-di(n-butyl)ethylamine, tri(n-propyl)amine, tri(i-propyl)amine, tri(n-butyl)amine, tri(i-butyl)amine, 1-methylacetidine, 1-methylpyrrolidine, and 1-methylpiperidine; triarylamine compounds such as triphenylamine; alkyldiarylamine compounds such as N-methyldiphenylamine, N-ethyldiphenylamine, 9-methylcarbazole, and 9-ethylcarbazole;Examples of the tertiary amine compounds include dialkylarylamine compounds such as N,N-diethylaniline, N,N-di(n-propyl)aniline, N,N-di(i-propyl)aniline, and N,N-di(n-butyl)aniline. However, taking into consideration the balance between the solubility of the amine adduct and the charge transport properties of the resulting charge transport thin film, tertiary amine compounds are preferred, trialkylamine compounds are more preferred, and triethylamine is even more preferred; The amine adduct can be obtained by adding the polythiophene derivative to the amine itself or a solution thereof and stirring thoroughly.

[0121] In the present invention, the above polythiophene derivative or its amine adduct may be treated with a reducing agent before use. In polythiophene derivatives or their amine adducts, some of the repeating units constituting them may have an oxidized chemical structure called a "quinoid structure." The term "quinoid structure" is used in contrast to the term "benzenoid structure." The latter is a structure containing an aromatic ring, while the former refers to a structure in which a double bond within the aromatic ring moves out of the ring (resulting in the disappearance of the aromatic ring), resulting in the formation of two exocyclic double bonds conjugated with other double bonds remaining in the ring. Those skilled in the art can easily understand the relationship between these two structures from the relationship between the structures of benzoquinone and hydroquinone. Quinoid structures for the repeating units of various conjugated polymers are well known to those skilled in the art. As an example, the quinoid structure corresponding to the repeating unit of a polythiophene derivative containing the repeating unit represented by the above formula (U1) is shown below as formula (U1').

[0122] [ka] (In the formula, R u1 and R u2 is as defined in the above formula (U1).

[0123] This quinoid structure is formed by a process in which a polythiophene derivative containing a repeating unit represented by formula (U1) undergoes an oxidation reaction with a dopant, a process known as a doping reaction, and forms part of a structure known as a "polaron structure" or a "bipolaron structure" that imparts charge transport properties to the polythiophene derivative. These structures are known. The introduction of a "polaron structure" and / or a "bipolaron structure" is essential for the fabrication of organic EL devices and quantum dot EL devices. In fact, during the fabrication of organic EL devices and quantum dot EL devices, this is achieved by intentionally inducing the doping reaction when a thin film formed from a charge transport ink composition is baked. The presence of a quinoid structure in the polythiophene derivative prior to the doping reaction is thought to be due to an unintended oxidation reaction equivalent to the doping reaction occurring during the polythiophene derivative's manufacturing process (particularly the sulfonation step therein).

[0124] There is a correlation between the amount of quinoid structures contained in the polythiophene derivative and the solubility and dispersibility of the polythiophene derivative in organic solvents; as the amount of quinoid structures increases, the solubility and dispersibility tend to decrease. Therefore, the introduction of quinoid structures after a thin film is formed from the charge-transporting ink composition does not cause any problems. However, if an excessive amount of quinoid structures is introduced into the polythiophene derivative due to the unintended oxidation reaction, it may cause problems in the production of the charge-transporting ink composition. It is known that polythiophene derivatives vary in solubility and dispersibility in organic solvents. One of the reasons for this is thought to be that the amount of quinoid structures introduced into the polythiophene due to the unintended oxidation reaction varies depending on the production conditions of each polythiophene derivative. Therefore, when the polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if an excessive amount of quinoid structures has been introduced into the polythiophene derivative, the quinoid structures are reduced by the reduction, and the solubility and dispersibility of the polythiophene derivative in organic solvents are improved, making it possible to stably produce an excellent charge-transporting ink composition that gives a thin film with excellent homogeneity.

[0125] The conditions for the reduction treatment are not particularly limited as long as they can reduce the quinoid structure and appropriately convert it into a non-oxidized structure, i.e., the benzenoid structure (for example, in the case of a polythiophene derivative containing a repeating unit represented by formula (U1) above, the quinoid structure represented by formula (U1') is converted into the structure represented by formula (U1) above). For example, this treatment can be carried out by simply contacting the polythiophene derivative or the amine adduct with a reducing agent in the presence or absence of a suitable solvent. There are no particular limitations on the reducing agent as long as it can perform the reduction appropriately, but suitable examples include aqueous ammonia, hydrazine, and the like, which are readily available commercially. The amount of the reducing agent cannot be generally specified because it varies depending on the amount of reducing agent used. However, it is usually 0.1 parts by mass or more per 100 parts by mass of the polythiophene derivative or amine adduct to be treated in order to ensure appropriate reduction, and 10 parts by mass or less in order to prevent excess reducing agent from remaining.

[0126] In one example of a specific reduction method, the polythiophene derivative or amine adduct is stirred overnight in 28% aqueous ammonia at room temperature. Reduction under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivative or amine adduct in organic solvents.

[0127] When an amine adduct of a polythiophene derivative is used in the charge transporting ink composition of the present invention, the reduction treatment may be carried out either before or after the formation of the amine adduct.

[0128] Note that this reduction treatment changes the solubility or dispersibility of the polythiophene derivative or its amine adduct in the solvent, and as a result, the polythiophene derivative or its amine adduct, which was not dissolved in the reaction system at the start of the treatment, may become dissolved by the completion of the treatment. In such cases, the polythiophene derivative or its amine adduct can be recovered by a method such as adding an organic solvent incompatible with the polythiophene derivative or its amine adduct (acetone, isopropyl alcohol, etc., in the case of sulfonated polythiophene) to the reaction system to cause a precipitate of the polythiophene derivative or its amine adduct, and then filtering the precipitate.

[0129] The weight-average molecular weight of the polythiophene derivative or its amine adduct containing a repeating unit represented by formula (U1) is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 100,000, and even more preferably about 10,000 to about 50,000. By setting the weight-average molecular weight at or above the lower limit, good conductivity can be obtained with good reproducibility, while by setting it at or below the upper limit, solubility in organic solvents can be improved. The weight-average molecular weight is a polystyrene-equivalent value determined by gel permeation chromatography.

[0130] The polythiophene derivative or amine adduct thereof contained in the charge transport ink composition of the present invention may be a single polythiophene derivative or amine adduct thereof containing a repeating unit represented by formula (U1), or two or more types thereof. The polythiophene derivative containing the repeating unit represented by formula (U1) may be a commercially available product, or may be one polymerized by a known method using a thiophene derivative or the like as a starting material, but in either case, it is preferable to use one purified by a method such as reprecipitation or ion exchange. The use of a purified product can further improve the properties of an organic EL device or a quantum dot EL device having a thin film obtained from the charge transport ink composition of the present invention.

[0131] Sulfonation of conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in U.S. Patent No. 8,017,241 to Seshadri et al., and sulfonated polythiophenes are described in WO 2008 / 073149 and WO 2016 / 171935.

[0132] In the present invention, at least a portion of the polythiophene derivative or its amine adduct containing a repeating unit represented by formula (U1) contained in the charge transporting ink composition is dissolved in an organic solvent.

[0133] In the present invention, as the charge transport substance, a polythiophene derivative containing a repeating unit represented by formula (U1) or an amine adduct thereof may be used in combination with a charge transport substance consisting of another charge transport compound, but it is preferable that only a polythiophene derivative containing a repeating unit represented by formula (U1) or an amine adduct thereof is used.

[0134] In the present invention, the ratio of the nickel oxide nanoparticles to the charge transporting substance is preferably nickel oxide nanoparticles:charge transporting substance=10:90 to 95:5 by mass, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30, in consideration of the effect of improving the charge transporting property of the resulting thin film and the effect of suppressing the quenching phenomenon of the device.

[0135] [3] Organic solvents The charge transport ink composition of the present invention contains an organic solvent. The solvent is not particularly limited as long as it disperses or dissolves solids. Specific examples include alcoholic solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, 1-octanol, 1-nonanol, 1-decanol, tetrahydrofurfuryl alcohol, terpineol, cyclohexanol, diacetone alcohol, benzyl alcohol, 2-phenoxyethanol, and 2-benzyloxyethanol; ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, 1,3-octylene glycol, diethylene glycol, and dipropylene glycol. Glycol-based solvents such as glycerol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, and 3-methyl-1,5-pentanediol; ketone-based solvents such as acetone, acetylacetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, cyclohexanone, methylcyclopentanone, and isophorone;Dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, n-hexyl acetate, benzyl acetate, 2-hydroxyethyl acetate, methyl lactate, ethyl lactate, methyl propionate, ethyl propionate, propyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl malonate, dimethyl sebacate, diethyl sebacate, methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, dioxalate Ester solvents such as ethyl ether, dibutyl oxalate, diethyl fumarate, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, triacetin, and γ-butyrolactone; ether solvents such as dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, anisole, and 4-methoxytoluene;Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol butyl methyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol The solvent may be appropriately selected from glycol ether solvents such as ethanol butyl ether; amide solvents such as N-methylformamide, N-methylacetamide, N-methylformanilide, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cyclohexylbenzene, chlorobenzene, tetralin, and decylbenzene; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, i-octane, i-nonane, and i-decane; halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, 1,2-dichloroethane, and chloroform; cyano solvents such as acetonitrile and 3-methoxypropionitrile; and sulfoxide solvents such as dimethyl sulfoxide.

[0136] In the present invention, among these, alcohol-based solvents, glycol-based solvents, ketone-based solvents, ester-based solvents and glycol ether-based solvents are preferred, and methanol, ethanol, 1-octanol, 1-nonanol, 1-decanol, terpineol, ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, isophorone, propylene carbonate, dibutyl maleate, diethyl sebacate, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol butyl methyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and tripropylene glycol butyl ether are more preferred. These organic solvents can be used either alone or in combination of two or more.

[0137] The charge transport ink composition of the present invention is best prepared using only an organic solvent as the solvent. In this case, "only an organic solvent" means that only an organic solvent is used as the solvent, and does not exclude the presence of trace amounts of water contained in the organic solvent or solids used.

[0138] [4] Thiol compounds The charge transport ink composition of the present invention may further contain a thiol compound represented by the following formula (X1) in order to further enhance the effect of suppressing the quenching phenomenon in the resulting device and to further improve the dispersibility of nickel oxide nanoparticles in the charge transport ink. R x1 -SH (X1)

[0139] In the formula, R x1 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent.

[0140] The substituents in the alkyl group, alkenyl group, and alkynyl group are each independently a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, an organooxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom.

[0141] The substituents in the aryl group, aralkyl group, and heteroaryl group are, independently of one another, a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphate group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, an alkyl group having 1 to 20 carbon atoms, 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, an aralkyl group having 7 to 20 carbon atoms, an organoxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom.

[0142] Above R x1 The alkyl group contained in may have at least one group selected from the group consisting of an oxygen atom, a carbonyl group and an ester group interposed between its carbon atoms.

[0143] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups.

[0144] Specific examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.

[0145] Specific examples of the alkynyl group having 2 to 20 carbon atoms include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group, an n-3-butynyl group, a 1-methyl-2-propynyl group, an n-1-pentynyl group, an n-2-pentynyl group, an n-3-pentynyl group, an n-4-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, a 1,1-dimethyl-n-propynyl group, an n-1-hexynyl group, an n-1-decynyl group, an n-1-pentadecinyl group, and an n-1-eicosynyl group.

[0146] Specific 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, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0147] Specific examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a p-methylphenylmethyl group, a m-methylphenylmethyl group, an o-ethylphenylmethyl group, a m-ethylphenylmethyl group, a p-ethylphenylmethyl group, a 2-propylphenylmethyl group, a 4-isopropylphenylmethyl group, a 4-isobutylphenylmethyl group, and an α-naphthylmethyl group.

[0148] Specific examples of the heteroaryl group having 2 to 20 carbon atoms include oxygen-containing heteroaryl groups such as a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, and a 5-isoxazolyl group; sulfur-containing heteroaryl groups such as a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, and a 5-isothiazolyl group; Aryl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 3-pyrazyl group, 5-pyrazyl group, 6-pyrazyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 6-pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 5-pyridazyl group, 6-pyridazyl group, 1,2,3-triazin-4-yl group, 1,2,3-triazin-5-yl group, 1,2,4-triazin-3-yl group a quinolinyl group, a 1,2,4-triazin-5-yl group, a 1,2,4-triazin-6-yl group, a 1,3,5-triazin-2-yl group, a 1,2,4,5-tetrazin-3-yl group, a 1,2,3,4-tetrazin-5-yl group, a 2-quinolinyl group, a 3-quinolinyl group, a 4-quinolinyl group, a 5-quinolinyl group, a 6-quinolinyl group, a 7-quinolinyl group, an 8-quinolinyl group, a 1-isoquinolinyl group, a 3-isoquinolinyl group, a 4-isoquinolinyl group, a 5-isoquinolinyl group, Examples of nitrogen-containing heteroaryl groups include a 6-isoquinolinyl group, a 7-isoquinolinyl group, an 8-isoquinolinyl group, a 2-quinoxanyl group, a 5-quinoxanyl group, a 6-quinoxanyl group, a 2-quinazolinyl group, a 4-quinazolinyl group, a 5-quinazolinyl group, a 6-quinazolinyl group, a 7-quinazolinyl group, an 8-quinazolinyl group, a 3-cinnolinyl group, a 4-cinnolinyl group, a 5-cinnolinyl group, a 6-cinnolinyl group, a 7-cinnolinyl group, and an 8-cinnolinyl group.

[0149] In the substituents of the alkyl group, alkenyl group and alkynyl group, examples of the aryl group having 6 to 20 carbon atoms include the same groups as those exemplified above.

[0150] The organoxy group includes an alkoxy group, an alkenyloxy group, an aryloxy group, etc. The alkyl group, alkenyl group and aryl group contained therein are the same as those described above.

[0151] Examples of the organoamino group include alkylamino groups having 1 to 12 carbon atoms, such as methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, nonylamino, decylamino, and dodecylamino; dialkylamino groups in which the alkyl group has 1 to 12 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, dicyclohexylamino, diheptylamino, dioctylamino, dinonylamino, and didecylamino; arylamino groups in which the aryl group has 6 to 20 carbon atoms, such as diphenylamino and dinaphthylamino; and morpholino groups. Furthermore, some or all of the hydrogen atoms of the alkyl group contained in the organoamino group may be substituted with halogen atoms.

[0152] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0153] Examples of the organosilyl group include trialkylsilyl groups, each of which is an alkyl group having 1 to 10 carbon atoms, such as trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl, hexyldimethylsilyl, octyldimethylsilyl, and decyldimethylsilyl. The alkyl groups contained in the organosilyl group may have some or all of their hydrogen atoms substituted with halogen atoms. Examples of halogen atoms include the same as those exemplified above.

[0154] Examples of the organothio group include alkylthio groups having 1 to 12 carbon atoms, such as methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, and dodecylthio; and arylthio groups having 6 to 20 carbon atoms, such as phenylthio and naphthylthio. The alkyl and aryl groups contained in the organothio group may have some or all of their hydrogen atoms substituted with halogen atoms. Examples of halogen atoms include the same as those exemplified above.

[0155] In the substituents of the alkyl group, alkenyl group and alkynyl group, examples of the halogen atom include the same as those exemplified above.

[0156] In the substituents possessed by the aryl group, aralkyl group, and heteroaryl group, examples of the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the alkynyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aralkyl group having 7 to 20 carbon atoms, the organooxy group, the organoamino group, the organosilyl group, the organothio group, and the halogen atom are the same as those exemplified above.

[0157] R in the above formula (X1) x1 As the alkyl group, an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms is preferred. Also, the above R x1 The substituent that the group has is preferably a hydroxy group, a carboxy group, an ester group, an organoxy group or a halogen atom.

[0158] R in the above formula (X1) x1 is an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aryl group having 6 to 14 carbon atoms which may have a substituent, and the substituents on the alkyl group and aryl group are each independently a hydroxy group, a carboxy group, an ester group, an organoxy group, or a halogen atom, which is more preferred.

[0159] Specific examples of the thiol compound represented by the above formula (X1) include, but are not limited to, those shown below.

[0160] [ka]

[0161] When the charge transport ink composition of the present invention contains the thiol compound, the content thereof is preferably 1 to 100 parts by mass, more preferably 1 to 60 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 100 parts by mass of the nickel oxide nanoparticles and the charge transport substance combined.

[0162] [5] Dopant materials The charge transporting ink composition of the present invention may contain a dopant substance for the purpose of improving the charge transporting ability, depending on the application of the thin film to be obtained. The dopant substance is not particularly limited as long as it dissolves in at least one solvent used in the ink composition, and both inorganic and organic dopant substances can be used. The inorganic and organic dopant substances may be used alone or in combination of two or more. When a dopant substance is contained, its content cannot be generally defined because it is determined appropriately taking into consideration the type of dopant, the desired degree of charge transportability, etc., but is usually within a range of 0.0001 to 100.0 parts by mass per 1 part of the charge transport substance.

[0163] Inorganic dopant substances include inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminum chloride (III) (AlCl3), titanium tetrachloride (IV) (TiCl4), boron tribromide (BBr3), boron trifluoride etherate (BF3·OEt2), iron chloride (III) (FeCl3), copper chloride (II) (CuCl2), antimony pentachloride (V) (SbCl5), and antimony pentafluoride (V) (SbF5). metal halides such as arsenic(V) pentafluoride (AsF5), phosphorus pentafluoride (PF5), and tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); halogens such as Cl2, Br2, I2, ICl, ICl3, IBr, and IF4; and heteropolyacids such as phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid.

[0164] In addition, examples of organic dopant substances include tetracyanoquinodimethanes such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane; tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), tetrachloro-7,7,8,8-tetracyanoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5 -Dichloro-7,7,8,8-tetracyanoquinodimethane and other halotetracyanoquinodimethanes (haloTCNQs); benzoquinone derivatives such as tetrachloro-1,4-benzoquinone (chloranil) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ); benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, Naphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 2, arylsulfonic acid compounds such as 7-dinonyl-4,5-naphthalenedisulfonic acid, 1,4-benzodioxanedisulfonic acid derivatives described in WO 2005 / 000832, arylsulfonic acid derivatives described in WO 2006 / 025342, dinonylnaphthalenesulfonic acid derivatives described in JP 2005-108828 A, arylsulfonic acid compounds described in WO 2022 / 181587, aromatic sulfone compounds such as polystyrene sulfonic acid, and fluorinated arylsulfonic acid polymer compounds described in WO 2023 / 008176;Examples of such arylsulfonic acid ester compounds include arylsulfonic acid ester compounds described in WO 2017 / 217455, WO 2017 / 217457, WO 2019 / 124412, and WO 2022 / 209892; and non-aromatic sulfone compounds such as 10-camphorsulfonic acid. These inorganic and organic dopant substances may be used alone or in combination of two or more.

[0165] [6] Charge transporting ink composition and charge transporting thin film The viscosity of the charge transporting ink composition is determined as appropriate depending on the thickness of the thin film to be formed and the solid content concentration, but is typically 1 to 50 mPa·s at 25° C. In the present invention, the solid content refers to the components other than the solvent contained in the charge transporting ink composition. The solids concentration of the charge transporting ink composition is determined appropriately taking into consideration the viscosity and surface tension of the composition, the thickness of the thin film to be formed, and the like, but is typically about 0.1 to 10.0 mass %, and in order to improve the coatability of the composition, it is preferably about 0.5 to 8.0 mass %, and more preferably about 1.0 to 6.0 mass %.

[0166] The method for preparing the charge transporting ink composition is not particularly limited, but examples include a method in which a charge transporting substance and, if necessary, a dopant substance are dissolved in an organic solvent, and a dispersion (sol) of nickel oxide nanoparticles is added thereto.

[0167] In particular, when preparing the charge transport ink composition, from the viewpoint of obtaining a thin film with a higher flatness with good reproducibility, it is desirable to dissolve the charge transport material, nickel oxide nanoparticles, and, if necessary, a dopant material, etc. in an organic solvent, and then filter the solution using a submicrometer-order filter or the like before use.

[0168] The charge transporting ink composition described above can be used to easily produce a charge transporting thin film, and is therefore suitable for use in producing electronic devices, particularly organic EL devices and quantum dot EL devices. In this case, the charge transporting thin film can be formed by applying the above-mentioned charge transporting ink composition onto a substrate and baking it. The method for applying the composition is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, and a slit coating method. It is preferable to adjust the viscosity and surface tension of the ink composition depending on the application method.

[0169] Furthermore, the atmosphere in which the charge transport ink composition is baked after application is not particularly limited, and a thin film having a uniform film surface and high charge transport properties can be obtained not only in air but also in an inert gas atmosphere such as nitrogen or in a vacuum.

[0170] The baking temperature is appropriately determined within a range of about 100 to 260°C, taking into consideration the use of the resulting thin film, the degree of charge transport property to be imparted to the resulting thin film, the type and boiling point of the solvent, etc. For example, when the resulting thin film is used as a hole transport layer of an organic EL device or a quantum dot EL device, the baking temperature is preferably about 140 to 250°C, and more preferably about 145 to 240°C. During firing, the temperature may be changed in two or more stages in order to achieve a more uniform film formation or to promote the reaction on the substrate, and heating may be carried out using an appropriate device such as a hot plate or an oven.

[0171] The thickness of the charge transport thin film is not particularly limited, but is preferably 5 to 300 nm when used as a functional layer provided between an anode and an emitting layer, such as a hole injection layer, hole transport layer, or hole injection transport layer, of an organic EL device or a quantum dot EL device. Methods for changing the film thickness include changing the solid concentration in the composition or changing the amount of solution on the substrate during application.

[0172] [7] Organic EL devices and quantum dot EL devices When the charge transport thin film is applied to an organic EL device or a quantum dot EL device, the charge transport thin film can be provided between a pair of electrodes that constitute the organic EL device or the quantum dot EL device. Representative configurations of organic EL devices and quantum dot EL devices include, but are not limited to, the following (a) to (f). In the following configurations, an electron blocking layer or the like can be provided between the light-emitting layer and the anode, and a hole (positive hole) blocking layer or the like can be provided between the light-emitting layer and the cathode, as needed. The hole injection layer, hole transport layer, or hole injection transport layer may also function as an electron blocking layer, and the electron injection layer, electron transport layer, or electron injection transport layer may also function as a hole (positive hole) blocking layer. Furthermore, an optional functional layer can be provided between each layer as needed. (a) Anode / 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 / hole injection layer / hole transport layer / light-emitting layer / cathode (f) Anode / hole injection transport layer / light-emitting layer / cathode

[0173] The terms "hole injection layer," "hole transport layer," and "hole injection transport layer" refer to layers formed between the light-emitting layer and the anode, which have the function of transporting holes from the anode to the light-emitting layer. When only one layer of a hole-transporting material is provided between the light-emitting layer and the anode, it is the "hole injection transport layer." When two or more layers of a hole-transporting material are provided between the light-emitting layer and the anode, the layer closest to the anode is the "hole injection layer," and the remaining layers are "hole transport layers." In particular, the hole injection (transport) layer is a thin film that is excellent not only in accepting holes from the anode but also in injecting holes into the hole transport (light-emitting) layer. The terms "electron injection layer," "electron transport layer," and "electron injection transport layer" refer to layers formed between the light-emitting layer and the cathode, which have the function of transporting electrons from the cathode to the light-emitting layer. When only one layer of an electron-transporting material is provided between the light-emitting layer and the cathode, it is the "electron injection transport layer." When two or more layers of electron-transporting materials are provided between the light-emitting layer and the cathode, the layer closest to the cathode is the "electron injection layer," and the other layers are "electron transport layers." The "light-emitting layer" is an organic layer that has a light-emitting function, and when a doping system is used, it contains a host material and a dopant material. In this case, the host material mainly functions to promote the recombination of electrons and holes and confine excitons within the light-emitting layer, while the dopant material functions to efficiently emit light from the excitons obtained by the recombination. In the case of a phosphorescent element, the host material mainly functions to confine excitons generated by the dopant within the light-emitting layer.

[0174] The charge-transporting thin film of the present invention can be used as a functional layer provided between an anode and an emission layer in an organic EL device or a quantum dot EL device, and is suitable as a hole injection layer, a hole transport layer, or a hole injection transport layer, more suitable as a hole injection layer or a hole transport layer, and even more suitable as a hole transport layer.

[0175] When an EL device is produced using the charge transporting ink composition of the present invention, the materials and production methods used include, but are not limited to, those listed below. An example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge transport ink composition of the present invention is as follows: It is preferable to previously perform a surface treatment on the electrodes, such as cleaning with alcohol or pure water, or UV ozone treatment or oxygen plasma treatment, within a range that does not adversely affect the electrodes. A hole injection layer and a hole transport layer made of the charge transport thin film of the present invention are formed on an anode substrate by the above-described method. This is then introduced into a vacuum deposition apparatus, and a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, instead of forming the light-emitting layer by deposition in this method, these layers are formed by a wet process using a light-emitting layer-forming composition containing a light-emitting polymer. If necessary, an electron blocking layer may be provided between the light-emitting layer and the hole transport layer.

[0176] Anode materials include transparent electrodes such as indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes made of metals such as aluminum or their alloys, preferably planarized. Polythiophene derivatives and polyaniline derivatives with high charge transport properties can also be used. Other metals that may be used to form the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

[0177] Materials for forming the hole injection layer include copper phthalocyanine, titanium oxide phthalocyanine, platinum phthalocyanine, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine, 2,7-bis[N,N-bis(4-methoxy-phenyl)amino]-9,9-spirobifluorene, 2,2'-bis[N,N-bis(4-methoxy-phenyl)amino]-9,9-spirobifluorene, N,N'-diphenyl-N,N'-di[4-(N,N-ditolylamino)phenyl]benzidine, N,N'-diphenyl-N,N'-di[4-(N,N-diphenylamino)phenyl]benzidine, N 4 ,N 4' -(biphenyl-4,4'-diyl)bis(N 4 ,N 4' ,N 4' -triphenylbiphenyl-4,4'-diamine)N 1 ,N 1' -(biphenyl-4,4'-diyl)bis(N 1 -phenyl-N4 ,N 4' -di-m-tolylbenzene-1,4-diamine), WO 2004 / 043117, WO 2004 / 105446, WO 2005 / 000832, WO 2005 / 043962, WO 2005 / 042621, WO 2005 / 107335, WO 2006 / 006459, WO 2006 / 025342, WO 2006 / 137473, WO 2007 / 049631, WO 2007 / 099808, WO 2008 / 010474, WO 2008 / 032 617, WO 2008 / 032616, WO 2008 / 129947, WO 2009 / 096352, WO 2010 / 041701, WO 2010 / 058777, WO 2010 / 058776, WO 2013 / 042623, WO 2013 / 129249, WO 2014 / 115865, WO 2014 / 132917, WO 2014 / 141998 and WO 2014 / 132834, and the like.

[0178] Materials for forming the light-emitting layer include, but are not limited to, low-molecular-weight light-emitting materials such as metal complexes such as aluminum complexes of 8-hydroxyquinoline, metal complexes of 10-hydroxybenzo[h]quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, metal complexes of (2-hydroxyphenyl)benzothiazole, and silole derivatives; and systems in which a light-emitting material and an electron transfer material are mixed with a polymer compound such as poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), or polyvinylcarbazole. Furthermore, when forming a light-emitting layer by vapor deposition, it may be co-deposited with a light-emitting dopant. Examples of the light-emitting dopant include, but are not limited to, metal complexes such as tris(2-phenylpyridine)iridium(III) (Ir(ppy)), naphthacene derivatives such as rubrene, quinacridone derivatives, and fused polycyclic aromatic rings such as perylene.

[0179] Examples of materials for forming the electron transport layer / hole blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

[0180] Materials for forming the electron injection layer include, but are not limited to, metal oxides such as lithium oxide (Li2O), magnesium oxide (MgO), and alumina (Al2O3), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF). Cathode materials include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like. Examples of materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole)iridium.

[0181] Examples of light-emitting polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), polyphenylenevinylene derivatives such as poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

[0182] The quantum dot material may include at least one semiconductor material selected from the group consisting of II-VI group semiconductors, III-V group semiconductors, I-III-VI group semiconductors, IV group semiconductors, and I-II-IV-VI group semiconductors. Specific examples of the semiconductor material include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe e, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; GaN, GaP, GaAs, G aSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, Ga InNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnS Examples of suitable cations include, but are not limited to, SnSe, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe, CuGaSe, CuInS, CuGaS, CuInSe, AgInS, AgGaSe, AgGaS, C, Si, and Ge.

[0183] As described above, the charge transport ink composition of the present invention is suitably used for forming functional layers such as a hole injection layer, a hole transport layer, and a hole injection transport layer that are provided between an anode and a light-emitting layer of an organic EL device or a quantum dot EL device. In addition, the charge transport ink composition of the present invention can also be used for forming charge transport thin films in electronic devices such as organic photoelectric conversion devices, organic thin-film solar cells, organic perovskite photoelectric conversion devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic optical inspectors, organic photoreceptors, organic field quenching devices, light-emitting electrochemical cells, quantum lasers, organic laser diodes, and organic plasmon light-emitting devices. [Example]

[0184] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0185] (1) Substrate cleaning: Substrate cleaning equipment (low-pressure plasma method) manufactured by Choshu Sangyo Co., Ltd. (2) Coating of charge transporting ink composition: Spin coater MS-A100, manufactured by Mikasa Co., Ltd. (3) Measurement of fluorescence intensity: Hitachi High-Technologies Corporation, F-7000 Hitachi spectrofluorometer (4) Fabrication of QD-EL elements: Multi-function deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (5) Measurement of electrical properties of QD-EL elements: Multi-channel IVL measurement device manufactured by EHC Co., Ltd.

[0186] [1] Preparation of nickel oxide nanoparticle dispersion [Manufacturing Example 1] 50.0 g of Avantama P-21 (Avantama), which is nickel oxide nanoparticles dispersed in ethanol, and 19.6 g of triethylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd., the same applies below) were placed in a recovery flask, and the ethanol contained in the Avantama P-21 was replaced with triethylene glycol monomethyl ether using an evaporator. The mixture was then filtered through a PTFE filter with a pore size of 1.0 μm to obtain a dispersion of nickel oxide nanoparticles dispersed in triethylene glycol monomethyl ether (solid concentration 6.0% by mass).

[0187] [2] Preparation of charge transport ink composition [Example 1-1] 0.045 g of the following arylamine compound A1 (synthesized according to the method described in International Publication No. WO 2015 / 050253), 2.72 g of triethylene glycol monomethyl ether, and 0.485 g of tripropylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.; the same applies hereinafter) were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes. Then, 1.75 g (0.105 g as solids) of triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles (prepared in Preparation Example 1) were added and stirred at room temperature for 1 hour. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0188] [ka]

[0189] [Example 1-2] 0.075 g of arylamine compound A1, 3.19 g of triethylene glycol monomethyl ether, and 0.485 g of tripropylene glycol monomethyl ether were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. Then, 1.25 g (0.075 g as solids) of the triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles prepared in Preparation Example 1 was added and stirred at room temperature for 1 hour. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0190] [Examples 1-3] 0.105 g of arylamine compound A1, 3.66 g of triethylene glycol monomethyl ether, and 0.485 g of tripropylene glycol monomethyl ether were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. Then, 0.75 g of the triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles (0.045 g as solids) prepared in Preparation Example 1 were added and stirred at room temperature for 1 hour. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0191] [Examples 1-4] A conical flask was charged with 0.045 g of arylamine compound A1, 2.71 g of triethylene glycol monomethyl ether, and 0.484 g of tripropylene glycol monomethyl ether, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 1.75 g (0.105 g as solids) of nickel oxide nanoparticles dispersed in triethylene glycol monomethyl ether prepared in Preparation Example 1 was added, and the mixture was stirred at room temperature for 1 hour. Then, 0.005 g of pentafluorobenzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.; the same applies hereinafter) was added, and the mixture was stirred at room temperature for an additional 30 minutes. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0192] [Examples 1-5] 0.045 g of arylamine compound A1, 2.70 g of triethylene glycol monomethyl ether, and 0.483 g of tripropylene glycol monomethyl ether were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. Then, 1.75 g of triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles (0.105 g as solids) prepared in Preparation Example 1 were added and stirred at room temperature for 1 hour. Then, 0.021 g of thiol compound T1 synthesized according to the method described in JP 2020-105491 A was added and stirred at room temperature for an additional 30 minutes. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0193] [ka]

[0194] [Examples 1-6] A charge transporting ink composition (solid concentration 3.0% by mass) was obtained in the same manner as in Example 1-5, except that 0.021 g of 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the thiol compound instead of thiol compound T1.

[0195] [Comparative Example 1-1] 2.02 g of triethylene glycol monomethyl ether and 0.485 g of tripropylene glycol monomethyl ether were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. 2.50 g of the triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles prepared in Preparation Example 1 were then added and stirred at room temperature for 1 hour. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0196] [Comparative Example 1-2] 2.02 g of triethylene glycol monomethyl ether and 0.485 g of tripropylene glycol monomethyl ether were added to an Erlenmeyer flask and stirred at room temperature for 30 minutes using a stirrer. 2.50 g of the triethylene glycol monomethyl ether-dispersed nickel oxide nanoparticles prepared in Preparation Example 1 were then added and stirred at room temperature for 1 hour. 0.008 g of pentafluorobenzenethiol was then added and stirred at room temperature for an additional 30 minutes. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 3.0% by mass).

[0197] [3] Fabrication and evaluation of photoluminescence (PL) evaluation substrates [Example 2-1] The charge-transporting ink composition prepared in Example 1-1 was applied to a quartz substrate using a spin coater and then baked on a hot plate in an air atmosphere at 120°C for 1 minute. This was then baked on a hot plate in an air atmosphere at 200°C for 30 minutes to form a uniform 40-nm charge-transporting thin film on the quartz substrate. The quartz substrate had been previously cleaned of surface impurities using an O2 plasma cleaning device (150 W, 30 seconds) before use. Next, a QD toluene dispersion (PureBlue.dots in Toluene_v2, manufactured by QNA Corporation; the same applies below) was applied to the quartz substrate with the thin film formed thereon using a spin coater under a nitrogen atmosphere and then baked at 100°C for 10 minutes to form a 40-nm thin film (QD layer), thereby preparing a PL evaluation substrate. To prevent performance degradation due to the effects of oxygen and water in the air, the PL evaluation substrate was sealed with a transparent sealing substrate before its performance evaluation. Sealing was performed using 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 PL evaluation substrate was placed between sealing substrates, and the sealing substrates were bonded together with an adhesive (MORESCO Corporation, MORESCO Moisture Cut WB90US(P)).

[0198] [Examples 2-2 to 2-6] PL evaluation substrates were prepared in the same manner as in Example 2-1, except that the compositions prepared in Examples 1-2 to 1-6 were used instead of the charge transporting ink composition prepared in Example 1-1.

[0199] [Comparative Examples 2-1 to 2-2] PL evaluation substrates were prepared in the same manner as in Example 2-1, except that the compositions prepared in Comparative Examples 1-1 and 1-2 were used instead of the charge transporting ink composition prepared in Example 1-1.

[0200] [Comparative Example 2-3] A QD toluene dispersion was applied to a quartz substrate using a spin coater in a nitrogen atmosphere, and then baked on a hot plate in a nitrogen atmosphere at 100°C for 10 minutes to form a 40 nm thin film (QD layer), thereby producing a PL evaluation substrate. To prevent deterioration of characteristics due to the influence of oxygen and water in the air, the PL evaluation substrate was sealed with a sealing substrate using the same method as in Example 1-1, and then its characteristics were evaluated.

[0201] The fluorescence intensity of the QD layer in the PL evaluation substrates prepared in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3 was measured. Specifically, 365 nm excitation light was irradiated from the sealing substrate side, and fluorescence spectra were obtained from 385 nm to 650 nm. Table 1 lists the detailed configuration of the substrates prepared above, as well as the fluorescence intensity at a wavelength of 457 nm, peak wavelength, and half-width. The fluorescence intensity values ​​listed are normalized values, with the fluorescence intensity at a wavelength of 457 nm of the fluorescence spectrum obtained from the substrate prepared in Comparative Example 2-3 set to 100.

[0202] [Table 1]

[0203] The PL intensity from QDs obtained using a composition containing arylamine compound A1 as a charge-transporting material was higher than that obtained without arylamine compound A1. This indicates that the inclusion of a charge-transporting material improved the QD quenching phenomenon caused by nickel oxide nanoparticles. Furthermore, the inclusion of a thiol compound in addition to arylamine compound A1 resulted in the same or even improved PL intensity. This is believed to be due to the thiol compound acting as a ligand on the surface of nickel oxide nanoparticles, passivating defects on the nickel oxide nanoparticle surface and enhancing the compatibility between nickel oxide nanoparticles and arylamine compound A1, resulting in a more homogeneous charge-transporting thin film.

[0204] [4] Preparation of charge-transporting ink composition for fabricating QD-EL devices [Manufacturing Example 2] 39.2 g of ST-OS (Nissan Chemical Industries, Ltd.), a water-dispersed silica sol, and 42.0 g of dipropylene glycol monomethyl ether (Kanto Chemical Industries, Ltd.; the same applies hereinafter) were placed in a recovery flask, and the water contained in ST-OS was solvent-substituted with dipropylene glycol monomethyl ether using an evaporator.The mixture was then filtered through a PTFE filter with a pore size of 1.0 μm, yielding a silica sol dispersed in dipropylene glycol monomethyl ether (solids concentration 16.0 mass%).

[0205] [Preparation Example 1] A glass vial was charged with 0.11 g of copper iodide (Fujifilm Wako Pure Chemical Industries, Ltd.), 0.16 g of 1-amino-2-butanol (Tokyo Chemical Industry Co., Ltd.), 2.60 g of diethylene glycol (Kanto Chemical Co., Inc.), and 3.01 g of dipropylene glycol monomethyl ether. The mixture was stirred at room temperature for 30 minutes using a stirrer, and then 0.071 g of pentafluorobenzenethiol was added and stirred at room temperature for 30 minutes. 1.05 g of the silica sol obtained in Production Example 2 was then added and stirred at room temperature for 30 minutes. The resulting mixture was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge-transporting ink composition (solids concentration: 4.0% by mass).

[0206] [5] Fabrication and evaluation of QD-EL devices [Example 3-1] The charge-transporting ink composition obtained in Preparation Example 1 was applied to an ITO substrate using a spin coater. The resulting coating was dried under reduced pressure of 10 Pa or less for 15 minutes. It was then baked on a hot plate in an air atmosphere at 230°C for 30 minutes to form a uniform 65 nm charge-transporting thin film on the ITO substrate. A 25 mm x 25 mm x 0.7 mm glass substrate with a patterned 50 nm indium tin oxide (ITO) film formed on its surface was used as the ITO substrate. Prior to use, impurities on the surface were removed using an O2 plasma cleaning device (150 W, 30 seconds). The charge-transporting ink composition obtained in Example 1-1 was then applied using a spin coater and dried in an air atmosphere at 120°C for 1 minute. It was then baked in an air atmosphere at 200°C for 30 minutes to form a uniform 40 nm thin film. Next, a QD toluene dispersion was applied using a spin coater under a nitrogen atmosphere, and then baked at 100°C for 10 minutes to form a 40 nm thin film (QD layer). Next, a ZnO dispersion (Avantama, N-10) was applied using a spin coater under a nitrogen atmosphere to form a 40 nm thin film on the QD layer. After that, a vacuum deposition apparatus (vacuum degree 1.0 × 10) was used. -5 A QD-EL device was fabricated by depositing aluminum at a deposition rate of 0.2 nm / sec to a thickness of 80 nm using a PECVD cathode.

[0207] To prevent deterioration of characteristics due to the effects of oxygen, water, etc. in the air, the QD-EL elements were sealed with sealing substrates before their characteristics were evaluated. Sealing was performed as follows: In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the organic EL elements were placed between sealing substrates, and the sealing substrates were bonded together with an adhesive (MORESCO Moisture Cut WB90US(P), manufactured by MORESCO Corporation). At this time, a moisture scavenger (HD-071010W-40, manufactured by DYNIC Corporation) was placed inside the sealing substrates together with the organic EL elements. The bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation dose: 6,000 mJ / cm). 2), and then annealed at 80°C for 1 hour to cure the adhesive.

[0208] [Example 3-2] A QD-EL device was fabricated in the same manner as in Example 3-1, except that the charge transporting ink composition obtained in Example 1-4 was used instead of the charge transporting ink composition obtained in Example 1-1.

[0209] [Comparative Examples 3-1 to 3-2] QD-EL elements were prepared in the same manner as in Example 3-1, except that the charge transporting ink compositions obtained in Comparative Examples 1-1 and 1-2 were used instead of the charge transporting ink composition obtained in Example 1-1.

[0210] For each of the elements of Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-2, the luminance was 100 cd / m when a voltage of 0 to 10 V was applied. 2 The driving voltage, current density, and luminous efficiency were measured at 1000 kJ / s, and the results are shown in Table 2.

[0211] [Table 2]

[0212] In the composition that does not contain arylamine A1 as a charge transport material, the charge transport efficiency is 100 cd / m when a voltage of up to 10 V is applied. 2 Although no light emission was obtained, the inclusion of arylamine A1 resulted in improved QD-EL properties. This is believed to be due to the inclusion of arylamine A1, which improves hole transport to the QD layer. Furthermore, the inclusion of a thiol compound further improved the QD-EL properties. This is believed to be due to the thiol compound acting as a ligand on the surface of the nickel oxide nanoparticles, passivating defects on the nickel oxide nanoparticle surface, and increasing compatibility with arylamine compound A1, resulting in a more uniform charge-transporting thin film.

Claims

1. The composition includes nickel oxide nanoparticles, a charge transport material, and an organic solvent, The charge transporting ink composition wherein the charge transporting substance is an arylamine derivative, or a polythiophene derivative or an amine adduct thereof.

2. 2. The charge transporting ink composition according to claim 1, wherein the arylamine derivative is represented by the following formula (T1): 【Chemical 1】 [In the formula, Ph 1 represents a group represented by formula (P1), 【Chemistry 2】 (In the formula, R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom. Ar 1 each independently represents a group represented by any one of formulas [B1] to [B11], 【Chemistry 3】 (In the formula, R 5 ~R 25 , R 28 ~R 49 and R 51 ~R 152 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group, an alkyl group having 1 to 20 carbon atoms, 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, each of which may be substituted with a halogen atom; R 26 and R 27 are, independently of each other, Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, each optionally substituted with R 50 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Ar 3 each independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl group having 6 to 20 carbon atoms)amino group, Z 1 is a halogen atom, a nitro group, a cyano group, or Z 2 represents 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, each of which may be substituted with Z 2 is a halogen atom, a nitro group, a cyano group, or Z 3 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, each optionally substituted with Z 3 represents a halogen atom, a nitro group, or a cyano group; Z 4 represents a halogen atom, a nitro group, a cyano group, Z 5 an aryl group having 6 to 20 carbon atoms which may be substituted with 5 represents a heteroaryl group having 2 to 20 carbon atoms which may be substituted by, an organosilyl group, or an aryloxy group which may be substituted by, Z 5 is a halogen atom, a nitro group, a nitro group, or Z 3 represents 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 Ar 2 each independently represents a group represented by any one of formulas [A1] to [A18], 【Chemistry 4】 (In the formula, R 153 is a hydrogen atom, Z 4 an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, each optionally substituted with R 154 and R 155 are, independently of each other, Z 1 an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, each optionally substituted with DPA represents a diphenylamino group; Ar 3 , Z 1 and Z 3 ~Z 5 indicates the same meaning as above.) k represents an integer of 1 to 10.

3. 2. The charge transporting ink composition according to claim 1, wherein the polythiophene derivative or the amine adduct thereof is a polythiophene derivative or the amine adduct thereof containing a repeating unit represented by the following formula (U1): 【Chemistry 5】 (In the formula, R u1 and R u2 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, a fluoroalkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, -O-[Z-O] p -R e , or a sulfo group, or R u1 and R u2 are bonded to each other, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and which may be substituted with a sulfo group, Z is an alkylene group having 1 to 40 carbon atoms which may be substituted with a halogen atom, p is an integer of 1 or more, and R e is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

4. The above R u1 is a sulfo group, and the R u2 is an alkoxy group having 1 to 40 carbon atoms or —O—[Z—O] p -R e or the above R u1 and R u2 4. The charge transporting ink composition according to claim 3, wherein the bond is --O--Y--O--.

5. 2. The charge transporting ink composition according to claim 1, further comprising a thiol compound represented by the following formula (X1): R x1 -SMH (X1) (In the formula, R x1 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent. The substituents on the alkyl group, alkenyl group, and alkynyl group are, independently of one another, a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, an aryl group having 6 to 20 carbon atoms, an organooxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom. The substituents in the aryl group, aralkyl group, and heteroaryl group are, independently of one another, a hydroxy group, a silanol group, a thiol group, a carboxy group, a phosphate group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, an alkyl group having 1 to 20 carbon atoms, 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, an aralkyl group having 7 to 20 carbon atoms, an organoxy group, an organoamino group, an organosilyl group, an organothio group, a sulfo group, a cyano group, or a halogen atom. The above R x1 The alkyl group contained in may have at least one group selected from the group consisting of an oxygen atom, a carbonyl group, and an ester group interposed between its carbon atoms.

6. R in the above formula (X1) x1 is an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms, and the substituents on the alkyl group and the aryl group are each independently a hydroxy group, a carboxy group, an ester group, an organoxy group, or a halogen atom.

7. A charge transporting thin film obtained from the charge transporting ink composition according to any one of claims 1 to 6.

8. An electronic device comprising the charge transporting thin film according to claim 7.

9. 9. The electronic device according to claim 8, wherein the charge transporting thin film is a hole injection layer, a hole transport layer, or a hole injection transport layer.

10. 10. The electronic device according to claim 9, wherein the electronic device is an organic EL device or a quantum dot EL device.

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