Charge-transporting varnish and method for producing same

Abstract

Provided is a charge-transporting varnish that provides a charge-transporting thin film having excellent hole injection properties and also has excellent storage stability, the charge-transporting varnish comprising SiO2 nanoparticles surface-treated with a silane coupling agent represented by formula (S1), a charge-transporting substance, and an organic solvent, wherein the residual silane coupling agent has been removed from the charge-transporting varnish. (Rv1 to Rv3 each independently represents a hydrogen atom, a chlorine atom, a hydroxy group, or an alkoxy group or the like which may have a substituent; at least one of Rv1 to Rv3 represents a hydrogen atom, a chlorine atom, a hydroxy group, or an alkoxy group which may have a substituent; L represents a single bond or a C1-10 alkylene group; and Rv4 represents a C1-10 alkyl group which may have at least one kind of substituent selected from halogen atoms or the like. When Rv4 is a C1-10 alkyl group which may have a substituent, L is a single bond.)

Description

Charge transport varnish and method for producing same

[0001] The present invention relates to a charge transporting varnish and a method for producing the same.

[0002] In organic electroluminescence (hereinafter referred to as organic EL) devices, organic functional films made of organic compounds are used as the light-emitting layer and charge injection layer. In particular, the hole injection layer is responsible for transferring charges between the anode and the hole transport layer or light-emitting layer, and plays an important role in achieving low-voltage operation and high brightness of the organic EL device. In addition, 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 of the organic EL device.

[0003] Methods for forming hole injection layers and hole transport layers are roughly divided into dry processes, typified by vapor deposition, and wet processes, typified by inkjet methods and spin coating methods. Comparing these processes, wet processes can efficiently produce thin films with high flatness over large areas. Therefore, as organic EL displays are currently being made larger in area, hole injection layers and hole transport layers that can be formed by wet processes are desired, and technologies related to hole injection materials and hole transport materials that can be formed by wet processes have been reported (Patent Document 1).

[0004] Furthermore, in recent years, with the development of display technology, quantum dot electroluminescence (hereinafter referred to as quantum dot EL) devices, which use quantum dot materials as light-emitting layers, have emerged 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 controllability of emission wavelength, high color purity, high luminous efficiency, and flexibility.

[0005] Currently, there is a demand for improved performance of organic EL elements and quantum dot EL elements, and improvements are constantly being sought for wet process materials for hole injection layers and hole transport layers. In particular, there is an increasing demand for materials that can provide charge transport thin films with high hole injection or hole transport properties, as these materials can contribute to improved performance such as the luminance characteristics of organic EL elements and quantum dot EL elements.

[0006] Furthermore, charge-transporting varnishes for forming charge-transporting thin films are stored for a certain period of time before being used to manufacture electronic devices. Depending on the storage conditions, the components contained therein may precipitate or undergo chemical reactions with each other during storage. The use of such charge-transporting varnishes can result in a deterioration in the characteristics of the resulting electronic devices. That is, even if materials from the same lot are used, the characteristics of the resulting electronic devices may differ depending on the time of use. If the electronic devices do not meet quality standards, they will be deemed defective. Therefore, from the perspective of improving the productivity and stabilizing the quality of electronic devices, improving the storage stability of charge-transporting varnishes is desirable. Furthermore, charge-transporting varnishes that have precipitated their components and are no longer suitable for use must be discarded, and improvements are therefore needed from both environmental and economic perspectives.

[0007] International Publication No. 2008 / 032616

[0008] The present invention has been made in view of the above circumstances, and aims to provide a charge-transporting varnish (hereinafter sometimes simply referred to as "varnish") that gives a charge-transporting thin film that is excellent in charge transport properties, particularly hole injection properties or hole transport properties, and also has excellent storage stability.

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that by using a charge-transporting varnish containing SiO nanoparticles surface-treated with a silane coupling agent having a specific structure, the highest occupied molecular orbital (HOMO) level of the resulting charge-transporting thin film becomes deeper than that of conventional thin films, and a charge-transporting thin film with excellent charge transport properties can be obtained. Furthermore, as a result of further research into the storage stability of varnish, the present inventors have identified that the cause of the deterioration of the storage stability of varnish is the unreacted silane coupling agent (residual silane coupling agent) remaining in the varnish. They have then found that varnishes from which the residual silane coupling agent has been removed have excellent storage stability, and have completed the present invention.

[0010] That is, the present invention provides the following charge transporting varnish and a method for producing the same: 1. A charge transporting varnish comprising SiO2 nanoparticles surface-treated with a silane coupling agent represented by the following formula (S1), a charge transporting substance, and an organic solvent, wherein the residual silane coupling agent has been removed. (In the formula, R v1 ~R v3 each independently represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkoxy group which may have a substituent, or an alkyl group which may have a substituent; R v1 ~R v3 at least one of the groups represents a hydrogen atom, a chlorine atom, a hydroxy group, or an alkoxy group which may have a substituent; L represents a single bond or an alkylene group having 1 to 10 carbon atoms; R v4 represents an alkyl group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; an alkoxy group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; or an aryl group having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. v4 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, L is a single bond.) 2. v1 ~R v3 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms which may have a substituent. 3. The charge transport varnish of 1 or 2, wherein the charge transport substance is a polythiophene derivative or an amine adduct thereof, or an arylamine derivative. 4. The charge transport varnish of 3, wherein the polythiophene derivative or the amine adduct thereof is a polythiophene derivative or an amine adduct thereof containing a repeating unit represented by the following formula (U1): (In the formula, R u1 and R u2are 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 u -O] p -R e , or a sulfo group, or R u1 and R u2 are bonded to form -O-Y u -O-, and Y u represents 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 u 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.) 5. u1 is a sulfo group, and the R u2 is an alkoxy group having 1 to 40 carbon atoms or —O—[Z u -O] p -R e or the above R u1 and R u2 are bonded to form -O-Y u 6. The charge transport varnish of 3, wherein the arylamine derivative is represented by any one of the following formulas (T1) to (T4): (In the formula, R 1 each independently represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, a t-butoxycarbonyl group, or a benzyloxycarbonyl group; R 2 each independently represents a hydrogen atom, a hydroxyl group, a silanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, a monovalent hydrocarbon group which may have a substituent, an organoxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfo group, or a halogen atom; and m and n each independently represent an integer of 1 or more, and satisfy the relationship m+n≦20. [In the formula, Ph 1 represents a group represented by formula (P1), (In the formula, R 3 ~R 6 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. 1 each independently represents a group represented by any one of formulas [B1] to [B11], (In the formula, R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 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 28 and R 29 are, independently of each other, Z 1 R 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 52 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 Ar 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 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 with2 is a halogen atom, a nitro group, a cyano group, or Z 3 Z represents 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 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, 5 is a halogen atom, a nitro group, a cyano group, or Z 3 Ar 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 2 each independently represents a group represented by any one of formulas [A1] to [A18], (In the formula, R 155 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 R 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 156 and R 157 are, independently of each other, Z 1 DPA represents a diphenylamino group; Ar represents 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 3 , Z 1 and Z 3 ~Z 5 has the same meaning as above.) k represents an integer of 1 to 10.] [wherein Z represents a group represented by any one of the following formulae (z1) to (z6)] (In the formula, R z1each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Ar each independently represents a group represented by the following formulas (J1) to (J4); (In formula (J1), R z2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; or a group represented by the following formulas (J5) to (J7): In the formula, D represents a diarylamino group in which each aryl group is independently an aryl group having 6 to 20 carbon atoms; and in formulas (J1) to (J7), R z3 ~R z77 each independently represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms. F each independently represent a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a fluoroaryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms which is substituted with a fluoroalkyl group having 1 to 20 carbon atoms, a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms and which may be substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms.] [In the formula, Ar c each independently represents a group represented by formula (Q); each Y independently represents an optionally substituted phenylene group; and each g independently represents an integer of 1 to 10. (In the formula, R q1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R q2each independently represents an aryl group which may be substituted and which may contain a heteroatom; Ar s each independently represents an arylene group which may be substituted and which may contain a heteroatom.) 7. The charge transport varnish of any one of 1 to 6, further comprising a dopant substance. 8. The charge transport varnish of 7, wherein the dopant substance comprises at least one selected from the group consisting of arylsulfonic acid compounds and heteropolyacids. 9. The charge transport varnish of any one of 1 to 8, further comprising one or more amine compounds. 10. The charge transport varnish of 9, wherein the amine compounds comprise a trialkylamine compound and an amine compound other than a trialkylamine compound. 11. The charge transport varnish of 10, wherein the amine compound other than a trialkylamine compound is a monoalkylamine compound. 12. A charge transport thin film obtained from the charge transport varnish of any one of 1 to 11. 13. An electronic device comprising the charge transport thin film of 12. 14. The electronic device of 13, wherein the charge transport thin film is a hole injection layer or a hole transport layer. 15. 16. A method for producing a charge transport varnish comprising SiO2 nanoparticles surface-treated with a silane coupling agent represented by the following formula (S1), a charge transport substance, and an organic solvent, the method comprising a step of removing residual silane coupling agent: (In the formula, R v1 ~R v3 each independently represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkoxy group which may have a substituent, or an alkyl group which may have a substituent; R v1 ~R v3 at least one of the groups represents a hydrogen atom, a chlorine atom, a hydroxy group, or an alkoxy group which may have a substituent; L represents a single bond or an alkylene group having 1 to 10 carbon atoms; R v4represents an alkyl group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; an alkoxy group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; or an aryl group having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. v4 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, L is a single bond.

[0011] The charge transport varnish of the present invention has excellent storage stability due to the removal of residual silane coupling agent. Excellent storage stability allows the prepared charge transport varnish to be stored for long periods of time, facilitating material management and stabilizing quality during use. This, in turn, is expected to stabilize the quality and improve productivity of electronic devices manufactured using the charge transport varnish. Furthermore, by using the charge transport varnish, a charge transport thin film with excellent charge transport properties (particularly hole injection and hole transport properties) can be obtained. This charge transport thin film can be suitably used as a thin film for electronic devices, including organic EL devices and quantum dot EL devices. In particular, when the charge transport varnish of the present invention is used to form a hole injection layer or hole transport layer for an organic EL device or quantum dot EL device, the resulting hole injection layer or hole transport layer contains SiO nanoparticles surface-treated with a silane coupling agent, thereby improving the film quality, such as having a deeper HOMO level than conventional layers. As a result, when a hole injection layer is formed using the charge transport varnish of the present invention, the hole injection property to the hole transport layer formed on the hole injection layer is improved.Furthermore, when a hole transport layer is formed using the charge transport varnish of the present invention, the hole transport property to the light-emitting layer formed on the hole transport layer is improved, and therefore, improvement in the luminance characteristics of the device is expected.

[0012] The present invention will be described in more detail below. The charge-transporting varnish according to the present invention comprises SiO2 nanoparticles surface-treated with a silane coupling agent having a specific structure (hereinafter sometimes referred to as "surface-treated SiO2 nanoparticles"), a charge-transporting substance, and an organic solvent, and is characterized in that the residual silane coupling agent has been removed. In the present invention, charge transportability is synonymous with conductivity, hole injection ability, and hole transportability. The charge-transporting varnish may itself have charge transportability, or the solid film obtained from it may have charge transportability.

[0013] [1] Surface-treated SiO2 nanoparticles are a characteristic component of the charge-transporting varnish of the present invention, and are SiO2 nanoparticles surface-treated with a silane coupling agent represented by the following formula (S1). Note that nanoparticles refer to fine particles whose primary particle average particle diameter is on the order of nanometers (typically 500 nm or less). SiO2 nanoparticles refer to SiO2 formed into nanoparticles.

[0014]

[0015] In formula (S1), R v1 ~R v3 each independently represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkoxy group which may have a substituent, or an alkyl group which may have a substituent; R v1 ~R v3 at least one of the groups represents a hydrogen atom, a chlorine atom, a hydroxy group, or an alkoxy group which may have a substituent; L represents a single bond or an alkylene group having 1 to 10 carbon atoms; R v4represents an alkyl group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; an alkoxy group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; or an aryl group having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.

[0016] R v1 ~R v3 The alkoxy group may have a linear, branched, or cyclic alkyl group, and specific examples thereof include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy groups. Alkoxy groups having 1 to 5 carbon atoms are preferred, alkoxy groups having 1 to 3 carbon atoms are more preferred, and methoxy and ethoxy groups are even more preferred.

[0017] R v1 ~R v3 The alkyl group may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups, with alkyl groups having 1 to 5 carbon atoms being preferred, alkyl groups having 1 to 3 carbon atoms being more preferred, and methyl and ethyl groups being even more preferred.

[0018] The above R v1 ~R v3 may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an amino group, and an organosilyl group. v1 ~R v3When has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0019] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms, with fluorine atoms being preferred.

[0020] Examples of organosilyl groups include trialkylsilyl groups in which each 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 each 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.

[0021] The alkylene group having 1 to 10 carbon atoms represented by L may be linear, branched, or cyclic. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decylene group. Among these, an alkylene group having 2 to 5 carbon atoms is preferred, an alkylene group having 2 to 4 carbon atoms is more preferred, and an ethylene group, a trimethylene group, or a tetramethylene group is even more preferred.

[0022] R v4 Examples of the halogen atom include the same as those exemplified above.

[0023] R v4The alkyl group having 1 to 10 carbon atoms may be either linear or branched, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, a 4-methylpentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and the like. An alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group, an ethyl group, an n-propyl group, or a 4-methylpentyl group is even more preferred.

[0024] R v4 The alkoxy group having 1 to 10 carbon atoms may have a linear, branched, or cyclic alkyl group, and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, and an n-decyloxy group. An alkoxy group having 1 to 5 carbon atoms is preferred, an alkoxy group having 1 to 3 carbon atoms is more preferred, and a methoxy group, an ethoxy group, or an n-propoxy group is even more preferred.

[0025] R v4 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.

[0026] R v4 Examples of the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms contained in the aryl group having 6 to 20 carbon atoms include the same groups as those exemplified above.

[0027] The above R v4 When has a substituent, the number of the substituents is preferably 1 to 10, and more preferably 1 to 7.

[0028] However, in the above formula (S1), R v4 When is an alkyl group having 1 to 10 carbon atoms which may have a substituent, L is a single bond.

[0029] As the silane coupling agent represented by the formula (S1), in order to deepen the HOMO level of the resulting charge transporting thin film, v1 ~R v3 is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent or an alkoxy group having 1 to 10 carbon atoms which may have a substituent. v1 ~R v3 Among these, at least one of which is an alkoxy group having 1 to 10 carbon atoms which may have a substituent, is more preferred, and at least one of which is an alkoxy group having 1 to 5 carbon atoms which may have a substituent, is even more preferred.

[0030] Specific examples of the silane coupling agent include trimethoxy(methyl)silane, trimethoxy(3-methoxypropyl)silane, trimethoxy(propyl)silane, trimethoxy(4-methoxyphenyl)silane, trimethoxyphenylsilane, methoxytrimethylsilane, [3-(1,1,2,3,3,3-hexafluoropropoxy)propyl]trimethoxysilane, trifluoropropyltrimethoxysilane, 1,1,1-trifluoro-2-(trifluoromethyl)-5-(trimethoxysilyl)pentan-2-ol, trimethoxy[3-(perfluorophenyl)propyl]silane, trimethoxyphenylsilane, ethoxytriethylsilane, methoxydimethyl(phenyl)silane, and pentafluorophenylethoxysilane. Examples of suitable silane include dimethylsilane, trimethylethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxy(methyl)phenylsilane, triethoxyethylsilane, decyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, triethoxymethylsilane, n-octyltriethoxysilane, 3-(trihydroxysilyl)-1-propanesulfonic acid, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, and 1,6-bis(triethoxysilyl)hexane, but are not limited to these.

[0031] In the present invention, among the above silane coupling agents, trimethoxy(methyl)silane, trimethoxy(3-methoxypropyl)silane, trimethoxy(propyl)silane, trimethoxy(4-methoxyphenyl)silane, trimethoxyphenylsilane, methoxytrimethylsilane, [3-(1,1,2,3,3,3-hexafluoropropoxy)propyl]trimethoxysilane, trifluoropropyltrimethoxysilane, 1,1,1-trifluoro-2-(trifluoromethyl)-5-(trimethoxysilyl)pentan-2-ol, and trimethoxy[3-(perfluorophenyl)propyl]silane are preferred.

[0032] The silane coupling agent may be a commercially available product, or may be obtained by reacting various allyl compounds with a metal catalyst using a known method of hydrosilylation (for example, see Non-Patent Document RSC Adv., 2015, 20603-20616).

[0033] In the present invention, the primary particle size of the SiO nanoparticles constituting the surface-treated SiO nanoparticles is not particularly limited as long as it is nano-sized, but is usually 5 nm or more, and from the viewpoint of ensuring good particle dispersibility, ease of production, etc., it is usually 200 nm or less, preferably 100 nm or less, and more preferably 30 nm or less.

[0034] The primary particle diameter of the surface-treated SiO nanoparticles is not particularly limited, but is usually 5 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. This particle diameter is the particle diameter at which the cumulative frequency distribution in volume-based particle size distribution measurement by dynamic light scattering method becomes 50% (median diameter D 50 )

[0035] In the surface-treated SiO nanoparticles used in the present invention, the amount of silane coupling agent modified on the surface of the SiO nanoparticles is not particularly limited. However, from the viewpoint of the dispersibility of the SiO nanoparticles and the transparency of the resulting thin film, it is preferable that the amount be 0.1 particles / nm or more and 4.0 particles / nm or less. 2 Preferably, it is less than 0.2 to 3.0 particles / nm 2 More preferably, 0.3 to 2.0 particles / nm 2 It is more preferable that the modification amount X (number / nm 2 ) are the particle size (nm) and specific gravity (g / cm) of the SiO2 nanoparticles 3 ) The specific surface area SA (nm 2 / g), the total amount of metal oxide particles M (g), the molecular weight Mw of the silane coupling agent, the amount Y (g) of the silane coupling agent, and Avogadro's constant L, and the value is calculated as Y = X * SA * M * Mw / L.

[0036] The amount of surface-treated SiO2 nanoparticles contained in the charge-transporting varnish of the present invention is not particularly limited, but from the viewpoint of improving the hole injection properties of the resulting thin film and enhancing the uniformity of the film, the lower limit of the solid content is usually 10 mass%, preferably 15 mass%, more preferably 20 mass%, even more preferably 30 mass%, even more preferably 40 mass%, and particularly preferably 50 mass%, and the upper limit is usually 99 mass%, preferably 95 mass%, more preferably 90 mass%, even more preferably 85 mass%, and even more preferably 80 mass%.

[0037] The surface-treated SiO2 nanoparticles used in the present invention may also be used in the form of a sol dispersed in a dispersion medium, such as 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, and dipropylene glycol monomethyl ether.

[0038] The solids concentration of the sol is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and even more preferably 10 to 30% by mass. The amount of sol used is determined appropriately taking into account the concentration so that the amount of surface-treated SiO nanoparticles finally contained in the varnish is the above-mentioned blending amount of SiO nanoparticles.

[0039] [2] Charge Transporting Substance The charge transporting substance used in the present invention is not particularly limited and can be appropriately selected from charge transporting compounds, charge transporting oligomers, charge transporting polymers, etc. used in the field of organic electroluminescence, etc. Specific examples include various charge transporting compounds and charge transporting oligomers such as arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, and N,N,N',N'-tetraarylbenzidine derivatives, thiophene derivatives such as oligothiophene derivatives, thienothiophene derivatives, and thienobenzothiophene derivatives, pyrrole derivatives such as oligopyrrole, and charge transporting polymers such as polythiophene derivatives, polyaniline derivatives, and polypyrrole derivatives. In the present invention, polythiophene derivatives or their amine adducts, and arylamine derivatives are particularly preferred.

[0040] The polythiophene derivative or its amine adduct is preferably a polythiophene derivative or its amine adduct containing a repeating unit represented by the following formula (U1): The arylamine derivative is preferably an arylamine derivative represented by any one of the formulae (T1) to (T4) described below:

[0041] [Polythiophene derivative containing a repeating unit represented by formula (U1) or an amine adduct thereof]

[0042] 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 Re 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0051] In the above formula (1), 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 —O—Y—O—, 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. a ~R d are each independently 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. 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 an integer of 1 to 5, and more preferably 1, 2, or 3.

[0052] 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.

[0053] 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 -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 R u1 and R u2 are bonded to each other to form —O—Y—O—.

[0054] For example, the polythiophene derivative according to a preferred embodiment of the present invention may be u1 is a sulfo group, and R u2 contains a repeating unit other than a sulfo group, or R u1 and R u2 Preferably, the polythiophene derivative contains a repeating unit of —O—Y—O— formed by bonding of R u1 is a sulfo group, and R u2 is an alkoxy group having 1 to 40 carbon atoms or —O—[Z—O] p -R e or R u1 and R u2 More preferably, the polythiophene derivative contains a repeating unit of —O—Y—O— formed by bonding of R u1 is a sulfo group, and R u2 is -O[C(R a R b )-C(R c R d ) -O] p -R e or -OR f More preferably, the polythiophene derivative comprises a repeating unit represented by R u1 is a sulfo group, and R u2 is -O[C(R a R b )-C(R c R d ) -O] p -R e or R u1 and R u2 More preferably, the polythiophene derivative contains a repeating unit represented by —O—Y—O— formed by bonding of R u1 is a sulfo group, and R u2 is —O—CH2CH2—O—CH2CH2—O—CH3, —O—CH2CH2—O—CH2CH2—OH, or —O—CH2CH2—OH, or R u1 and R u2are bonded to each other to form repeating units which are groups represented by the following formulae (Y1) and (Y2).

[0055]

[0056] Specific preferred examples of the polythiophene derivative include polythiophenes containing at least one repeating unit represented by the following formulae (U1-1) to (U1-5).

[0057]

[0058] A suitable structure of the polythiophene derivative is, for example, a polythiophene derivative having a structure represented by the following formula (U1a): In the following formula, the units may be bonded randomly or as a block polymer.

[0059]

[0060] In the formula, a to d represent the molar ratio of each unit, and satisfy the following conditions: 0≦a≦1, 0≦b≦1, 0<a+b≦1, 0≦c<1, 0≦d<1, a+b+c+d=1.

[0061] 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, A-B-A 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).

[0062] In the present invention, the content of the repeating unit represented by formula (U1) in the polythiophene derivative is preferably more than 50 mol %, 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 % of all repeating units contained in the polythiophene derivative.

[0063] 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 formula (U1), and more preferably a polymer containing at least one of repeating units represented by formulas (U1-1) to (U1-5).

[0064] 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.

[0065] Examples of 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- monoalkylamine compounds such as 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, N-methyl N-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, N-n-propylisopropylamine, N-n-propyl-n-butylamine, N-n-propyl-s-butylamine, diisopropylamine, N-n-butylisopropylamine, N-t-butylisopropylamine, di(n- dialkylamine compounds such as di(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;Diarylamine compounds such as 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, and 13H-dibenzo[a,i]carbazole; N-methylaniline, N-ethylaniline, N-n-propylaniline, N-iso ... secondary amine compounds such as alkylarylamine compounds such as N,N-isopropylaniline, N-n-butylaniline, N-s-butylaniline, N-isobutylaniline, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-n-propyl-1-naphthylamine, indoline, isoindoline, 1,2,3,4-tetrahydroquinoline, and 1,2,3,4-tetrahydroisoquinoline; trialkylamine compounds such as N-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 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-transporting 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.

[0066] In the present invention, the polythiophene derivative or its amine adduct may be treated with a reducing agent. 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 refers to a structure containing an aromatic ring, whereas the former refers to a structure in which a double bond within the aromatic ring moves outside the ring (resulting in the disappearance of the aromatic ring), forming two exocyclic double bonds conjugated with other double bonds remaining within 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 repeating units of various conjugated polymers are well known to those skilled in the art. As an example, a quinoid structure corresponding to a repeating unit of a polythiophene derivative containing a repeating unit represented by the above formula (U1) is shown in the following formula (U1').

[0067] (In the formula, R u1 and R u2 is as defined in the above formula (U1).

[0068] This quinoid structure is generated by a process in which a polythiophene derivative containing a repeating unit represented by formula (U1) undergoes an oxidation reaction with a dopant, a so-called 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 in 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 varnish 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 in the polythiophene derivative during its manufacturing process (particularly the sulfonation step therein).

[0069] 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 a charge-transporting varnish 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, the production of the charge-transporting varnish may be hindered. Polythiophene derivatives are known to have varying solubility and dispersibility in organic solvents. One of the causes 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 is introduced into the polythiophene derivative, the quinoid structures are reduced by reduction, improving the solubility and dispersibility of the polythiophene derivative in organic solvents. This enables the stable production of a good charge-transporting varnish that provides a thin film with excellent uniformity.

[0070] 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. The reducing agent is also not particularly limited as long as it can appropriately reduce the polythiophene derivative or the amine adduct. Suitable examples of the reducing agent include aqueous ammonia and hydrazine, 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 the amine adduct to be treated in order to appropriately reduce the polythiophene derivative or the amine adduct, and 10 parts by mass or less in order to prevent excess reducing agent from remaining.

[0071] In one example of a specific reduction method, the polythiophene derivative or the 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 the amine adduct in organic solvents.

[0072] When an amine adduct of a polythiophene derivative is used in the charge-transporting varnish of the present invention, the reduction treatment may be carried out either before or after the formation of the amine adduct.

[0073] Note that, as a result of this reduction treatment changing the solubility or dispersibility of the polythiophene derivative or its amine adduct in the solvent, 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.

[0074] 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 electrical conductivity can be obtained with good reproducibility, while by setting it at or below the upper limit, solubility in organic solvents is improved. The weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography.

[0075] The polythiophene derivative or its amine adduct contained in the charge-transporting varnish of the present invention may be a polythiophene derivative or its amine adduct containing a repeating unit represented by formula (U1), or two or more of them may be used. The polythiophene derivative containing a repeating unit represented by formula (U1) may be a commercially available product, or may be polymerized by a known method using a thiophene derivative or the like as a starting material. In either case, it is preferable to use a product purified by a method such as reprecipitation or ion exchange. By using a purified product, the properties of an organic EL device or a quantum dot EL device equipped with a thin film obtained from the charge-transporting varnish of the present invention can be further improved.

[0076] 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.

[0077] 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 varnish is dissolved in an organic solvent.

[0078] [Arylamine derivative represented by formula (T1)] (In the formula, R 1 each independently represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, a t-butoxycarbonyl group, or a benzyloxycarbonyl group; R 2 each independently represents a hydrogen atom, a hydroxyl group, a silanol group, a thiol group, a carboxyl group, a phosphate group, a phosphate ester group, an ester group, a thioester group, an amide group, a nitro group, a monovalent hydrocarbon group which may have a substituent, an organoxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfo group, or a halogen atom; and m and n each independently represent an integer of 1 or more, and satisfy the relationship m+n≦20.

[0079] R 1 The monovalent hydrocarbon group represented by the formula (I) is not particularly limited, but is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0080] Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; bicycloalkyl groups such as bicyclohexyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 1-, 2-, or 3-butenyl, and hexenyl; aryl groups such as phenyl, xylyl, tolyl, biphenyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylcyclohexyl.

[0081] The monovalent hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, and a sulfo group. When the monovalent hydrocarbon group has a substituent, it is sufficient that some or all of the hydrogen atoms are substituted with the substituent. From the viewpoint of electrical properties, the number of substituents is preferably 1 to 5, and more preferably 1 to 3. Furthermore, the substituent may include a portion in which the substituents are linked to each other to form a ring.

[0082] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., with a fluorine atom being preferred.

[0083] The alkoxy group may have an alkyl group that is linear, branched, or cyclic. Specific examples thereof include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy. Alkoxy groups having 1 to 5 carbon atoms are preferred, alkoxy groups having 1 to 3 carbon atoms are more preferred, and methoxy and ethoxy groups are even more preferred.

[0084] The above R 1are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or a t-butoxycarbonyl group, and particularly preferably a hydrogen atom or a t-butoxycarbonyl group. 1 However, those in which both are hydrogen atoms, those in which both are t-butoxycarbonyl groups, or those in which one is a hydrogen atom and the other is a t-butoxycarbonyl group are preferred.

[0085] R 2 The monovalent hydrocarbon group represented by the formula (I) is not particularly limited, but is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0086] Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; bicycloalkyl groups such as bicyclohexyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 1-, 2-, or 3-butenyl, and hexenyl; aryl groups such as phenyl, xylyl, tolyl, biphenyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylcyclohexyl. In the present invention, among these, aryl groups are preferred, and phenyl, biphenyl, and naphthyl are more preferred.

[0087] R 2 Examples of the organoxy group represented by the formula (I) include an alkoxy group, an alkenyloxy group, an aryloxy group, etc. Specific examples of the alkoxy group include the same groups as those mentioned above.

[0088] Specific examples of the alkenyloxy group include a vinyloxy group, a 1-propenyloxy group, a 2-propenyloxy group, a 1-methyl-2-propenyloxy group, a 1-, 2- or 3-butenyloxy group, and a hexenyloxy group.

[0089] Specific examples of the aryloxy group include a phenoxy group, a xylyloxy group, a tolyloxy group, a biphenyloxy group, and a naphthoxy group.

[0090] Specific examples of the organoamino group include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, and laurylamino group; dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, and didecylamino group; cycloalkylamino groups such as cyclohexylamino group; dicycloalkylamino groups such as dicyclohexylamino group; morpholino group; and arylamino groups such as biphenylamino group.

[0091] Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, an octyldimethylsilyl group, and a decyldimethylsilyl group.

[0092] Specific examples of the organothio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a nonylthio group, a decylthio group, and a laurylthio group.

[0093] Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

[0094] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0095] The phosphate ester group is —P(O)(OQ 1 ) (OQ 2 ) are listed.

[0096] The ester group is —C(O)OQ 1 , -OC(O)Q 1 Examples include:

[0097] The thioester group is —C(S)OQ 1 , -OC(S)Q 1 Examples include:

[0098] The amide group is —C(O)NHQ 1 , -NHC(O)Q 1 , -C(O)NQ 1 Q 2 , -NQ 1 C(O)Q 2 Examples include:

[0099] Here, the above Q 1 and Q 2 represents an alkyl group, an alkenyl group, or an aryl group, and examples of these include the same groups as those exemplified above for the monovalent hydrocarbon group.

[0100] R 2 In the above, the number of carbon atoms in the monovalent hydrocarbon group, organooxy group, organoamino group, organosilyl group, organothio group, acyl group, phosphate ester group, ester group, thioester group, amide group, etc. is not particularly limited, but generally is 1 to 20 carbon atoms, and preferably 1 to 8 carbon atoms.

[0101] Among these, R 2 are preferably, independently of one another, a hydrogen atom, an optionally substituted monovalent hydrocarbon group, an organoxy group, an organoamino group, or a halogen atom, with a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or a halogen atom being particularly preferred. Furthermore, the monovalent hydrocarbon group is preferably a phenyl group, a biphenyl group, or a naphthyl group. The halogen atom is preferably a fluorine atom. The organoamino group is preferably an arylamino group, with a biphenylamino group being more preferred.

[0102] Furthermore, the above R 2 are more preferably all hydrogen atoms.

[0103] In the formula (T1), m and n are each independently an integer of 1 or greater and satisfy the condition m+n≦20, but in particular, it is preferable that m+n≦10, and it is more preferable that m+n≦5. By adjusting the ranges of m and n to fall within the above ranges, it becomes easy to ensure solubility in various solvents while exhibiting good charge transport properties.

[0104] In order to enhance solubility and achieve uniform charge transport properties, the arylamine derivative of formula (T1) is preferably an oligoaniline compound having no molecular weight distribution, in other words, a polydispersity of 1. From the viewpoints of suppressing volatilization of the material and achieving charge transport properties, the lower limit of the molecular weight is preferably 200 or more, more preferably 400 or more. In consideration of solubility, the upper limit is preferably 5,000 or less, more preferably 3,000 or less.

[0105] 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 2018 / 135580.

[0106] [Arylamine derivative represented by formula (T2)]

[0107] In formula (T2), Ph 1 represents a group represented by formula (P1).

[0108]

[0109] Here, R 3 ~R 6 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] Specific examples of alkynyl groups 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.

[0114] 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.

[0115] Specific examples of heteroaryl groups 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; an aryl group, a 2-imidazolyl group, a 4-imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-pyrazyl group, a 3-pyrazyl group, a 5-pyrazyl group, a 6-pyrazyl group, a 2-pyrimidyl group, a 4-pyrimidyl group, a 5-pyrimidyl group, a 6-pyrimidyl group, a 3-pyridazyl group, a 4-pyridazyl group, a 5-pyridazyl group, a 6-pyridazyl group, a 1,2,3-triazin-4-yl group, a 1,2,3-triazin-5-yl group, a 1,2,4-triazin-3-yl 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.

[0116] In particular, R 3 ~R 6 is 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.

[0117] Below, Ph 1 Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0118]

[0119] Ar in the above formula (T2) 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'].

[0120]

[0121]

[0122] Here, R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 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 28 and R 29 are, independently 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 52is 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 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, 5 is a halogen atom, a nitro group, a cyano group, or Z 3 and 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 a halogen atom, 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, and 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 3 ~R 6 Examples include those similar to those described above.

[0123] Above Z 4Examples 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. Also included are 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.

[0124] 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.

[0125] 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 substituents is preferably 1 to 6, and more preferably 1 to 3.

[0126] In particular, R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154is preferably a hydrogen atom, a fluorine atom, a cyano group, a diphenylamino group which may be substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, more preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 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. 28 and R 29 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 by is more preferred, and Z 1 a phenyl group optionally substituted with 1 a 1-naphthyl group optionally substituted by 1 Even more preferred is a 2-naphthyl group optionally substituted with R 52 Examples of the group include a hydrogen atom and 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 by 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 by 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 4 More preferably, the alkyl group having 1 to 10 carbon atoms may be substituted with a hydrogen atom, Z 1a phenyl group optionally substituted with 1 a 1-naphthyl group optionally substituted by 1 a 2-naphthyl group optionally substituted by 1 a 2-pyridyl group optionally substituted by 1 a 3-pyridyl group optionally substituted by 1 a 4-pyridyl group optionally substituted by 4 A methyl group optionally substituted with is more preferred.

[0127] 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 3 ~R 6 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. 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.

[0128] Below, Ar 1 Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0129]

[0130]

[0131]

[0132] (In the formula, R 52 has the same meaning as above.)

[0133]

[0134]

[0135]

[0136]

[0137] Ar in the above formula (T2) 2 each independently represents a group represented by any one of formulas [A1] to [A18].

[0138]

[0139] where R 155 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 156 and R 157 are, independently of each other, Z 1 DPA represents a diphenylamino group; Ar represents 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 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 3 ~R 6 Examples include those similar to those described above.

[0140] In particular, R 155 Examples of the group include a hydrogen atom and 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 by4 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 by 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 4 More preferably, the alkyl group having 1 to 10 carbon atoms may be substituted with a hydrogen atom, Z 1 a phenyl group optionally substituted with 1 a 1-naphthyl group optionally substituted by 1 a 2-naphthyl group optionally substituted by 1 a 2-pyridyl group optionally substituted by 1 a 3-pyridyl group optionally substituted by 1 a 4-pyridyl group optionally substituted by 4 A methyl group optionally substituted with R is more preferred. 156 and R 157 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 by is more preferred, and Z 1 a phenyl group optionally substituted with 1 a 1-naphthyl group optionally substituted by 1 Even more preferred is a 2-naphthyl group optionally substituted with

[0141] Below, Ar 2 Specific examples of groups suitable for the group are listed below, but the present invention is not limited to these.

[0142] (In the formula, DPA has the same meaning as above.)

[0143]

[0144]

[0145]

[0146]

[0147] (In the formula, R 155 has the same meaning as above.)

[0148]

[0149] In the formula (T2), 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 (T2) is more preferably an arylamine derivative represented by formula (T2-1). Furthermore, as described below, the arylamine derivative represented by formula (T2) is preferably an arylamine derivative represented by formula (T2-1) because 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.

[0150]

[0151] In formula (T2-1), Ph 1 and k have the same meaning as above, Ar 4 represents a group represented by any one of formulas [D1] to [D13], and is particularly preferably a group represented by any one of formulas [D1'] to [D13']. 4 Specific examples of Ar include 1 Specific examples of suitable groups for include the same as those mentioned above.

[0152] (In the formula, R 28 , R 29 , R 52 , Ar 3and DPA have the same meanings as above.)

[0153] (In the formula, R 28 , R 29 , R 52 , Ar 3 and DPA have the same meanings as above.)

[0154] Moreover, as described later, the arylamine derivative represented by formula (T2) is preferably an arylamine derivative represented by formula (T2-2), 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.

[0155]

[0156] The above Ar 5 represents a group represented by any one of formulas [E1] to [E14].

[0157] (In the formula, R 52 has the same meaning as above.)

[0158] In the above formula (T2), k represents an integer of 1 to 10. From the viewpoint of increasing the solubility of the compound in organic solvents, k is preferably an integer of 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and optimally 1.

[0159] In addition, R 28 , R 29 , R 52 and R 155 ~R 157 In this case, Z 1 represents 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 by 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 by2 More preferred is an alkynyl group having 2 to 3 carbon atoms which may be substituted by 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.

[0160] R 28 , R 29 , R 52 and R 155 ~R 157 In this case, Z 4 represents 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 5 An 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.

[0161] R 28 , R 29 , R 52 and R 155 ~R 157 In this case, Z 2 represents 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, Z3 A phenyl group optionally substituted with is more preferred.

[0162] R 28 , R 29 , R 52 and R 155 ~R 157 In this case, Z 5 represents 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 by 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 by 3 More preferred is an alkynyl group having 2 to 3 carbon atoms which may be substituted by 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.

[0163] R 28 , R 29 , R 52 and R 155 ~R 157 In this case, Z 3 is preferably a halogen atom, more preferably a fluorine atom.

[0164] On the other hand, R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 In this case, Z 1 represents 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 2An alkynyl group having 2 to 3 carbon atoms which may be substituted by 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.

[0165] R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 In this case, Z 4 represents 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, Z 5 A phenyl group optionally substituted with is even more preferred.

[0166] R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 In this case, Z 2 represents 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 A phenyl group optionally substituted with is even more preferred.

[0167] R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 In this case, Z 5 represents 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 3An alkynyl group having 2 to 3 carbon atoms which may be substituted by 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.

[0168] R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 In this case, Z 3 is preferably a halogen atom, more preferably a fluorine atom.

[0169] In the present invention, R 52 and R 155 Specific examples of groups suitable as include, but are not limited to, the following groups:

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] In the present invention, the number of carbon atoms in the alkyl group, alkenyl group, and alkynyl group is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The number of carbon atoms in the aryl group and heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

[0178] When the arylamine derivative represented by the formula (T2) has an organosilyl group, a part or all of the organosilyl group may form a complex with the SiO nanoparticles described later. In this case, the arylamine derivative functions not only as a charge transport material but also as a silane coupling agent.

[0179] The arylamine derivative represented by formula (T2) of the present invention can be synthesized by a known method, for example, by the method described in WO 2015 / 050253.

[0180] [Arylamine derivative represented by formula (T3)]

[0181] Examples of the arylamine derivative represented by formula (T3) include, but are not limited to, those shown below.

[0182]

[0183] In formula (T3), Z represents a group represented by any one of the following formulae (z1) to (z6): When Z is a group represented by formula (z3) or (z4), the carbon atom contained in this group is adjacent to the nitrogen atom in formula (T3).

[0184]

[0185] In formulas (z1) to (z6), R z1 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom.

[0186] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; 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.

[0187] Z is preferably a group represented by formula (z1), (z2), (z3), (z4) or (z5), more preferably a group represented by formula (z1), (z3) or (z5), and still more preferably a group represented by formula (z1).

[0188] In formula (T3), Ar each independently represents a group represented by the following formulae (J1) to (J4).

[0189]

[0190] In formula (J1), R z2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; or a group represented by any of the following formulae (J5) to (J7):

[0191] (In the formula, D represents a diarylamino group in which each aryl group is independently an aryl group having 6 to 20 carbon atoms. R z54 ~R z77 (More on this later.)

[0192] Examples of the alkyl group having 1 to 20 carbon atoms include the same as those described above. 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. Examples of the diarylamino group include a diphenylamino group, a dinaphthylamino group, a dianthrylamino group, an N-phenyl-N-naphthylamino group, an N-phenyl-N-anthrylamino group, and an N-naphthyl-N-anthrylamino group.

[0193] As the groups represented by formulae (J5) to (J7), those represented by the following formulae (J5-1) to (J7-1) are preferred.

[0194]

[0195] Of these, R z2 As the alkyl group, a hydrogen atom, 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 group represented by formula (J5-1), a group represented by formula (J6-1), and the like are preferred, a group represented by formula (J5-1), a group represented by formula (J6-1), and a phenyl group are more preferred, and a phenyl group is even more preferred.

[0196] In formulas (J1) to (J7), R z3 ~R z77 each independently represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include those mentioned above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the haloalkyl group include those in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms mentioned above. Of these, R z3 ~R z77is preferably a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a cyano group, a nitro group, a halogen atom, or a trifluoromethyl group, and even more preferably all of them are hydrogen atoms.

[0197] Examples of the groups represented by formulae (J1) to (J7) include, but are not limited to, the following.

[0198] (In the formula, R z2 ~R z53 is the same as above.)

[0199] In formula (T3), Ar F each independently represent a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a fluoroaryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which is substituted with a fluoroalkyl group having 1 to 20 carbon atoms, a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms, and which may be substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms.

[0200] The fluoroaryl group is not particularly limited as long as it is an aryl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3 ,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-fluoro-1-naphthyl group, 3-fluoro-1-naphthyl group, 4-fluoro-1-naphthyl group, 6-fluoro b-1-naphthyl group, 7-fluoro-1-naphthyl group, 8-fluoro-1-naphthyl group, 4,5-difluoro-1-naphthyl group, 5,7-difluoro-1-naphthyl group, 5,8-difluoro-1-naphthyl group, 5,6,7,8-tetrafluoro-1-naphthyl group, heptafluoro-1-naphthyl group, 1-fluoro-2-naphthyl group, 5-fluoro-2-naphthyl group, 6-fluoro-2-naphthyl group, 7-fluoro-2-naphthyl group, 5,7-difluoro-2-naphthyl group, heptafluoro-1-naphthyl group, Examples include butafluoro-2-naphthyl group, 10-fluoro-9-anthryl group, nonafluoro-1-anthryl group, nonafluoro-2-anthryl group, nonafluoro-9-anthryl group, 9-fluoro-1-phenanthryl group, 1-fluoro-9-phenanthryl group, 2-fluoro-9-phenanthryl group, nonafluoro-1-phenanthryl group, nonafluoro-2-phenanthryl group, nonafluoro-3-phenanthryl group, and nonafluoro-9-phenanthryl group.

[0201] As the fluoroaryl group, in consideration of a balance between the solubility of the arylamine derivative in an organic solvent, the ease of availability of raw materials for the arylamine derivative, and the like, a phenyl group substituted with three or more fluorine atoms, which may be substituted with a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms, is preferred.

[0202] The aryl group having 6 to 20 carbon atoms (hereinafter, for convenience, also referred to as a substituted aryl group) which is substituted with the fluoroalkyl group having 1 to 20 carbon atoms, the fluorocycloalkyl group having 3 to 20 carbon atoms, the fluorobicycloalkyl group having 4 to 20 carbon atoms, the fluoroalkenyl group having 2 to 20 carbon atoms, or the fluoroalkynyl group having 2 to 20 carbon atoms and which may be substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms, is not particularly limited as long as it is an aryl group in which at least one hydrogen atom on a carbon atom is substituted with a fluoroalkyl group having 1 to 20 carbon atoms, a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms. Examples thereof include a 2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 5-(trifluoromethyl)phenyl group, a 6-(trifluoromethyl)phenyl group, a 7-(trifluoromethyl)phenyl group, a 8-(trifluoromethyl)phenyl group, a 9-(trifluoromethyl)phenyl group, a 10-(trifluoromethyl)phenyl group, a 11-(trifluoromethyl)phenyl group, a 12-(trifluoromethyl)phenyl group, a 13-(trifluoromethyl)phenyl group, a 14-(trifluoromethyl)phenyl group, a 15-(trifluoromethyl)phenyl group, a 16-(trifluoromethyl)phenyl group, a 17-(trifluoromethyl)phenyl group, a 18-(trifluoromethyl)phenyl group, a 19-(trifluoromethyl)phenyl group, a 21-(trifluoromethyl)phenyl group, a 22-(tri Examples thereof include a 4-(perfluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a 4-ethoxy-3-(trifluoromethyl)phenyl group, a 3-fluoro-4-trifluoromethylphenyl group, a 4-fluoro-3-trifluoromethylphenyl group, a 4-fluoro-2-trifluoromethylphenyl group, a 2-fluoro-5-(trifluoromethyl)phenyl group, a 3-fluoro-5-(trifluoromethyl)phenyl group, a 3,5-di(trifluoromethyl)phenyl group, a 2,4,6-tri(trifluoromethyl)phenyl group, a 4-(pentafluoroethyl)phenyl group, a 4-(3,3,3-trifluoropropyl)phenyl group, a 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, a 4-(perfluorovinyl)phenyl group, a 4-(perfluoropropenyl)phenyl group, and a 4-(perfluorobutenyl)phenyl group.

[0203] Considering the balance between the solubility of the arylamine derivative in organic solvents and the ease of availability of raw materials for the arylamine derivative, the substituted aryl group is preferably a phenyl group that is substituted with a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms, and that may also be substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms (hereinafter, for convenience, also referred to as a substituted phenyl group), more preferably a phenyl group substituted with 1 to 3 trifluoromethyl groups, and even more preferably a p-trifluoromethylphenyl group.

[0204] The fluoroalkyl group is not particularly limited as long as it is a linear or branched alkyl group 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 1,1,2,2,2-pentafluoroethyl 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 Difluoropropyl group, 1,1,2-trifluoropropyl group, 1,1,3-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 , a 1,3,3,3-tetrafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,3,3,3-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 heptafluoropropyl group, and the like.

[0205] The fluoroalkoxy group is not particularly limited as long as it is an alkoxy group 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, and a 1,2,2-trifluoroethoxy group. , 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,2,2,2-tetrafluoroethoxy group, 1,1,2,2,2-pentafluoroethoxy 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, Fluoropropoxy 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 group, a 1,3,3,3-tetrafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,3,3,3-tetrafluoropropoxy group, a 1,1,2,2,3-pentafluoropropoxy group, a 1,2,2,3,3-pentafluoropropoxy group, a 1,1,3,3,3-pentafluoropropoxy group, a 1,2,3,3,3-pentafluoropropoxy group, a 2,2,3,3,3-pentafluoropropoxy group, and a heptafluoropropoxy group.

[0206] The fluorocycloalkyl group is not particularly limited as long as it is a cycloalkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a 1-fluorocyclopropyl group, a 2-fluorocyclopropyl group, a 2,2-difluorocyclopropyl group, a 2,2,3,3-tetrafluorocyclopropyl group, a pentafluorocyclopropyl group, a 2,2-difluorocyclobutyl group, a 2,2,3,3-tetrafluorocyclobutyl group, a 2,2,3,3,4,4-hexafluorocyclobutyl group, a heptafluorocyclobutyl group, a 2,2,3,3,4,4-hexa ... Examples of such groups include a fluorocyclobutyl group, a 1-fluorocyclopentyl group, a 3-fluorocyclopentyl group, a 3,3-difluorocyclopentyl group, a 3,3,4,4-tetrafluorocyclopentyl group, a nonafluorocyclopentyl group, a 1-fluorocyclohexyl group, a 2-fluorocyclohexyl group, a 4-fluorocyclohexyl group, a 4,4-difluorocyclohexyl group, a 2,2,3,3-tetrafluorocyclohexyl group, a 2,3,4,5,6-pentafluorocyclohexyl group, and an undecafluorocyclohexyl group.

[0207] The fluorobicycloalkyl group is not particularly limited as long as it is a bicycloalkyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a 3-fluorobicyclo[1.1.0]butan-1-yl group, a 2,2,4,4-tetrafluorobicyclo[1.1.0]butan-1-yl group, a pentafluorobicyclo[1.1.0]butan-1-yl group, a 3-fluorobicyclo[1.1.1]pentan-1-yl group, a 2,2,4,4,5-pentafluorobicyclo[1.1.1]pentan-1-yl group, a 2,2,4,4,5,5-hexafluorobicyclo[1.1.1]pentan-1-yl group, a 5-fluorobicyclo[3.1.0]hexan-6-yl group, a 6-fluorobicyclo[3.1.0]hexan-6-yl group, 6,6-difluorobicyclo[3.1.0]hexan-2-yl group, 2,2,3,3,5,5,6,6-octafluorobicyclo[2.2.0]hexan-1-yl group, 1-fluorobicyclo[2.2.1]heptan-2-yl group, 3-fluorobicyclo[2.2.1]heptan-2-yl group, 4-fluorobicyclo[2.2.1]heptan-1-yl group, 5-fluorobicyclo[2.2.1]heptan-1-yl group, Examples include an orobicyclo[3.1.1]heptan-1-yl group, a 1,3,3,4,5,5,6,6,7,7-decafluorobicyclo[2.2.1]heptan-2-yl group, an undecafluorobicyclo[2.2.1]heptan-2-yl group, a 3-fluorobicyclo[2.2.2]octan-1-yl group, and a 4-fluorobicyclo[2.2.2]octan-1-yl group.

[0208] The fluoroalkenyl group is not particularly limited as long as it is an alkenyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a 1-fluoroethenyl group, a 2-fluoroethenyl group, a 1,2-difluoroethenyl group, a 1,2,2-trifluoroethenyl group, a 2,3,3-trifluoro-1-propenyl group, a 3,3,3-trifluoro-1-propenyl group, a 2,3,3,3-tetrafluoro-1-propenyl group, a pentafluoro-1-propenyl group, a 1-fluoro-2-propenyl group, a 1,1-difluoro-2-propenyl group, a 2,3-difluoro-2-propenyl group, a 3,3-difluoro-2-propenyl group, a 2,3,3-trifluoro-2-propenyl group, a 1,2,3,3-tetrafluoro-2-propenyl group, and a pentafluoro-2-propenyl group.

[0209] The fluoroalkynyl group is not particularly limited as long as it is an alkynyl group in which at least one hydrogen atom on a carbon atom is substituted with a fluorine atom, and examples thereof include a fluoroethynyl group, a 3-fluoro-1-propynyl group, a 3,3-difluoro-1-propynyl group, a 3,3,3-trifluoro-1-propynyl group, a 1-fluoro-2-propynyl group, and a 1,1-difluoro-2-propynyl group.

[0210] Among these, Ar F is preferably the above-mentioned optionally substituted fluoroaryl group having 6 to 20 carbon atoms or the above-mentioned substituted aryl group, more preferably the above-mentioned optionally substituted fluorophenyl group or the above-mentioned substituted phenyl group, and even more preferably the above-mentioned optionally substituted trifluorophenyl group, the above-mentioned optionally substituted tetrafluorophenyl group, the above-mentioned optionally substituted pentafluorophenyl group or a phenyl group substituted with 1 to 3 trifluoromethyl groups. F are preferably the same group.

[0211] Below, Ar F Specific examples of suitable groups are listed below, but are not limited to these.

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] Specific examples of the arylamine derivative represented by formula (T3) are listed below, but the invention is not limited thereto.

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226] The arylamine derivative represented by formula (T3) of the present invention can be synthesized by a known method, for example, by the method described in WO 2017 / 122649.

[0227] [Arylamine derivative represented by formula (T4)]

[0228] In formula (T4), Ar c each independently represents a group represented by the following formula (Q), each Y independently represents an optionally substituted phenylene group, and each g independently represents an integer of 1 to 10, preferably Ar c each independently represents a group represented by the following formula (Q') or (Q'').

[0229]

[0230] In formulas (Q), (Q') and (Q''), R q1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R q2 each independently represents an aryl group which may be substituted and which may contain a heteroatom; Ar s each independently represents an arylene group which may be substituted and which may contain a heteroatom.

[0231] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. 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.

[0232] The alkyl group in the alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, n-decyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, 2-n-propylhexyloxy, 2-n-butylhexyloxy, 2-ethyldecyloxy, and 3-ethylhexyloxy groups.

[0233] Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

[0234] The halogenated alkyl group having 1 to 20 carbon atoms is a group in which at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, and 2-(perfluorohexyl)ethyl groups.

[0235] R q1 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and even more preferably all are hydrogen atoms.

[0236] R in the above formulas (Q), (Q') and (Q'') q2 The aryl group of the formula (R), which may be substituted and may contain a heteroatom, is an arylene group which may contain a heteroatom as a constituent atom, and may have a structure in which rings are condensed or linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less. q2Specific examples of the substituent of the aryl group, which may be substituted and may contain a hetero atom, include a halogen atom, a nitro group, a cyano 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, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those mentioned above.

[0237] 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 groups.

[0238] Specific examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecinyl, and n-1-eicosynyl groups.

[0239] R q2 As R, an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom is preferred, an optionally substituted phenyl group or an optionally substituted naphthyl group is more preferred, a phenyl group or a naphthyl group is even more preferred in both cases, and a phenyl group is even more preferred in both cases. q2 Specific examples of suitable groups are listed below, but are not limited to these.

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247] Ar in the above formulas (Q), (Q') and (Q'') s The arylene group which may be substituted and may contain a heteroatom is an arylene group which may contain a heteroatom as a constituent atom, and may have a structure in which rings are condensed or linked. The number of carbon atoms is not particularly limited, but is usually 6 to 60, preferably 40 or less, and more preferably 30 or less. s Specific examples of the substituent of the arylene group, which may be substituted and may contain a hetero atom, include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the halogenated alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms are the same as those described above. s is a group represented by any one of the following formulas (101) to (118).

[0248]

[0249]

[0250]

[0251] R q3each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; V 1 are each independently C(R q4 ) 2 (R q4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms; NR q5 (R q5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; ), S, O, or SO2; V 2 is NR q5 (R q5 represents the same meaning as above. ), S or O. R q3 ~R q5 In the formula (I), examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the halogenated alkyl group having 1 to 20 carbon atoms are the same as those described above.

[0252] In particular, R q3 are each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. q4 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and all the more preferably a methyl group. q5 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, and still more preferably a hydrogen atom, a methyl group, or a phenyl group.

[0253] Ar s As the group, a group represented by any one of the following formulas (101A) to (118A) is preferred.

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261] (In the formula, R q3 , V 1 and V 2 has the same meaning as above.)

[0262] Below, Ar s Suitable specific examples are listed below, but the present invention is not limited to these.

[0263]

[0264]

[0265]

[0266]

[0267] (In the formula, R q4 and R q5 has the same meaning as above.)

[0268] (In the formula, R q4 and R q5 has the same meaning as above.)

[0269] (In the formula, R q4 and R q5 has the same meaning as above.)

[0270] (In the formula, R q4 and R q5 has the same meaning as above.)

[0271] (In the formula, Rq4 and R q5 has the same meaning as above.)

[0272] (In the formula, R q4 and R q5 has the same meaning as above.)

[0273] (In the formula, R q4 and R q5 has the same meaning as above.)

[0274] (In the formula, R q4 and R q5 has the same meaning as above.)

[0275] (In the formula, R q4 and R q5 has the same meaning as above.)

[0276] (In the formula, R q4 and R q5 has the same meaning as above.)

[0277] (In the formula, R q4 and R q5 has the same meaning as above.)

[0278] (In the formula, R q4 and R q5 has the same meaning as above.)

[0279] (In the formula, R q4 and R q5 has the same meaning as above.)

[0280] (In the formula, R q4 and R q5 has the same meaning as above.)

[0281] (In the formula, R q4 and R q5 has the same meaning as above.)

[0282] (In the formula, R q4 and Rq5 has the same meaning as above.)

[0283]

[0284] (In the formula, R q5 has the same meaning as above.)

[0285] (In the formula, R q5 has the same meaning as above.)

[0286] Examples of the optionally substituted phenylene group for Y in formula (T4) include a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group which may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or the like, and an optionally substituted 1,4-phenylene group or a 1,3-phenylene group is preferred.

[0287] In the above formula (T4), g's each independently represent an integer of 1 to 10. In consideration of the solubility of the compound in an organic solvent and the transparency of the resulting thin film, an integer of 1 to 7 is preferred, an integer of 1 to 5 is more preferred, an integer of 1 to 3 is even more preferred, and 1 or 2 is still more preferred. In consideration of the ease of availability of the raw material compounds, 1 is optimal.

[0288] In the present invention, Ar s is preferably a group represented by formula (107), more preferably a group represented by any one of formulas (107A) to (107C), still more preferably a group represented by any one of formulas (107A-1) to (107C-5), and even more preferably a group represented by formula (107B-1) or (107C-1).

[0289] In the present invention, from the viewpoint of ease of synthesis, in formula (T4), Ar c are preferably the same group. c is preferably a group represented by formula (Q-1) (Ar C1 ), and more preferably a group represented by formula (Q-2) (Ar C2 ) or a group represented by formula (Q-3) (Ar C3 )

[0290] (In the formula, R q1 , R q2 , R q4 has the same meaning as above.)

[0291] In a preferred embodiment, the arylamine compound of the present invention is represented by the following formula (T4-1), and in a more preferred embodiment, it is represented by either of the following formulas (T4-2) and (T4-3).

[0292] (In the formula, Y, Ar C1 and g have the same meaning as above.)

[0293] (In the formula, Y, Ar C2 and g have the same meaning as above.)

[0294] (In the formula, Y, Ar C3 and g have the same meaning as above.)

[0295] The arylamine derivative represented by formula (T4) of the present invention can be synthesized by a known method, for example, by the method described in WO 2020 / 241730.

[0296] The content of the charge-transporting substance in the charge-transporting varnish of the present invention is generally, taking into consideration the desired film thickness, the viscosity of the varnish, etc., a lower limit of the solid content is generally 1.0 mass %, preferably 2.0 mass %, and more preferably 5 mass %, and an upper limit of the solid content is generally 50 mass %, preferably 40 mass %, and more preferably 30 mass %.

[0297] In the present invention, the charge transport substance may be a combination of the above-mentioned polythiophene derivative or its amine adduct, or arylamine derivative, and a charge transport substance consisting of a charge transport compound other than these, but it is preferable that the charge transport substance contains only the above-mentioned polythiophene derivative or its amine adduct, or arylamine derivative.

[0298] [3] Organic Solvent The organic solvent used in preparing the charge-transporting varnish of the present invention can be a highly polar solvent capable of dissolving the charge-transporting material used. If necessary, a low-polarity solvent may be used because it has better process compatibility than a high-polarity solvent. In the present invention, a low-polarity solvent is defined as one having a dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as one having a dielectric constant of 7 or more at a frequency of 100 kHz.

[0299] Examples of low-polarity solvents include: chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0300] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0301] [4] Dopant Substance The charge-transporting varnish of the present invention may contain a dopant substance for the purpose of improving the charge transport ability, etc., depending on the application of the resulting thin film. The dopant substance is not particularly limited as long as it is soluble in at least one solvent used in the varnish, and both inorganic and organic dopant substances can be used. Inorganic and organic dopant substances may be used alone or in combination of two or more. The amount of the dopant substance cannot be generally specified because it is determined appropriately taking into account the type of dopant and the desired level of charge transportability, but is typically within a mass ratio range of 0.0001 to 100.0 parts by weight of the charge-transporting substance.

[0302] Examples of inorganic dopant substances include inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; metal halides such as aluminum(III) chloride (AlCl), titanium(IV) tetrachloride (TiCl), boron tribromide (BBr), boron trifluoride etherate (BF.OEt), iron(III) chloride (FeCl), copper(II) chloride (CuCl), antimony(V) pentachloride (SbCl), antimony(V) pentafluoride (SbF), arsenic(V) pentafluoride (AsF), phosphorus pentafluoride (PF), and tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); halogens such as Cl, Br, I, ICl, ICl, IBr, and IF; and heteropolyacids such as phosphomolybdic acid and phosphotungstic acid.

[0303] 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- Halotetracyanoquinodimethanes (haloTCNQs) such as dichloro-7,7,8,8-tetracyanoquinodimethane; 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, 2,7-di Examples of suitable sulfonic acid compounds include aryl sulfonic acid compounds such as nonyl-4,5-naphthalenedisulfonic acid, 1,4-benzodioxanedisulfonic acid derivatives described in WO 2005 / 000832, arylsulfonic acid derivatives described in WO 2006 / 025342, and dinonylnaphthalenesulfonic acid derivatives described in JP 2005-108828 A; aromatic sulfone compounds such as polystyrene sulfonic acid; fluorinated arylsulfonic acid polymer compounds described in WO 2023 / 008176; 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.

[0304] Among these dopant substances, aryl sulfonic acid compounds are preferred in the present invention, and may be low-molecular-weight aryl sulfonic acid compounds or high-molecular-weight aryl sulfonic acid compounds. Preferred examples of low-molecular-weight aryl sulfonic acid compounds include aryl sulfonic acid compounds represented by formula (H1) or (H2).

[0305]

[0306] A 1 represents O or S, with O being preferred. 2 represents a naphthalene ring or an anthracene ring, with a naphthalene ring being preferred. 3 represents a divalent to tetravalent perfluorobiphenyl group, s represents A 1 and A 3 and is an integer satisfying 2≦s≦4, 3 is a perfluorobiphenyldiyl group, preferably a perfluorobiphenyl-4,4'-diyl group, and s is preferably 2. 2 represents the number of sulfo groups bonded to the hydroxyl group, and is an integer satisfying the relationship 1≦q≦4, with 2 being optimal.

[0307] A 4 ~A 8 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms; 4 ~A 8 At least three of the groups are halogen atoms.

[0308] Examples of halogenated alkyl groups having 1 to 20 carbon atoms include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 1,1,2,2,3,3,3-heptafluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 1,1,2,2,3,3,4,4,4-nonafluorobutyl group.

[0309] Examples of halogenated alkenyl groups having 2 to 20 carbon atoms include perfluorovinyl groups, perfluoropropenyl groups (allyl groups), perfluorobutenyl groups, etc. Other examples of halogen atoms and alkyl groups having 1 to 20 carbon atoms include those similar to those mentioned above, but the halogen atom is preferably a fluorine atom.

[0310] Among these, A 4 ~A 8 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, and A 4 ~A 8 At least three of A are preferably fluorine atoms, and are selected from the group consisting of a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, and a fluorinated alkenyl group having 2 to 5 carbon atoms, and 4 ~A 8 At least three of A are preferably fluorine atoms, and A is preferably a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms. 4 , A 5 and A 8 It is more preferable that each of the hydrogen atoms of the alkyl group and the perfluoroalkenyl group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

[0311] r represents the number of sulfo groups bonded to the naphthalene ring and is an integer satisfying 1≦r≦4, preferably 2 to 4, and most preferably 2.

[0312] When a low-molecular-weight organic compound is used as the dopant substance, the molecular weight thereof is preferably 3,000 or less, more preferably 2,500 or less, in consideration of solubility in organic solvents. In particular, the molecular weight of the low-molecular-weight arylsulfonic acid compound used as the dopant substance is not particularly limited, but is preferably 2,000 or less, more preferably 1,500 or less, in consideration of solubility in organic solvents.

[0313] In the present invention, examples of arylsulfonic acid compounds that can be suitably used include, but are not limited to, the following compounds:

[0314]

[0315] The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, in terms of mole ratio per 1 part of the charge transporting substance such as a polythiophene derivative or an arylamine derivative.

[0316] Furthermore, the dopant substance may be a substance that exhibits or improves its function as a dopant substance for the first time when, for example, a part of the molecule is removed by an external stimulus, such as heating during baking, in the process of obtaining a charge-transporting thin film, which is a solid film, from the varnish, such as an arylsulfonate ester compound protected by a group from which the sulfo group is easily removed.

[0317] The aryl sulfonate ester compound is not particularly limited as long as it has a sulfonate ester group bonded to an aromatic ring. The molecular weight of the aryl sulfonate ester compound is not particularly limited. In a preferred embodiment of the present invention, the molecular weight of the aryl sulfonate ester compound is preferably 100 or more, more preferably 200 or more, and preferably 5,000 or less, more preferably 4,000 or less, even more preferably 3,000 or less, and even more preferably 2,000 or less. In a preferred embodiment of the present invention, the number of sulfonate ester groups in the aryl sulfonate ester compound is preferably 2 or more, more preferably 3 or more, and preferably 6 or less, more preferably 5 or less. In a preferred embodiment of the present invention, the aryl sulfonate ester compound preferably contains an aromatic ring substituted with fluorine.

[0318] Examples of the aryl sulfonate ester compound include the aryl sulfonate ester compounds disclosed in WO 2017 / 217455, the aryl sulfonate ester compounds disclosed in WO 2017 / 217457, and the aryl sulfonate ester compounds described in WO 2019 / 124412. Preferred aryl sulfonate compounds are those represented by the following formula (B1) or (B1′):

[0319]

[0320] In formulas (B1) and (B1′), A 01 is an s-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, which may have a substituent, or an s-valent group derived from a compound represented by the following formula (B1a) or (B1b) (i.e., a group obtained by removing s hydrogen atoms on the aromatic rings of a compound represented by the following formula (B1a) or (B1b)):

[0321] (In the formula, W 1 and W 2 are each independently —O—, —S—, —S(O)—, —S(O)—, or —N—, —Si—, —P—, or —P(O)— which may have a substituent.

[0322] An s-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings is a group obtained by removing s hydrogen atoms from a hydrocarbon having 6 to 20 carbon atoms and containing one or more aromatic rings. Examples of the hydrocarbon containing one or more aromatic rings include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Of these, groups derived from benzene, biphenyl, etc. are preferred as the s-valent hydrocarbon group.

[0323] The hydrocarbon group may further have some or all of its hydrogen atoms substituted with a substituent, such as a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), nitro, cyano, hydroxy, amino, silanol, thiol, carboxy, sulfonate ester, phosphoric acid, phosphate ester, ester, thioester, amide, monovalent hydrocarbon, organooxy, organoamino, organosilyl, organothio, acyl, or sulfo group.

[0324] Here, the monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; alkenyl groups having 2 to 10 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, tolyl, 1-naphthyl, and 2-naphthyl groups; and aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenylethyl groups.

[0325] Specific examples of the organoxy group include alkoxy, alkenyloxy, aryloxy, etc. The alkyl, alkenyl and aryl groups contained therein are the same as those described above.

[0326] Specific 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 groups; dialkylamino groups in which each alkyl group has 1 to 12 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, dicyclohexylamino, diheptylamino, dioctylamino, dinonylamino, and didecylamino groups; and a morpholino group.

[0327] Specific examples of the organosilyl group include trialkylsilyl groups, each of which has 1 to 10 carbon atoms, such as trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl, hexyldimethylsilyl, octyldimethylsilyl, and decyldimethylsilyl. Specific 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. Specific examples of the acyl group include acyl groups having 1 to 10 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and benzoyl.

[0328] The monovalent hydrocarbon group, organooxy group, organoamino group, organosilyl group, organothio group and acyl group preferably have 1 to 8 carbon atoms.

[0329] Among these substituents, a fluorine atom, a sulfo group, an alkyl group, an organoxy group, and an organosilyl group are more preferred.

[0330] In formula (B1), A 02 is —O—, —S—, or —NH—. Of these, —O— is preferred because it is easy to synthesize.

[0331] In formula (B1), A 03is a (q+1)-valent aromatic group having 6 to 20 carbon atoms. The (q+1)-valent aromatic group is a group obtained by removing (q+1) hydrogen atoms on the aromatic ring from an aromatic compound having 6 to 20 carbon atoms. In the present invention, the aromatic compound means an aromatic hydrocarbon or an aromatic heterocyclic compound. Examples of the aromatic compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene, etc., and among these, A 3 The aromatic group represented by the formula (I) is preferably a group derived from naphthalene or anthracene.

[0332] In formulas (B1) and (B1′), X 1 is an alkylene group having 2 to 5 carbon atoms, and this alkylene group may have -O-, -S- or a carbonyl group between its carbon atoms (carbon-carbon bond), and some or all of its hydrogen atoms may be further substituted with alkyl groups having 1 to 20 carbon atoms. 1 Preferred examples of the alkyl group include ethylene, trimethylene, methyleneoxymethylene, and methylenethiomethylene groups, and some or all of the hydrogen atoms in these groups may be further substituted with an alkyl group having 1 to 20 carbon atoms. Examples of this alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and bicyclohexyl groups.

[0333] In formulas (B1) and (B1′), X 2 is a single bond, —O—, —S—, or NR—. R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. As this monovalent hydrocarbon group, an alkyl group such as a methyl, ethyl, or n-propyl group is preferred. X 2 is preferably a single bond, —O— or —S—, more preferably a single bond or —O—.

[0334] In formulas (B1) and (B1′), X 3is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted. This monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and bicyclohexyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, and 1-butene. Examples of such groups include alkenyl groups having 2 to 20 carbon atoms, such as phenyl, 2-butenyl, 3-butenyl, and hexenyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 2-biphenylyl, 3-biphenylyl, and 4-biphenylyl; and aralkyl groups having 7 to 20 carbon atoms, such as benzyl, phenylethyl, and phenylcyclohexyl. Furthermore, some or all of the hydrogen atoms of the monovalent hydrocarbon groups may be further substituted with a substituent. Examples of such substituents include A 01 The same as those mentioned in the description of X. 3 As the alkyl group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferred.

[0335] In formulas (B1) and (B1′), s is an integer satisfying 1≦s≦4, preferably 2. q is an integer satisfying 1≦q≦4, preferably 2.

[0336] The arylsulfonate ester compounds represented by formulas (B1) and (B1') exhibit high solubility in a wide range of solvents, including low-polarity solvents, making it possible to adjust the physical properties of the solution using a wide variety of solvents, resulting in excellent coating properties. Therefore, it is preferable to apply the compound in the form of a sulfonate ester and generate sulfonic acid during drying or baking of the coating film. The temperature at which sulfonic acid is generated from the sulfonate ester is preferably stable at room temperature and below the baking temperature, so is preferably 40 to 260°C. Furthermore, considering high stability in the varnish and ease of desorption during baking, a temperature of 80 to 230°C is preferred, and 120 to 180°C is more preferred.

[0337] The arylsulfonic acid ester compound represented by formula (B1) is preferably one represented by any one of the following formulae (B1-1) to (B1-3).

[0338]

[0339] In formula (B1-1), A 11 A is an s-valent group derived from perfluorobiphenyl (i.e., a group obtained by removing s fluorine atoms from perfluorobiphenyl). 12 is —O— or —S—, with —O— being preferred. 13 is a (q+1)-valent group derived from naphthalene or anthracene (i.e., a group obtained by removing (q+1) hydrogen atoms from naphthalene or anthracene), with groups derived from naphthalene being preferred.

[0340] In formula (B1-1), R s1 ~R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R s5 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

[0341] Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, etc. Among these, alkyl groups having 1 to 3 carbon atoms are preferred.

[0342] The monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; and aryl groups such as phenyl, naphthyl, and phenanthryl.

[0343] R s1 ~R s4 Among them, R s1 or R s3 is preferably a linear alkyl group having 1 to 3 carbon atoms, and the remainder is preferably a hydrogen atom. s1 is a linear alkyl group having 1 to 3 carbon atoms, and R s2 ~R s4 is preferably a hydrogen atom. The linear alkyl group having 1 to 3 carbon atoms is preferably a methyl group. s5 As the alkyl group, a linear alkyl group having 2 to 4 carbon atoms or a phenyl group is preferred.

[0344] In formula (B1-1), s is an integer that satisfies 1≦s≦4, and is preferably 2. q is an integer that satisfies 1≦q≦4, and is preferably 2.

[0345] In formula (B1-2), A 14 is an s-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, which may be substituted. The s-valent hydrocarbon group is a group obtained by removing s hydrogen atoms from a hydrocarbon having 6 to 20 carbon atoms and containing one or more aromatic rings. Examples of the hydrocarbon include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.

[0346] In addition, some or all of the hydrogen atoms of the hydrocarbon group may be further substituted with a substituent, and such substituents include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro, cyano, hydroxy, amino, silanol, thiol, carboxy, sulfonate ester, phosphoric acid, phosphate ester, ester, thioester, amide, monovalent hydrocarbon, organooxy, organoamino, organosilyl, organothio, acyl, and sulfo groups. 14 As the alkyl group, groups derived from benzene, biphenyl, etc. are preferred.

[0347] In formula (B1-2), A 15 is —O— or —S—, with —O— being preferred.

[0348] In formula (B1-2), A 16 is a (q+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms. The (q+1)-valent aromatic hydrocarbon group is a group obtained by removing (q+1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms. Examples of this aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene, etc. Among these, A 16 As the alkyl group, a group derived from naphthalene or anthracene is preferred, and a group derived from naphthalene is more preferred.

[0349] In formula (B1-2), R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group. s8 is a linear or branched monovalent aliphatic hydrocarbon group, provided that R s6 , R s7 and R s8 The total number of carbon atoms in R is 6 or more. s6 , R s7 and R s8 The upper limit of the total number of carbon atoms is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.

[0350] Specific examples of the linear or branched monovalent aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl groups; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl groups.

[0351] R s6 is preferably a hydrogen atom, and R s7 and R s8 is preferably an alkyl group having 1 to 6 carbon atoms. s7 and R s8 may be the same or different.

[0352] In formula (B1-2), s is an integer that satisfies 1≦s≦4, and is preferably 2. q is an integer that satisfies 1≦q≦4, and is preferably 2.

[0353] In formula (B1-3), R s9 ~R s13 are each independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms.

[0354] The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups.

[0355] The halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of an alkyl group having 1 to 10 carbon atoms have been substituted with halogen atoms. The halogenated alkyl group may be linear, branched, or cyclic, and specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl groups.

[0356] The halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of an alkenyl group having 2 to 10 carbon atoms have been substituted with halogen atoms. Specific examples thereof include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, and perfluoro-3-butenyl groups.

[0357] Of these, R s9 As R, a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 2 to 10 carbon atoms, etc. are preferred, a nitro group, a cyano group, a halogenated alkyl group having 1 to 4 carbon atoms, a halogenated alkenyl group having 2 to 4 carbon atoms, etc. are more preferred, and a nitro group, a cyano group, a trifluoromethyl group, a perfluoropropenyl group, etc. are even more preferred. s10 ~R s13 As the atom, a halogen atom is preferable, and a fluorine atom is more preferable.

[0358] In formula (B1-3), A 17 is —O—, —S— or —NH—, with —O— being preferred.

[0359] In formula (B1-3), A 18is a (q+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms. The (q+1)-valent aromatic hydrocarbon group is a group obtained by removing (q+1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among these, A 18 As the alkyl group, a group derived from naphthalene or anthracene is preferred, and a group derived from naphthalene is more preferred.

[0360] In formula (B1-3), R s14 ~R s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. The monovalent aliphatic hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; and alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl. Of these, alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 8 carbon atoms are even more preferred.

[0361] In formula (B1-3), R s18 represents a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 It is. s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

[0362] R s18 As the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R s14 ~R s17 Examples include those mentioned in the description of R. s18is a monovalent aliphatic hydrocarbon group, R s18 As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is even more preferable.

[0363] R s19 Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by the formula (I) include the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group, as well as aryl groups such as a phenyl group, a naphthyl group, and a phenanthryl group. s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group. Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.

[0364] In formula (B1-3), q is an integer that satisfies 1≦q≦4, and is preferably 2.

[0365] As the arylsulfonic acid ester compound represented by formula (B1-3), those represented by the following formula (B1-3-1) or (B1-3-2) are particularly preferred.

[0366]

[0367] In formulas (B1-3-1) and (B1-3-2), A 17 , A 18 , R s9 ~R s17 , R s19 and q have the same meaning as above. s20 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include R s18 Examples of the above-mentioned methods are the same as those described above.

[0368] In the arylsulfonic acid ester compound represented by formula (B1-3-1), R s14 ~R s17 Among them, R s14 or R s16 is preferably a linear alkyl group having 1 to 3 carbon atoms, and the remainder is preferably a hydrogen atom. s14 is a linear alkyl group having 1 to 3 carbon atoms, and Rs15 ~R s17 is preferably a hydrogen atom. As the linear alkyl group having 1 to 3 carbon atoms, a methyl group is preferred. s19 As the alkyl group, a linear alkyl group having 2 to 4 carbon atoms or a phenyl group is preferred.

[0369] In the arylsulfonic acid ester compound represented by formula (B1-3-2), R s14 , R s16 and R s20 The total number of carbon atoms in R is preferably 6 or more. s14 , R s16 and R s20 The upper limit of the total number of carbon atoms in R is preferably 20 or less, more preferably 10 or less. s14 is preferably a hydrogen atom, and R s16 and R s20 is preferably an alkyl group having 1 to 6 carbon atoms. s16 and R s20 may be the same or different from each other.

[0370] The arylsulfonic acid ester compounds represented by formula (B1) may be used singly or in combination of two or more.

[0371] Specific examples of suitable aryl sulfonate compounds include, but are not limited to, those shown below.

[0372]

[0373]

[0374] The amount of the arylsulfonic acid ester compound used is preferably about 0.01 to 20.0, more preferably about 0.05 to 15, in terms of mole ratio per 1 part of the organic functional material such as a polythiophene derivative or an arylamine derivative.

[0375] The dopant material may also be a fluorinated aryl sulfonic acid polymer compound.

[0376] The fluorinated arylsulfonic acid polymer compound is characterized by containing a repeating unit represented by the following formula (F1):

[0377]

[0378] In formula (F1), Ar F represents a fluorinated arylene group. F The fluorinated arylene group of the formula (I) is not particularly limited as long as at least one hydrogen atom on the arylene group is substituted with a fluorine atom, but it is preferable that at least one of the remaining hydrogen atoms is substituted with an electron-withdrawing group other than a sulfo group. Examples of the electron-withdrawing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; nitro group; cyano group; acyl group; carboxy group; carboxylic acid ester group; and acyl groups such as formyl group and acetyl group. In particular, Ar F The fluorinated arylene group is preferably an arylene group substituted with two or more fluorine atoms, and more preferably a perfluoroarylene group.

[0379] Ar F There is no particular limitation on the number of carbon atoms in the arylene group constituting Ar, but the number of carbon atoms is preferably 6 to 20, and more preferably 6 to 16. Specific examples thereof include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 4,4'-biphenylylene, and anthracenyl groups, with a phenylene group being preferred and a 1,4-phenylene group being more preferred. Therefore, Ar F As the alkyl group, a tetrafluorophenylene group is preferred, and a 2,3,5,6-tetrafluoro-1,4-phenylene group is more preferred.

[0380] X represents O, S, NH, CONH or NHCO, with O and S being preferred, and O being more preferred.

[0381] A preferred fluorinated arylsulfonic acid polymer compound of the present invention is one represented by the following formula (F1-1):

[0382] (In the formula, n1 represents an integer of 1 to 4.)

[0383] More preferred fluorinated arylsulfonic acid polymer compounds include those represented by the following formula (F1-2).

[0384] (In the formula, n1 represents an integer of 1 to 4.)

[0385] A more suitable fluorinated arylsulfonic acid polymer compound is one represented by the following formula (F1-3).

[0386]

[0387] Ar S has at least one SO3R on the ring w represents an aryl group having a group, and R w represents a hydrogen atom or an alkali metal atom such as Li, Na, or K, and is preferably a hydrogen atom. S There is no particular limitation on the number of carbon atoms in the aryl group constituting Ar, but it is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. Specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups, with naphthyl groups being preferred, and 1-naphthyl groups being more preferred. S The number of SO3R groups contained in Ar may be one or more, but is preferably 2 to 4, and more preferably 2. S As the compound represented by the following formula (Ar S -1) to (Ar S -6).

[0388] (In the formula, R w represents the same meaning as above. n2 represents an integer of 2 to 4.

[0389] (In the formula, R w has the same meaning as above.)

[0390] (In the formula, R w has the same meaning as above.)

[0391] (In the formula, R w has the same meaning as above.)

[0392] The fluorinated arylsulfonic acid polymer compound of the present invention may be a polymer containing only a repeating unit represented by the above formula (1). However, from the viewpoint of increasing solubility in organic solvents, a polymer further containing a repeating unit represented by the following formula (F2) is preferred.

[0393]

[0394] In formula (F2), R' represents a monovalent organic group. Examples of this monovalent organic group include a monovalent hydrocarbon group, a heteroaryl group, and a -COOR" group (wherein R" represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). There are no particular restrictions on the number of carbon atoms in the monovalent hydrocarbon group, but a carbon number of 1 to 20 is preferred, a carbon number of 6 to 20 is more preferred, and a carbon number of 6 to 10 is even more preferred. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

[0395] Specific examples of heteroaryl groups include heteroaryl groups having 2 to 20 carbon atoms, such as 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, and 4-pyridyl groups.

[0396] Examples of the alkyl group having 1 to 10 carbon atoms for R″ include the same groups as those exemplified above, and among these, alkyl groups having 1 to 5 carbon atoms are preferred.

[0397] In addition, the monovalent hydrocarbon group, heteroaryl group, and alkyl group having 1 to 10 carbon atoms represented by R" may have some or all of their hydrogen atoms substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, and a hydroxyl group. Examples of the halogen atom include the same atoms as those exemplified above.

[0398] Among these, in consideration of improving the device characteristics and life characteristics of an organic EL device obtained by using the fluorinated arylsulfonic acid polymer compound of the present invention as a dopant substance, R' is preferably an aryl group substituted with a halogen atom, more preferably a fluorinated aryl group, and even more preferably a perfluoroaryl group. In particular, R' is preferably a phenyl group substituted with a halogen atom, more preferably a fluorinated phenyl group, and even more preferably a perfluorophenyl group.

[0399] When the fluorinated arylsulfonic acid polymer compound of the present invention contains a repeating unit represented by formula (F2), the content ratio of the unit of formula (F1) to the unit of formula (F2) is not particularly limited. However, in consideration of improving device characteristics when used as a dopant substance, the molar ratio of formula (F1):formula (F2) is preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5, even more preferably from 3:1 to 1:3, and still more preferably 1:1.

[0400] The molecular weight of the fluorinated arylsulfonic acid polymer compound of the present invention is not particularly limited, but from the viewpoint of improving heat resistance and ensuring solubility in solvents, the weight average molecular weight Mw is preferably 1,000 to 50,000, more preferably 1,500 to 10,000, and even more preferably 2,000 to 10,000. The molecular weight distribution (Mw / Mn) is preferably 1 to 3, more preferably 1 to 2. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard sample.

[0401] The fluorinated arylsulfonic acid polymer compound of the present invention can be obtained by polymerizing a monomer represented by the following formula (F1A) and, if necessary, a monomer represented by the following formula (F2A) in the presence of a solvent and a radical polymerization initiator by a known radical polymerization method. In this case, two or more types of monomers represented by formula (F1A) may be used in combination, and two or more types of monomers represented by formula (F2A) may be used in combination.

[0402] (In the formula, Ar F , Ar S , X and R f1 has the same meaning as above.)

[0403] Heteropolyacids can also be suitably used as dopant substances. Heteropolyacids are polyacids that have a structure in which a heteroatom is located at the center of the molecule, typically represented by a Keggin-type chemical structure shown in formula (D1) or a Dawson-type chemical structure shown in formula (D2), and are formed by condensing an isopolyacid, which is an oxyacid of vanadium (V), molybdenum (Mo), tungsten (W), or the like, with an oxyacid of a different element. Examples of such oxyacids of different elements include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

[0404]

[0405] Specific examples of heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid, which may be used alone or in combination of two or more. The heteropolyacids used in the present invention are commercially available or can be synthesized by known methods. In particular, when only one type of heteropolyacid is contained, it is preferable that the one type of heteropolyacid contains tungsten. That is, phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, and the like are preferred, with phosphotungstic acid and silicotungstic acid being more preferred.

[0406] In addition, heteropolyacids can be used in the present invention even if they have a large or small number of elements in the structure represented by the general formula in quantitative analysis such as elemental analysis, as long as they are commercially available or appropriately synthesized according to a known synthesis method. That is, for example, phosphotungstic acid is generally represented by the chemical formula H3(PW 12 O 40 )·nHO, but whether the number of P (phosphorus), O (oxygen), or W (tungsten) in this formula is large or small in quantitative analysis, it can be used in the present invention as long as it is commercially available or appropriately synthesized according to a known synthesis method. In this case, the mass of the heteropolyacid specified in the present invention does not refer to the mass of pure phosphotungstic acid (phosphotungstic acid content) in a synthesized or commercially available product, but rather refers to the total mass, including water of hydration and other impurities, in a form available as a commercially available product or in a form that can be isolated by a known synthesis method.

[0407] The amount of heteropolyacid used can be about 0.001 to 50.0 parts by mass per 1 part of the charge transporting substance such as a polythiophene derivative or an arylamine derivative, but is preferably about 0.01 to 20.0 parts, and more preferably about 0.1 to 10.0 parts.

[0408] [5] Amine Compound When a polythiophene derivative or its amine adduct is used as the charge transport substance in the charge transport varnish of the present invention, an amine compound (excluding compounds corresponding to the charge transport substance in [2] above) may be contained for the purpose of improving its dispersibility or solubility, etc. Such an amine compound is not particularly limited as long as it is soluble in at least one solvent used in the varnish, and one type may be used alone, or two or more types may be used.

[0409] Specific examples of the primary amine compound include methylamine, ethylamine, n-propylamine, isopropylamine, 3-ethoxypropylamine, 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, and n-pentadecylamido. monoalkylamine compounds such as aniline, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, and n-eicosanylamine; and 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.

[0410] Specific examples of the secondary amine compound include N-ethylmethylamine, N-methyl-n-propylamine, N-methylisopropylamine, N-methyl-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, N-n-propylisopropylamine, N-n-propyl N-n-butylamine, N-n-propyl-s-butylamine, diisopropylamine, N-n-butylisopropylamine, N-t-butylisopropylamine, di(n-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- Dialkylamine compounds such as 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- Examples thereof include diarylamine compounds such as dibenzo[a,i]carbazole; and alkylarylamine compounds such as N-methylaniline, N-ethylaniline, N-n-propylaniline, N-isopropylaniline, N-n-butylaniline, N-s-butylaniline, N-isobutylaniline, N-methyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-n-propyl-1-naphthylamine, indoline, isoindoline, 1,2,3,4-tetrahydroquinoline, and 1,2,3,4-tetrahydroisoquinoline.

[0411] Specific examples of the tertiary amine compound include N,N-dimethylethylamine, N,N-dimethyl-n-propylamine, N,N-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, and N,N-di(n-butyl)ethylamine. trialkylamine compounds such as 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; and 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.

[0412] In particular, when the charge-transporting varnish of the present invention contains an amine compound, the amine compound preferably contains a primary amine compound, and more preferably contains a monoalkylamine, particularly a monoalkylamine having from 2 to 20 carbon atoms, because this has an excellent ability to improve the dispersibility and solubility of the charge-transporting substance, such as the polythiophene derivative or its amine adduct, used in the present invention.

[0413] When the charge-transporting varnish of the present invention contains the above-mentioned amine compound, the content thereof is usually about 10 times or less by mass relative to the charge-transporting substance used in the present invention.

[0414] [6] Preparation of Charge-Transporting Varnish and Removal of Residual Silane Coupling Agent In the present invention, the preparation of the charge-transporting varnish includes a step of removing residual silane coupling agent at any timing in the production process.

[0415] The removal method is not particularly limited as long as it can remove the silane coupling agent remaining in the surface-treated SiO2 nanoparticle dispersion. Examples of the method include ultrafiltration membrane method, centrifugation method, distillation method, etc. Among these, the ultrafiltration membrane method is preferred because of its high removal efficiency. In addition, ultrasonic treatment may be combined in order to separate the organosilicon compound that is only physically adsorbed from the SiO2 nanoparticles.

[0416] When removing the residual silane coupling agent by the ultrafiltration membrane method, in the present invention, for example, a stirring type Ultraholder UHP-62K manufactured by ADVANTEC Toyo Co., Ltd. can be suitably used. A suitable embodiment of ultrafiltration in the present invention is, for example, using an Ultrafilter Q2000 as the filtration membrane, adding 170 mL of methanol to approximately 30 mL of the dispersion to be filtered, and pressurizing with 0.04 mPa of air or nitrogen to perform ultrafiltration, but this is not limited thereto. Furthermore, in order to more reliably remove the residual silane coupling agent, ultrafiltration may be repeated multiple times, and may be repeated about 2 to 5 times as necessary.

[0417] The treatment to remove the residual silane coupling agent can be carried out at any timing during the preparation of the charge-transporting varnish. However, in consideration of the removal efficiency, it is preferable to carry out the treatment at the stage of the surface-treated SiO nanoparticle dispersion after the SiO nanoparticles have been treated with a specified silane coupling agent.

[0418] The method for preparing the charge-transporting varnish is not particularly limited except for the removal of residual silane coupling agent. Examples include a method in which a charge-transporting substance and, if necessary, a dopant substance are dissolved in a high-polarity solvent, and then a low-polarity solvent and surface-treated SiO2 nanoparticles that have been treated to remove residual silane coupling agent are added thereto; and a method in which a high-polarity solvent and a low-polarity solvent are mixed, and then a charge-transporting substance and, if necessary, a dopant substance are dissolved therein, and then surface-treated SiO2 nanoparticles that have been treated to remove residual silane coupling agent are added thereto.

[0419] In particular, when preparing a charge-transporting varnish, from the viewpoint of obtaining a thin film with higher flatness with good reproducibility, it is desirable to dissolve the charge-transporting substance and, if necessary, the dopant substance in an organic solvent, and then filter the resulting solution using a submicrometer-order filter or the like before use.

[0420] The viscosity of the charge-transporting varnish obtained in this manner is determined as appropriate depending on the thickness of the thin film to be produced 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 contained in the charge-transporting varnish other than the solvent. The solid content concentration of the charge-transporting varnish is determined as appropriate taking into account the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, and other factors, but is typically about 0.1 to 10.0% by mass. In consideration of improving the coatability of the varnish, it is preferably about 0.5 to 8.0% by mass, and more preferably about 1.0 to 6.0% by mass.

[0421] [7] Charge-Transporting Thin Film In the present invention, a charge-transporting thin film can be easily produced by using the charge-transporting varnish described above. Therefore, it can be suitably used when 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 charge-transporting varnish described above to a substrate and baking it. The method for applying the varnish is not particularly limited, and examples include dipping, spin coating, transfer printing, roll coating, brush coating, inkjet coating, spraying, and slit coating. It is preferable to adjust the viscosity and surface tension of the varnish depending on the application method.

[0422] Furthermore, the atmosphere in which the charge-transporting varnish is baked after application is not particularly limited, and a thin film with a uniform film surface and high charge transport properties can be obtained not only in an air atmosphere but also in an inert gas such as nitrogen or in a vacuum. However, depending on the type of dopant substance used, a thin film with charge transport properties can sometimes be reproducibly obtained by baking the varnish in an air atmosphere.

[0423] 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 injection 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 baking, the temperature may be changed in two or more stages for the purpose of achieving more uniform film formation or promoting a reaction on the substrate, and heating may be performed using an appropriate device such as a hot plate or an oven.

[0424] 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 a light-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 solids concentration in the varnish or changing the amount of solution on the substrate during application.

[0425] [8] Organic EL Devices and Quantum Dot EL Devices When the above-described charge transport thin film is applied to an organic EL device or a quantum dot EL device, the organic EL device or the quantum dot EL device can be configured to include the above-described charge transport thin film between a pair of electrodes constituting the organic EL device or the quantum dot EL device. Typical configurations of organic EL devices or quantum dot EL devices include, but are not limited to, the following (a) to (f). In the configurations described below, an electron blocking layer or the like can be provided between the light-emitting layer and the anode, and a hole blocking layer or the like can be provided between the light-emitting layer and the cathode, as necessary. Furthermore, the hole injection layer, the hole transport layer, or the hole injection transport layer may also function as an electron blocking layer, and the electron injection layer, the electron transport layer, or the electron injection transport layer may also function as a hole blocking layer. Furthermore, an optional functional layer can be provided between each layer as necessary. (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

[0426] 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 the ability to accept holes from the anode but also in the ability to inject holes into the hole transport (light-emitting) layer.

[0427] 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 transport 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 an electron-transporting material are provided between the light-emitting layer and the cathode, the layer closest to the cathode is the "electron injection layer," and the remaining layers are "electron transport layers." The term "light-emitting layer" refers to an organic layer that emits light. When a doping system is employed, it contains a host material and a dopant material. In this case, the host material primarily promotes the recombination of electrons and holes and confines excitons within the light-emitting layer, while the dopant material efficiently emits the excitons obtained by recombination. In the case of phosphorescent devices, the host material primarily confines excitons generated by the dopant within the light-emitting layer.

[0428] The charge-transporting thin film of the present invention can be used as a functional layer provided between an anode and an emitting 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, and is more suitable as a hole-injection layer or a hole-transport layer.

[0429] Materials used and production methods for producing an EL device using the charge-transporting varnish of the present invention include, but are not limited to, those listed below. An example of a method for producing an OLED device having a hole injection layer or hole transport layer made of a thin film obtained from the charge-transporting varnish of the present invention is as follows. It is preferable to previously wash the electrodes with alcohol, pure water, or the like, or to perform surface treatment such as UV ozone treatment or oxygen-plasma treatment, to the extent that this does not adversely affect the electrodes.

[0430] In one example of a method for producing an OLED device having a hole injection layer made of a thin film obtained from the charge transport varnish of the present invention, a hole injection layer made of the charge transport thin film of the present invention is formed on an anode substrate by the above-described method. This is then introduced into a vacuum deposition apparatus, and a hole transport layer, a light-emitting layer, an electron transport layer, an electron transport layer / hole blocking layer, and a cathode metal are sequentially deposited by vapor deposition. Alternatively, instead of forming the hole transport layer and the light-emitting layer by vapor deposition in this method, these layers are formed by a wet process using a hole transport layer-forming composition containing a hole transport polymer and 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.

[0431] In one example of a method for producing an OLED device having a hole transport layer made of a thin film obtained from the charge transport varnish of the present invention, 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 an emissive layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited by vapor deposition. Alternatively, instead of forming the emissive layer by vapor deposition in this method, these layers are formed by a wet process using a composition for forming an emissive layer containing a light-emitting polymer. If necessary, an electron blocking layer may be provided between the emissive layer and the hole transport layer.

[0432] Examples of 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 alloys thereof, preferably those that have undergone planarization. Polythiophene derivatives and polyaniline derivatives with high charge transport properties can also be used. Other metals that can be used to make metal anodes include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

[0433] Examples of 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-N 4 , 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. However, it is not limited to these.

[0434] Examples of materials for forming the hole transport layer include triarylamines such as (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine (α-NPD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), and 4,4',4"-tris[1-naphthyl(phenyl)amino]triphenylamine (1-TNATA), and oligothiophenes such as 5,5"-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5',2"-terthiophene (BMA-3T).

[0435] Examples of materials for forming the light-emitting layer include, but are not limited to, low-molecular-weight light-emitting materials such as metal complexes (e.g., 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 (e.g., poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), or polyvinylcarbazole. Furthermore, when the light-emitting layer is formed by vapor deposition, it may be co-deposited with a light-emitting dopant. Examples of light-emitting dopants include, but are not limited to, metal complexes (e.g., tris(2-phenylpyridine)iridium(III) (Ir(ppy)), naphthacene derivatives (e.g., rubrene), quinacridone derivatives, and fused polycyclic aromatic rings (e.g., perylene).

[0436] 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.

[0437] Materials for forming the electron injection layer include, but are not limited to, metal oxides such as lithium oxide (LiO), magnesium oxide (MgO), and alumina (AlO), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF). Cathode materials include, but are not limited to, aluminum, magnesium-silver alloys, and aluminum-lithium alloys. Materials for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole)iridium.

[0438] Examples of hole transporting polymers include poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4-diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)], and poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-endcapped with Examples of such a compound include polysilsesquioxane, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'(N-(4-sec-butylphenyl)diphenylamine)], poly(9-vinylcarbazole), and poly(4-butyl-N,N-diphenylaniline).

[0439] Examples of the light-emitting polymer 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).

[0440] The quantum dot material may include at least one semiconductor material selected from the group consisting of II-VI semiconductors, III-V semiconductors, I-III-VI semiconductors, IV semiconductors, and I-II-IV-VI 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, and CdHgZnT. 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 gallium arsenide include, but are not limited to, Cu ...

[0441] As described above, the charge-transporting varnish 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 in an organic EL device or a quantum dot EL device. However, it can also be used for forming charge-transporting 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.

[0442] 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.

[0443] (1) Application of charge transport varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (2) Ultrafiltration membrane method: Stirring type Ultraholder UHP-62K manufactured by Advantec Toyo Co., Ltd., Ultrafilter Q2000 manufactured by Advantec Toyo Co., Ltd. (3) Preparation of organic EL element: Multifunctional vapor deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd. (4) Measurement of electrical properties of organic EL element: Multi-channel IVL measurement device manufactured by EHC Co., Ltd.

[0444] [1] Synthesis of Compounds [Synthesis Example 1] According to the methods described in Production Examples 2-1 and 2-2 of WO 2020 / 203407, an amine adduct of a polythiophene derivative, which is a polymer containing a repeating unit represented by the following formula (U1a), was synthesized.

[0445] (wherein a to d are the same as above.)

[0446] Synthesis Example 2 An arylsulfonic acid compound represented by formula (b-1) was synthesized according to the method described in WO 2006 / 025342.

[0447]

[0448] [2] Production of Surface-Treated Silica Sol [Production Example 1] 96.7 g of ST-OS (manufactured by Nissan Chemical Industries, Ltd.), which is a water-dispersed silica sol, and methanol (manufactured by Kanto Chemical Co., Ltd.; the same applies hereinafter) were placed in a recovery flask, and the water contained in the ST-OS was solvent-substituted with methanol using an evaporator, thereby obtaining a methanol-dispersed silica sol (solid content concentration: 16.7% by mass).

[0449] [Production Example 2] 29.9 g of the methanol-dispersed silica sol obtained in Production Example 1 and 20.1 g of methanol were placed in a reaction vessel, and the solid content concentration was adjusted to 10.0 mass%. 0.24 g (1.8 mmol) of trimethoxy(methyl)silane (Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred at 60°C under nitrogen for 3 hours. After cooling to room temperature, the mixture was filtered through a PTFE filter with a pore size of 1.0 µm to obtain surface-treated silica sol A [solid content (surface-treated silica) concentration 8.3 mass%].

[0450] [3] Removal of silane coupling agent [Production Example 3] A portion of the surface-modified silica sol A obtained in Production Example 2 was subjected to ultrafiltration membrane method to remove "unreacted and physically adsorbed silane coupling agent," thereby obtaining surface-modified silica sol B.

[0451] [4] Solvent substitution of surface-treated silica sol [Production Example 4] 18.2 g of the surface-modified silica sol A obtained in Production Example 2 and dipropylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Inc.; the same applies hereinafter) were placed in a recovery flask, and the methanol contained in the silica sol was subjected to solvent substitution with dipropylene glycol monomethyl ether using an evaporator, thereby obtaining silica sol C dispersed in dipropylene glycol monomethyl ether (solid content concentration: 12.2 mass%).

[0452] [Production Example 5] 18.6 g of the surface-modified silica sol B obtained in Production Example 3 and dipropylene glycol monomethyl ether were placed in a recovery flask, and the methanol contained in the silica sol was solvent-substituted with dipropylene glycol monomethyl ether using an evaporator, thereby obtaining silica sol D dispersed in dipropylene glycol monomethyl ether (solid content concentration: 11.1% by mass).

[0453] [5] Preparation of composition for preparing varnish [Preparation Example 1] 1.0 g of the polythiophene derivative amine adduct obtained in Synthesis Example 1 was added to 16.9 g of 1,3-dimethyl-2-imidazolidinone (manufactured by Kanto Chemical Co., Ltd.; the same applies hereinafter) and 2.1 g of 3-ethoxypropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 80°C for 3 hours using a hot stirrer to obtain a dark blue mixed solution.

[0454] Preparation Example 2 A 1,3-dimethyl-2-imidazolidinone solution containing 10% by mass of the arylsulfonic acid compound obtained in Synthesis Example 2 was prepared by stirring using a hot stirrer at 400 rpm and 50°C for 1 hour.

[0455] [6] Preparation of Charge-Transporting Varnish [Example 1-1] 2.34 g of 1,3-dimethyl-2-imidazolidinone, 4.99 g of dipropylene glycol (manufactured by Junsei Chemical Co., Ltd., the same applies hereinafter), and 1.38 g of dipropylene glycol monomethyl ether were placed in a recovery flask and stirred at room temperature for 30 minutes using a stirrer. Then, 1.07 g of the 1,3-dimethyl-2-imidazolidinone solution of the arylsulfonic acid compound obtained in Preparation Example 2 was added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Then, 0.86 g of the mixed solution obtained in Preparation Example 1 was added, and the mixture was stirred at room temperature for 30 minutes. Next, 4.05 g of the surface-treated silica sol D produced in Preparation Example 5 was added to the resulting mixed solution, and the mixture was 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 varnish (solids concentration: 4.0% by mass).

[0456] Comparative Example 1-1 A charge-transporting varnish (solid content concentration: 4% by mass) was obtained in the same manner as in Example 1-1, except that 3.69 g of the surface-treated silica sol C produced in Production Example 4 was used instead of the surface-treated silica sol D produced in Production Example 5.

[0457] [7] Storage of Charge-Transporting Varnish [Example 2-1] 1.5 g of the charge-transporting varnish prepared in Example 1-1 was placed in a 20 mL clean glass bottle, and the atmosphere inside the container was replaced with N2 in a glove box. Furthermore, this sample bottle was placed in an aluminum zip bag and stored in a refrigerator at 5°C for 2 months.

[0458] Example 2-2 The storage conditions were changed to room temperature, and the same procedure as in Example 2-1 was used for storage.

[0459] Comparative Example 2-1 Storage was carried out in the same manner as in Example 2-1, except that the charge transporting varnish of Comparative Example 1-1 was used instead of the charge transporting varnish of Example 1-1.

[0460] Comparative Example 2-2 The same procedure as in Example 2-2 was repeated except that the charge transporting varnish of Comparative Example 1-1 was used instead of the charge transporting varnish of Example 1-1.

[0461] The details of these Examples and Comparative Examples are summarized in Table 7.

[0462]

[0463] [8] Fabrication and Evaluation of Hole-Only Device (HOD) [Example 3-1] The charge-transporting varnish stored in Example 2-1 was applied to an ITO substrate using a spin coater and then dried at 120°C for 1 minute in an air atmosphere. The substrate was then baked at 230°C for 15 minutes in an air atmosphere to form a uniform 65 nm thin film (hole injection layer) on the ITO substrate. A 25 mm x 25 mm x 0.7 mm glass substrate with a patterned 50 nm thick 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). Next, the ITO substrate with the thin film formed thereon was vacuum-evaporated (vacuum level 1.0 x 10 -5 NPB was evaporated to a thickness of 80 nm using a vacuum evaporation method (Pa) at a deposition rate of 2.0 nm / s. Aluminum was then evaporated to a thickness of 80 nm at a deposition rate of 0.2 nm / s to form a cathode, thereby fabricating a hole-only device.

[0464] To prevent deterioration of characteristics due to the influence of oxygen, water, etc. in the air, the hole-only device was sealed with a sealing substrate before its 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 element was 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 substrate together with the organic EL element. 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 harden the adhesive.

[0465] Example 3-2 A hole-only device was fabricated in the same manner as in Example 3-1, except that the charge-transporting varnish in Example 3-1 was changed to the charge-transporting varnish stored in Example 2-2.

[0466] Comparative Examples 3-1 and 3-2 Hole-only devices were fabricated in the same manner as in Example 3-1, except that the charge-transporting varnish in Example 3-1 was changed to the charge-transporting varnishes stored in Comparative Examples 2-1 and 2-2, respectively.

[0467] The current-voltage characteristics were evaluated for each of the devices of Examples 3-1 and 3-2 and Comparative Examples 3-1 and 3-2. Specifically, the current density (mA / cm) was measured when a voltage of −5 V to +5 V was applied in 0.25 V increments to the hole-only devices. 2 Table 8 shows the current densities when a voltage of +5 V was applied to the elements of Examples 3-1 and 3-2 and Comparative Examples 3-1 and 3-2.

[0468]

[0469] As shown in Table 8, when a voltage of +5 V was applied to the hole-only device of Example 3-1, the current density was higher than that of the hole-only device prepared in Comparative Example 3-1. Similarly, the current density obtained in Example 3-2 was higher than that of Comparative Example 3-2. These results indicate that the charge-transporting varnish using ultrafiltered silica sol has improved storage stability.

Claims

1. A charge transporting varnish comprising SiO2 nanoparticles surface-treated with a silane coupling agent represented by the following formula (S1), a charge transporting substance, and an organic solvent, wherein the residual silane coupling agent has been removed. (In the formula, R v1 ~R v3 each independently represents a hydrogen atom, a chlorine atom, a hydroxyl group, an alkoxy group which may have a substituent, or an alkyl group which may have a substituent; R v1 ~R v3 at least one of the groups represents a hydrogen atom, a chlorine atom, a hydroxyl group, or an alkoxy group which may have a substituent; L represents a single bond or an alkylene group having 1 to 10 carbon atoms; R v4 represents an alkyl group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; an alkoxy group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; or an aryl group having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. v4 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, L is a single bond.

2. The above R v1 ~R v3 2. The charge transporting varnish according to claim 1, wherein is an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted alkoxy group having 1 to 10 carbon atoms.

3. The charge transporting varnish according to claim 1, wherein the charge transporting substance is a polythiophene derivative or an amine adduct thereof, or an arylamine derivative.

4. The charge transporting varnish according to claim 3, wherein the polythiophene derivative or its amine adduct is a polythiophene derivative or its amine adduct containing a repeating unit represented by the following formula (U1): (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 u -O] p -R e or a sulfo group, or R u1 and R u2 is bonded to form -O-Y u -O-, and Y u represents 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 u 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, 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.

5. R above u1 is a sulfo group, and the R u2 is an alkoxy group having 1 to 40 carbon atoms or -O-[Z u -O] p -R e or the above R u1 and R u2 is bonded to form -O-Y u 5. The charge transporting varnish according to claim 4, wherein the group is --O--.

6. The charge transporting varnish according to claim 3, wherein the arylamine derivative is represented by any one of the following formulas (T1) to (T4). (In the formula, R 1 each independently represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, a t-butoxycarbonyl group, or a benzyloxycarbonyl group; R 2 each independently represents a hydrogen atom, a hydroxyl 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, a monovalent hydrocarbon group which may have a substituent, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfo group, or a halogen atom; and each of m and n independently represents an integer of 1 or more, and m+n≦20 is satisfied. [In the formula, Ph 1 represents a group represented by formula (P1), (In the formula, R 3 ~R 6 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. 1 each independently represents a group represented by any one of formulas [B1] to [B11], (In the formula, R 7 ~R 27 , R 30 ~R 51 and R 53 ~R 154 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 28 and R 29 are each independently Z 1 R represents 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 52 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 Ar represents 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 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 2 is a halogen atom, a nitro group, a cyano group, or Z 3 Z represents 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 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; Z 5 is a halogen atom, a nitro group, a cyano group, or Z 3 Ar 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 2 each independently represents a group represented by any one of formulas [A1] to [A18], (In the formula, R 155 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 by Z 1 R represents 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 by 156 and R 157 are each independently Z 1 Ar represents 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 3 , Z 1 and Z 3 ~Z 5 has the same meaning as above.) k represents an integer of 1 to 10.] [In the formula, Z represents a group represented by any one of the following formulas (z1) to (z6); (In the formula, R z1 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; each Ar independently represents a group represented by the following formulas (J1) to (J4); (In formula (J1), R z2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms; or In the formula, D represents a diarylamino group in which each aryl group is independently an aryl group having 6 to 20 carbon atoms; z3 ~R z77 each independently represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms. F each independently represents a fluoroaryl group having 6 to 20 carbon atoms which may be substituted with a cyano group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which is substituted with a fluoroalkyl group having 1 to 20 carbon atoms, a fluorocycloalkyl group having 3 to 20 carbon atoms, a fluorobicycloalkyl group having 4 to 20 carbon atoms, a fluoroalkenyl group having 2 to 20 carbon atoms, or a fluoroalkynyl group having 2 to 20 carbon atoms and which may be substituted with a cyano group, a halogen atom, or a fluoroalkoxy group having 1 to 20 carbon atoms.] [In the formula, Ar c each independently represents a group represented by formula (Q), each Y independently represents an optionally substituted phenylene group, and each g independently represents an integer of 1 to 10. (In the formula, R q1 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R q2 each independently represents an aryl group which may be substituted and may contain a heteroatom; Ar s each independently represents an arylene group which may be substituted and which may contain a heteroatom.

7. The charge transporting varnish of claim 1 further comprising a dopant material.

8. The charge transporting varnish according to claim 7, wherein said dopant substance comprises at least one substance selected from the group consisting of arylsulfonic acid compounds and heteropolyacids.

9. The charge transporting varnish of claim 1, further comprising one or more amine compounds.

10. The charge transporting varnish according to claim 9, wherein the amine compound comprises a trialkylamine compound and an amine compound other than a trialkylamine compound.

11. The charge transporting varnish according to claim 10, wherein the amine compound other than the trialkylamine compound is a monoalkylamine compound.

12. A charge-transporting thin film obtained from the charge-transporting varnish according to any one of claims 1 to 11.

13. An electronic device comprising the charge transporting thin film according to claim 12.

14. The electronic device according to claim 13, wherein said charge transporting thin film is a hole injection layer or a hole transport layer.

15. The electronic device according to claim 14, which is an organic EL device or a quantum dot EL device.

16. A method for producing a charge transporting varnish comprising SiO2 nanoparticles surface-treated with a silane coupling agent represented by the following formula (S1), a charge transporting substance, and an organic solvent, the method including a step of removing any remaining silane coupling agent. (In the formula, R v1 ~R v3 each independently represents a hydrogen atom, a chlorine atom, a hydroxyl group, an alkoxy group which may have a substituent, or an alkyl group which may have a substituent; R v1 ~R v3 at least one of the groups represents a hydrogen atom, a chlorine atom, a hydroxyl group, or an alkoxy group which may have a substituent; L represents a single bond or an alkylene group having 1 to 10 carbon atoms; R v4 represents an alkyl group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; an alkoxy group having 1 to 10 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, and a hydroxy group; or an aryl group having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a halogen atom, a sulfo group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. v4 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, L is a single bond.

Images