WO2023189399A1

WO2023189399A1 - Polymer and use thereof

Info

Publication number: WO2023189399A1
Application number: PCT/JP2023/009226
Authority: WO
Inventors: 陽介倉田; 圭介首藤
Original assignee: 日産化学株式会社
Priority date: 2022-03-28
Filing date: 2023-03-10
Publication date: 2023-10-05
Also published as: TW202346396A

Abstract

Provided is a polymer suitable for use in forming charge-transporting thin films for use in organic EL elements, etc., the polymer being characterized by including, for example, the repeating units represented by the formulae.

Description

Polymers and their uses

The present invention relates to polymers and their uses.

An organic functional film made of an organic compound is used as a light emitting layer or a charge injection layer in an organic electroluminescent (hereinafter referred to as organic EL) element. In particular, the hole injection layer transfers charge between the anode and the hole transport layer or the light emitting layer, and plays an important function in achieving low voltage driving and high brightness of the organic EL element.

Formation methods for hole injection layers can be broadly divided into dry processes, typified by vapor deposition, and wet processes, typified by spin coating and inkjet methods. Comparing these processes, wet processes are generally superior. Thin films with high area flatness can be efficiently manufactured. Therefore, as organic EL displays are becoming larger in size, there is a demand for a hole injection layer that can be formed by a wet process, and there have been reports on technology related to hole injection materials that can be formed by a wet process. (Patent Document 1).

Additionally, in recent years, with the development of display technology, quantum dot electroluminescent (hereinafter referred to as quantum dot EL) elements that use quantum dot materials as light emitting layers have appeared, and are showing prospects for wide application. Quantum dot EL devices can be manufactured at low cost using a wet process, while their properties include control of emission wavelength, high color purity, high luminous efficiency, and use in flexible applications, making them ideal for use in display technology, lighting, etc. is attracting a lot of attention in the field of

In view of these circumstances, the present applicant has developed a charge transporting material that can be applied to various wet processes and provides a thin film that can realize excellent EL device characteristics when applied to the hole injection layer of an organic EL device. In addition, compounds suitable as charge transporting substances and dopants that exhibit solubility in organic solvents used therein have been developed (see Patent Documents 2 to 8 and Non-Patent Document 1).

In addition, when laminating another functional film on top of the formed thin film, in order to maintain the function of the thin film, care should be taken to prevent the thin film from being attacked by the functional film forming composition applied thereon. Therefore, high solvent resistance is required.

International Publication No. 2008/032616 International Publication No. 2008/129947 International Publication No. 2006/025342 International Publication No. 2010/058777 International Publication No. 2005/000832 International Publication No. 2009/096352 International Publication No. 2020/218316 International Publication No. 2017/217455

Similar to the techniques of the above-mentioned patent documents that have been developed so far, the present invention also aims to provide a polymer that can be suitably used for forming charge transporting thin films used in organic EL devices and the like.

As a result of extensive studies to solve the above problems, the present inventors have discovered that repeating units having a triarylamine structure, diaryl ether structure, or diaryl sulfide structure and a dialkylfluorene structure in their side chains, and fluorinated arylene A polymer containing a repeating unit having a group and an aryl group containing at least one sulfonic acid ester group in its side chain has high solubility in organic solvents, has excellent functions as a charge transport substance, and has a high charge transport property. They discovered that it is possible to create a thin film with excellent properties and solvent resistance, and completed the present invention.

That is, the present invention provides the following polymer and its use.
1. A polymer characterized by containing a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (B1).

[{In formula (A1), R ^M is a hydrogen atom or a methyl group. R ^1a and R ^2a each independently represent a single bond or a phenylene group, and some or all of the hydrogen atoms of the phenylene group are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, or an acryloyl group. may be substituted with a methacryloyl group, an oxetanyl group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
X ^1a is -N(Ar ^3a )-, -S- or -O-.
Ar ^1a is a divalent group obtained by removing two hydrogen atoms on the aromatic ring of an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or a dialkylfluorene represented by the following formula (A2). A group in which some or all of the hydrogen atoms on the aromatic rings of these groups are a cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, or epoxy group. , may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
Ar ^2a and Ar ^3a are each independently an aryl group having 6 to 20 carbon atoms or a monovalent group obtained by removing one hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2). Some or all of the hydrogen atoms on the aromatic ring of these groups are cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, epoxy group, carbon number It may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
When X ^1a is -N(Ar ^3a )-, Ar ^2a and Ar ^3a may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.
When R ^2a is a phenylene group, R ^2a and Ar ^2a may be bonded to each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded.
However, at least one of Ar ^1a to Ar ^3a is a group obtained by removing the hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2).

(In the formula, R ^3a and R ^4a are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure. be.)}
(In formula (B1), Ar _F represents a fluorinated arylene group, X ^1b represents O, S, NH, CONH or NHCO, and Ar _S represents at least one SO ₃ D ¹ D ² on the ring. Represents an aryl group having D ³ group, D ¹ represents a substituted or unsubstituted divalent hydrocarbon group, and D ² represents a single bond, O, S, or a substituted or unsubstituted divalent amino group. , D ³ represents a substituted or unsubstituted monovalent hydrocarbon group, but if D ² is a single bond, it may be a hydrogen atom.)
2. Polymer 1, wherein the repeating unit represented by the above formula (A1) is represented by the following formula (A1-1).

(In the formula, R ^M , R ^1a , R ^2a and Ar ^1a to Ar ^3a represent the same meanings as above.)
3. 1 or 2 polymers in which the above R ^1a is a single bond.
4. Any one of the polymers 1 to 3, wherein R ^2a is a phenylene group.
5. Any one of the polymers 1 to 4, wherein Ar ^1a is a 9,9-dimethyl-9H-fluorene-2,7-diyl group.
6. Any one of the polymers 1 to 5, wherein Ar _F is a perfluoroarylene group.
7. 6. The polymer of 6, wherein Ar _F is a tetrafluorophenylene group.
8. The polymer according to any one of 1 to 7, wherein the Ar _S is an aryl group having two or more of the SO ₃ D ¹ D ² D ³ groups on the ring.
9. 8. The polymer of 8, wherein the aryl group is a naphthyl group.
10. Any one of the polymers 1 to 9, wherein X ^1b is O.
11. A charge-transporting substance consisting of any one of polymers 1 to 10.
12. A charge transporting varnish comprising any one of the polymers 1 to 11 and a solvent.
13. Furthermore, 12 charge transporting varnishes containing a charge transporting substance other than any one of the polymers 1 to 11.
14. 13. The charge transporting varnish of 13, wherein the other charge transporting substance is an arylamine derivative (excluding the above polymer) or a thiophene derivative.
15. A charge transporting thin film obtained from the charge transporting varnish according to any one of items 12 to 14.
16. Electronic device comprising 15 charge transporting thin films.
17. An organic electroluminescent device comprising 15 charge transporting thin films.
18. 17. The organic electroluminescent device of 17, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.
19. Quantum dot electroluminescent device comprising 15 charge transporting thin films.
20. 19. The quantum dot electroluminescent device of 19, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.

The polymer of the present invention has high solubility in organic solvents and has excellent functions as a charge transporting substance, so it provides a charge transporting thin film with excellent electrical properties, and an organic EL device equipped with the thin film has the following properties: It exhibits good characteristics and is particularly excellent in life performance. Furthermore, since the obtained thin film has high solvent resistance, film thinning and swelling when other functional films are formed thereon are reduced.
The polymer of the present invention having such characteristics can be suitably used in thin films for electronic devices such as organic EL devices and quantum dot EL devices, particularly in compositions for forming thin films for organic EL displays and quantum dot EL displays. I can do it.

The present invention will be explained in more detail below.
[1] Polymer The polymer of the present invention is characterized by containing a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (B1).

In formula (A1), R ^M is a hydrogen atom or a methyl group. R ^1a and R ^2a each independently represent a single bond or a phenylene group, and some or all of the hydrogen atoms of the phenylene group are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, or an acryloyl group. may be substituted with a methacryloyl group, an oxetanyl group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.

Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, with a 1,4-phenylene group being preferred.

The above alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. A straight group having 1 to 20 carbon atoms such as sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group , a bicyclooctyl group, a bicyclononyl group, a bicyclodecyl group, and a cyclic alkyl group having 3 to 20 carbon atoms.

The halogenated alkyl group having 1 to 20 carbon atoms is not particularly limited as long as it is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms are substituted with halogen atoms. Specific examples include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2, 2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4 , 4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, etc. can be mentioned.

R ^1a is preferably a single bond, and R ^2a is preferably a phenylene group.

In formula (A1), X ^1a is -N(Ar ^3a )-, -S- or -O-.

In formula (A1), Ar ^1a represents an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or two hydrogen atoms on the aromatic ring of dialkylfluorene represented by the following formula (A2). It is a divalent group obtained by removing a part or all of the hydrogen atoms on the aromatic ring of these groups, such as a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, an acryloyl group, or a methacryloyl group. , an oxetanyl group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms and the halogenated alkyl group having 1 to 20 carbon atoms include those mentioned above.

(In the formula, R ^3a and R ^4a are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure. be.)

The above arylene groups having 6 to 20 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthalene-diyl group, 2,3-naphthalene-diyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, 1,2-anthracenediyl group, 1, 3-anthracenediyl group, 1,4-anthracenediyl group, 1,5-anthracenediyl group, 1,6-anthracenediyl group, 1,7-anthracenediyl group, 1,8-anthracenediyl group, 2,3- Examples include anthracenediyl group, 2,6-anthracenediyl group, 2,7-anthracenediyl group, 2,9-anthracenediyl group, 2,10-anthracenediyl group, and 9,10-anthracenediyl group.

Examples of the above heteroarylene group having 3 to 20 carbon atoms include 9-phenylcarbazole-3,6-diyl group, 9-phenylcarbazole-2,7-diyl group, 9-phenylcarbazole-3,6-dimethyl-2, Examples include a 7-diyl group, groups represented by the following formulas (H1) to (H33), and the like.

In formula (A2), R ^3a and R ^4a are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure. It is the basis.

The above alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. A straight group having 1 to 20 carbon atoms such as sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. Chain or branched alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group , a bicyclooctyl group, a bicyclononyl group, a bicyclodecyl group, and a cyclic alkyl group having 3 to 20 carbon atoms. Among these, methyl group and ethyl group are preferred, and methyl group is more preferred.

The above alkoxy group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 1 carbon number such as isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyl group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. ~20 linear or branched alkoxy groups; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group, Examples include cyclic alkoxy groups having 3 to 20 carbon atoms such as bicyclobutyloxy, bicyclopentyloxy, bicyclohexyloxy, bicycloheptyloxy, bicyclooctyloxy, bicyclononyloxy, and bicyclodecyloxy.

Examples of the alkyl group having 2 to 20 carbon atoms containing at least one ether structure include linear or branched alkyl groups in which at least one methylene group is substituted with an oxygen atom. However, the methylene group bonded to the fluorene skeleton is not substituted with an oxygen atom, and the adjacent methylene groups are not substituted with oxygen atoms at the same time. As such a group, a group represented by formula (A2-1) is preferable, and a group represented by formula (A2-2) is more preferable, considering the availability of the raw material compound.
-(R ^5a O) _p -R ^6a (A2-1)
-(CH ₂ CH ₂ O) _p -CH ₃ (A2-2)
(In the formula, R ^5a represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R ^6a represents a linear or branched alkylene group having 1 to 20 carbon atoms (number of carbon atoms in R) x p). p is an integer of 1 to 9. From the viewpoint of compatibility with the dopant, p is preferably 2 or more, more preferably 3 or more, and from the viewpoint of the ease of obtaining the raw material compound. , preferably 5 or less, more preferably 4 or less.)

Examples of the alkyl group having 2 to 20 carbon atoms containing at least one ether structure include -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ , -CH ₂ O(CH ₂ ) ₂ CH ₃ , -CH ₂ OCH(CH ₃ ) ₂ , -CH ₂ O(CH ₂ ) ₃ CH ₃ , -CH ₂ OCH ₂ CH(CH ₃ ) ₂ , -CH ₂ OC(CH ₃ ) ₃ , -CH ₂ O(CH ₂ ) ₄ CH ₃ , -CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ O(CH ₂ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ OCH ₂ CH(CH ₃ )CH ₂ CH ₃ , -CH ₂ OCH ₂ C(CH ₃ ) ₃ , -CH ₂ OCH(CH ₃ )CH(CH ₃ ) ₂ , -CH ₂ OC(CH ₃ ) ₂ CH ₂ CH ₃ , -CH ₂ OCH(CH ₂ CH ₃ ) ₂ , -CH ₂ O(CH ₂ ) ₅ CH ₃ , -CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ O (CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , -CH ₂ O(CH ₂ ) ₃ CH(CH ₃ ) ₂ , -CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , -CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ O(CH ₂ ) ₆ CH ₃ , -CH ₂ O(CH ₂ ) ₇ CH ₃ , -CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ O(CH ₂ ) ₈ CH ₃ , -CH ₂ O(CH ₂ ) ₉ CH ₃ , -CH ₂ O(CH ₂ ) ₁₀ CH ₃ , -CH ₂ O(CH ₂ ) ₁₁ CH ₃ , -CH ₂ O(CH ₂ ) ₁₂ CH ₃ , -CH ₂ O(CH ₂ ) ₁₃ CH ₃ , -CH ₂ O(CH ₂ ) ₁₄ CH ₃ , -CH ₂ O(CH ₂ ) ₁₅ CH ₃ , -CH ₂ O(CH ₂ ) ₁₆ CH ₃ , -CH ₂ O(CH ₂ ) ₁₇ CH ₃ , -CH ₂ O (CH ₂ ) ₁₈ CH ₃ , -CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ OCH(CH ₃ ) ₂ , -CH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ OC(CH ₃ ) ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₄ CH ₃ , -CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ OCH ₂ CH (CH ₃ )CH ₂ CH ₃ , -CH ₂ CH ₂ OCH ₂ C(CH ₃ ) ₃ , -CH ₂ CH ₂ OCH(CH ₃ )CH(CH ₃ ) ₂ , -CH ₂ CH ₂ OC(CH ₃ ) ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ OCH(CH ₂ CH ₃ ) ₂ , -CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , -CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH(CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , -CH ₂ CH ₂ O( CH ₂ ) ₃ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₇ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₉ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₀ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₂ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , -CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ , -CH ₂ CH ₂ O (CH ₂ ) ₁₇ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OC (CH ₃ ) ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₄ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₂ CH ₃ , CH ₂ CH ₂ CH ₂ O( CH ₂ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₅ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ )CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ C(CH ₃ ) ₃ , -CH ₂ CH ₂ CH ₂ OCH(CH ₃ )CH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₂ OCH(CH ₂ CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OCH(CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₃ )( CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₂ CH(CH ₃ )CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₃ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH(CH ₂ CH ₃ )(CH ₂ ) ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ OC(CH ₃ ) ₂ CH(CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₆ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₇ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH(CH ₂ CH ₃ )(CH ₂ ) ₃ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH 2 CH 2 OCH ₂ CH ₂ _OCH ₂ _CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH 2 OCH 2 CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ _{CH 2} _OCH ₂ CH ₂ _OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH 2 OCH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ _{CH 2} _CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃
, -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH 2 CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ _OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH 2 CH ₂ OCH 2 CH 2 CH ₂ OCH ₂ CH ₂ CH ₂ _OCH ₂ CH ₂ _CH ₂ _OCH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH 2 CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ _OCH ₂ CH _{2 CH 2} _CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH 2 OCH 2 CH ₂ OCH ₂ CH ₂ OCH ₂ _{CH 2} _OCH ₂ _CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₈ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₉ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₀ CH ₃ , - CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₁ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₂ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₃ CH ₃ , -CH ₂ Examples include CH ₂ CH ₂ O(CH ₂ ) ₁₄ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₅ CH ₃ , -CH ₂ CH ₂ CH ₂ O(CH ₂ ) ₁₆ CH ₃ and the like.

Divalent groups obtained by removing two hydrogen atoms on the aromatic ring of dialkylfluorene represented by formula (A2) include 9,9-dimethyl-9H-fluorene-2,7-diyl group, 9, 9-diethyl-9H-fluorene-2,7-diyl group, 9,9-dipropyl-9H-fluorene-2,7-diyl group, 9,9-dibutyl-9H-fluorene-2,7-diyl group, 9 ,9-dihexyl-9H-fluorene-2,7-diyl group, 9,9-dioctyl-9H-fluorene-2,7-diyl group, 9,9-bis(2-ethylhexyl)-9H-fluorene- 2,7-diyl group, 9,9-dimethoxy-9H-fluorene-2,7-diyl group, 9,9-diethoxy-9H-fluorene-2,7-diyl group, 9,9-bis[2-( Examples include, but are not limited to, 2-(2-methoxyethoxy)ethoxy)ethyl]-9H-fluorene-2,7-diyl group.

Among these, as Ar ^1a , a group obtained by removing two hydrogen atoms on the aromatic ring of dialkylfluorene represented by formula (A2) is preferable, and in particular, 9,9-dimethyl-9H-fluorene-2, 7-diyl group is preferred.

In formula (A1), Ar ^2a and Ar ^3a are each independently obtained by removing one hydrogen atom on the aromatic ring of the aryl group having 6 to 20 carbon atoms or the dialkylfluorene represented by formula (A2). It is a monovalent group, and some or all of the hydrogen atoms on the aromatic ring of these groups are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, an acryloyl group, a methacryloyl group, an oxetanyl group, It may be substituted with an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms and the halogenated alkyl group having 1 to 20 carbon atoms include those mentioned above.

The above aryl group having 6 to 20 carbon atoms includes phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, Examples include 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, and the like.

Monovalent groups obtained by removing one hydrogen atom on the aromatic ring of dialkylfluorene represented by formula (A2) include 9,9-dimethyl-9H-fluoren-2-yl group, 9,9- Dimethyl-9H-fluoren-3-yl group, 9,9-diethyl-9H-fluoren-2-yl group, 9,9-diethyl-9H-fluoren-3-yl group, 9,9-dipropyl-9H-fluorene -2-yl group, 9,9-dipropyl-9H-fluoren-3-yl group, 9,9-dibutyl-9H-fluoren-2-yl group, 9,9-dibutyl-9H-fluoren-3-yl group , 9,9-dihexyl-9H-fluoren-2-yl group, 9,9-dihexyl-9H-fluoren-3-yl group, 9,9-dioctyl-9H-fluoren-2-yl group, 9,9- Dioctyl-9H-fluoren-3-yl group, 9,9-bis(2-ethylhexyl)-9H-fluoren-2-yl group, 9,9-bis(2-ethylhexyl)-9H-fluoren- 3-yl group, 9,9-dimethoxy-9H-fluoren-2-yl group, 9,9-dimethoxy-9H-fluoren-3-yl group, 9,9-diethoxy-9H-fluoren-2-yl group, 9,9-diethoxy-9H-fluoren-3-yl group, 9,9-bis[2-(2-(2-methoxyethoxy)ethoxy)ethyl]-9H-fluoren-2-yl group, 9,9- Examples include, but are not limited to, bis[2-(2-(2-methoxyethoxy)ethoxy)ethyl]-9H-fluoren-3-yl group and the like.

When X ^1a is -N(Ar ^3a )-, Ar ^2a and Ar ^3a may be bonded to each other to form a ring with the nitrogen atom to which they are bonded. At this time, the structure of the ring is preferably a carbazole ring.

When R ^2a is a phenylene group, R ^2a and Ar ^2a may be bonded to each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded. At this time, the structure of the above ring is preferably a carbazole ring, a dibenzothiophene ring or a dibenzofuran ring.

However, at least one of Ar ^1a to Ar ^3a is a group obtained by removing a hydrogen atom on the aromatic ring of dialkylfluorene represented by formula (A2).

The repeating unit represented by formula (A1) is preferably one in which X ^1a is -N(Ar ^3a )-, and more preferably one represented by the following formula (A1-1).

(In the formula, R ^M , R ^1a , R ^2a and Ar ^1a to Ar ^3a represent the same meanings as above.)

Further, as the repeating unit represented by formula (A1-1), one represented by the following formula (A1-2) is even more preferable.

(In the formula, R ^M , R ^1a , R ^2a and Ar ^1a to Ar ^3a have the same meanings as above.)

In formula (B1), Ar _F represents a fluorinated arylene group.
The fluorinated arylene group of Ar _F is not particularly limited as long as at least one hydrogen atom on the arylene group is replaced with a fluorine atom, but at least one of the remaining hydrogen atoms is an electron-withdrawing group other than a sulfo group. It is preferable that it is substituted with.
Examples of electron-withdrawing groups 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; acyl group such as formyl group and acetyl group. Can be mentioned.
In particular, the fluorinated arylene group of Ar _F is preferably an arylene group substituted with two or more fluorine atoms, and more preferably a perfluoroarylene group.

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

X represents O, S, NH, CONH or NHCO, preferably O or S, and more preferably O.

More preferred embodiments of the repeating unit represented by the above formula (B1) include those represented by the following formula (B1-1).

(In the formula, n1 represents an integer from 1 to 4.)

More preferred embodiments of the repeating unit represented by the above formula (B1) include those represented by the following formula (B1-2).

(In the formula, n1 represents an integer from 1 to 4.)

More preferred embodiments of the repeating unit represented by the above formula (B1) include those represented by the following formula (B1-3).

Ar _S represents an aryl group having at least one SO ₃ D ¹ D ² D ³ group on the ring, D ¹ represents a substituted or unsubstituted divalent hydrocarbon group, D ² represents a single bond, O, S, or a substituted or unsubstituted divalent amino group, and D ³ represents a substituted or unsubstituted monovalent hydrocarbon group, but if D ² is a single bond, even if it is a hydrogen atom. good.

The number of carbon atoms in the aryl group constituting Ar _S is not particularly limited, but preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. Specific examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4 -phenanthryl group, 9-phenanthryl group, etc., but naphthyl group is preferable, and 1-naphthyl group is more preferable.
Further, the number of SO ₃ D ¹ D ² D ³ groups that Ar _S has may be one or more, but preferably 2 to 4, and more preferably 2.

The substituted or unsubstituted divalent hydrocarbon group for D ¹ is, for example, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, alkylene group having 1 to 2 carbon atoms, alkylene group having 1 to 2 carbon atoms, or 1 to 2 carbon atoms; ~2 Alkylenethio Alkylene group with 1 to 2 carbon atoms, Alkylene carbonyl group with 1 to 2 carbon atoms, Alkylene group with 1 to 2 carbon atoms, and some or all of the hydrogen atoms of these groups can further be hydroxyl group, amino group, silanol group, Thiol group, carboxyl group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, ester group, thioester group, amide group, nitro group, monovalent hydrocarbon group, organooxy group, organoamino group, organosilyl group, Examples include those substituted with an organothio group, an acyl group, a sulfone group, a halogen atom, and the like. In the present invention, an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene and pentamethylene groups, with methylene, ethylene, propylene and trimethylene groups being preferred.

D ² is a single bond, O, S, or a substituted or unsubstituted divalent amino group, and O is preferred in the present invention. Here, examples of the divalent substituted amino group include -N(CH ₃ )-, -N(C ₂ H ₅ )-, and -N(C ₃ H ₇ )-.

D ³ represents a substituted or unsubstituted monovalent hydrocarbon group, but may be a hydrogen atom when D ² is a single bond. Substituted or unsubstituted monovalent hydrocarbon groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, decyl. Alkyl groups such as groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; bicycloalkyl groups such as bicyclohexyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, Alkenyl groups such as 2-butenyl, 3-butenyl, hexenyl groups; aromatic ring groups (aryl groups) such as phenyl, xylyl, tolyl, biphenyl, naphthyl groups; aralkyl groups such as benzyl, phenylethyl, phenylcyclohexyl groups; Examples include those in which some or all of the hydrogen atoms of the group are further substituted with the above-mentioned substituents. According to the invention, methyl, ethyl, n-propyl, n-butyl and phenyl groups are preferred.

The above D ¹ to D ³ more preferably have a structure represented by the following formula (D).

In formula (D), R ^1d and R ^2d each independently represent a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, and R ^3d represents a linear or branched monovalent aliphatic hydrocarbon group. Represents an aliphatic hydrocarbon group or an alkoxy group. However, the total number of carbon atoms in R ^1d , R ^2d and R ^3d is 2 or more. The total number of carbon atoms in R ^1d , R ^2d and R ^3d is not particularly limited, but is preferably 20 or less, more preferably 10 or less.

The linear or branched monovalent aliphatic hydrocarbon group is not particularly limited, but includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl. , n-octyl, 2-ethylhexyl, alkyl groups having 1 to 18 carbon atoms such as decyl; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl , 3-butenyl, hexenyl, and other alkenyl groups having 2 to 18 carbon atoms.

As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and specifically, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, n-pentoxy and phenoxy Examples include groups.

As R ^1d , a methyl group is more preferable. As R ^2d , a hydrogen atom is preferable. R ^3d is preferably an alkoxy group, more preferably a methoxy, ethoxy, n-propoxy, n-butoxy and phenoxy group, even more preferably an ethoxy, n-butoxy and phenoxy group.

The structure represented by the above formula (D) is obtained by converting a predetermined arylsulfonic acid halide into a predetermined alcohol compound, for example, with reference to the method described in International Publication No. 2020/218316 (Patent Document 7). , can be introduced by esterification using an alcohol compound represented by the following formula (D'). In the present invention, the repeating unit represented by formula (B1) has such a sulfonic acid ester group, thereby improving solubility in an organic solvent. Furthermore, after the charge transporting thin film is formed, the sulfonic acid ester groups are decomposed by the heating process and sulfonic acid groups are generated, which improves the hydrophilicity of the thin film and improves its resistance to low polar solvents such as toluene. improves. This reduces thinning and swelling of the resulting charge transporting thin film.

(In the formula, R ^1d to R ^3d represent the same meanings as above.)

Suitable examples of Ar _S include those represented by the following formulas (Ar _S -1) to (Ar _S -6).

(In the formula, D ¹ to D ³ represent the same meanings as above. n represents an integer from 2 to 4.)

(In the formula, D ¹ to D ³ have the same meanings as above.)

(In the formula, D ¹ to D ³ have the same meanings as above.)

(In the formula, D ¹ to D ³ have the same meanings as above.)

More preferred embodiments of the above Ar _S include those represented by the following formulas (Ar _S -7) to (Ar _S -12).

(In the formula, R ^1d to R ^3d represent the same meanings as above. n represents an integer from 2 to 4.)

(In the formula, R ^1d to R ^3d represent the same meanings as above.)

(In the formula, R ^1d to R ^3d have the same meanings as above.)

(In the formula, R ^1d to R ^3d represent the same meanings as above.)

The polymer of the present invention may be a polymer containing only the repeating unit represented by the above formula (A1) and the repeating unit represented by the above formula (B1). Further, the polymer of the present invention may be a random copolymer, an alternating copolymer, or a block copolymer.

The content ratio of the units of formula (A1) and the units of formula (B1) is not particularly limited, but in consideration of improving the charge transport properties and solvent resistance of the obtained thin film, the molar ratio is as follows: Formula (A1):Formula (B1)=20:1 to 1:20 is preferable, 10:1 to 1:10 is more preferable, and 5:1 to 1:5 is even more preferable.

In addition, repeating units other than the repeating unit represented by formula (A1) and the repeating unit represented by formula (B1) may be included as long as the effects of the present invention are not impaired. Other repeating units include those containing polymerizable functional groups such as an acryloyl group, an acrylamide group, a methacryloyl group, a methacrylamide group, a vinyl ether group, and maleic anhydride. Further, from the viewpoint of increasing solubility in organic solvents, a repeating unit represented by the following formula (B2) is preferred.

In formula (B2), R' represents a monovalent organic group.
Examples of the monovalent organic group include a monovalent hydrocarbon group, a heteroaryl group, a -COOR" group (R" represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and the like.
There is no particular restriction on the number of carbon atoms in the monovalent hydrocarbon group, but it preferably has 1 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, Alkyl groups such as n-nonyl and n-decyl groups; phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl , aryl groups such as 9-phenanthryl group, and the like.

Specific examples of heteroaryl groups include 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, 4-pyridyl, etc. with 2 to 20 carbon atoms Examples include heteroaryl groups.

Examples of the alkyl group having 1 to 10 carbon atoms for R'' include the same groups as exemplified above, but among them, an alkyl group having 1 to 5 carbon atoms is preferred.

In addition, in the monovalent hydrocarbon group, heteroaryl group, and alkyl group having 1 to 10 carbon atoms of R'', some or all of the hydrogen atoms thereof may be substituted with a substituent.Such a substituent Examples of the halogen atom include a halogen atom, a cyano group, a nitro group, a carboxy group, a sulfo group, a hydroxyl group, etc. Examples of the halogen atom include the same atoms as exemplified above.

Among these, R' is preferably an aryl group substituted with a halogen atom, more preferably a fluorinated aryl group, in consideration of improving the device characteristics and life characteristics of the resulting organic EL device or quantum dot EL device. , perfluoroaryl groups are even more preferred.
In particular, a phenyl group substituted with a halogen atom is preferred, a fluorinated phenyl group is more preferred, and a perfluorophenyl group is even more preferred.

When the polymer of the present invention contains a repeating unit represented by formula (B2), the content ratio is not particularly limited, but in consideration of improving device characteristics and solvent resistance, the molar ratio is: [Sum of formula (A1) and formula (B1)]: formula (B2) = preferably 10:1 to 1:10, more preferably 5:1 to 1:5, even more preferably 3:1 to 1:3 Preferably, 1:1 is more preferable.

The molecular weight of the polymer 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, 1,500 to 10, 000 is more preferable, and 2,000 to 10,000 is even more preferable. Further, the molecular weight distribution (Mw/Mn) is not particularly limited, but is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Note that this weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[3] Method for producing polymer The polymer of the present invention is produced by a known radical polymerization method using a monomer represented by the following formula (a1) and a monomer represented by the following formula (b1) in the presence of a solvent and a radical polymerization initiator. It can be obtained by polymerization. In this case, the monomers represented by formula (a1) may be used in combination of two or more types, and the monomers represented by formula (b1) may be used in combination of two or more types.

(In the formula, R ^M , R ^1a , R ^2a , Ar ^1a , Ar ^2a , Ar _F , Ar _S , X ^1a and X ^1b represent the same meanings as above.)

Furthermore, in addition to the above monomers, a monomer represented by the following formula (a2) may be added as necessary.

(In the formula, R' represents the same meaning as above.)

As the radical polymerization initiator, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used.
A radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) ), alkyl peresters (peroxyneodecanoic acid tert-butyl ester, peroxypivalic acid tert-butyl ester, peroxy 2-ethylcyclohexanoic acid tert-amyl ester, etc.), persulfates (potassium persulfate, (sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile (AIBN), 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.), and the like. The radical thermal polymerization initiators may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3' , 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4- [p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s- Triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2 -Methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenylketone, bis(5-2,4-cyclo Pentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone , 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4 '-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2 -(3-Methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1- Examples include (2-benzoyl)ethanone. The radical photopolymerization initiators may be used alone or in combination of two or more.

The solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced polymer. Specific examples include water; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, tetra Methylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 2-propanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve , methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene Glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, toluene, diethyl ether, cyclohexanone, Ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3 Examples include organic solvents such as -methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

The polymerization temperature during radical polymerization can be any temperature in the range of 30 to 150°C, but is preferably in the range of 50 to 100°C.

The monomer represented by the above formula (a1) can be synthesized by combining various coupling reactions. As an example of the synthesis method, for example, as shown in scheme a below, a styrene compound represented by formula (a1-1) and an amine compound represented by formula (a1-2) below are subjected to a coupling reaction. There are several methods.

(In the formula, R ^M , R ^1a , R ^2a , X ^1a , Ar ^1a and Ar ^2a have the same meanings as above.)

In scheme a, X ^A is any group used in the coupling reaction. Specific examples of such groups include, for example, boronic acid groups such as -B(OH) ₂ and boronic acid ester groups when using the Suzuki-Miyaura coupling reaction.

In scheme a, each X ^B is independently a halogen atom or a pseudohalogen group. Examples of the halogen atom represented by X ^B include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a bromine atom or an iodine atom being preferred. Examples of the ^{pseudohalogen} group represented by Examples include sulfonyloxy group.

The solvent used in the coupling reaction is not particularly limited as long as it does not adversely affect the reaction, but examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), Halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, etc.) , diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), amides (N,N-dimethylformamide (DMF), N,N-dimethylacetamide, etc.) ), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), urea derivatives (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethylsulfoxide, sulfolane, etc.), nitriles (acetonitrile, propiolactone, etc.) nitrile, butyronitrile, etc.). Among these, preferred solvents are aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.) and aromatic hydrocarbons (benzene, nitrobenzene, toluene, etc.) from the viewpoint of efficiently obtaining the target product. , o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.) ), more preferably aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, THF, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.).

Catalysts used in the above coupling reaction include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (PdCl ₂ (dppf)), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ )), ₄ ), bis(triphenylphosphine)dichloropalladium (Pd(PPh ₃ ) ₂ Cl ₂ ), bis(benzylideneacetone)palladium (Pd(dba) ₂ ), tris(benzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) ), bis(tri-tert-butylphosphine)palladium (Pd(Pt-Bu ₃ ) ₂ ), palladium(II) acetate (Pd(OAc) ₂ ), and other palladium catalysts. These catalysts may be used with known suitable ligands.

The amount of the catalyst used is preferably an amount such that the molar ratio is 0.01 to 0.2, more preferably 0.03 to 0.1 with respect to the amine compound represented by formula (a1-2). . When a ligand is used, the amount used can be 0.1 to 3.0 equivalents, preferably 0.8 to 1.5 equivalents, relative to the metal complex used.

Additionally, a base may be used in the above coupling reaction. Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkoxyalkali metals such as tert-butoxylithium, tert-butoxysodium, and tert-butoxypotassium; sodium carbonate, potassium carbonate, etc. Alkali metal carbonate; alkali metal hydrogen carbonate such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal carbonate such as calcium carbonate; organolithium such as n-butyllithium, sec-butyllithium, tert-butyllithium; triethylamine, diisopropyl Examples include amines such as ethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine, but there are no particular limitations as long as they can be used in this type of reaction. In particular, sodium carbonate and potassium carbonate are preferred because they are easy to handle. The amount of the base used is usually about 1 to 20, preferably 4 to 8, in molar ratio to the amine compound represented by formula (a1-2).

In the above coupling reaction, the charging ratio of the styrene compound represented by the formula (a1-1) and the amine compound represented by the following formula (a1-2) is such that the styrene compound represented by the formula (a1-1) On the other hand, the amount of the amine compound represented by formula (a1-2) is preferably 0.2 to 2.0 in terms of molar ratio, and more preferably 0.5 to 1.0.

In the above coupling reaction, the reaction temperature is appropriately set in the range from the melting point to the boiling point of the solvent, taking into consideration the type and amount of the raw material compounds and catalysts used, but is usually about 20 to 120°C, preferably The temperature is 60-100°C. Further, the reaction time cannot be absolutely defined because it varies depending on the raw material compounds used, the reaction temperature, etc., but is usually about 0.5 to 12 hours.

After the reaction is completed, the desired monomer can be obtained by post-treatment according to a conventional method.

The monomer of formula (b1) above can be obtained by esterifying an arylsulfonic acid compound, which can be produced by a known method disclosed in Patent Document 6, by a known method. Esterification of the above-mentioned arylsulfonic acid compound can be carried out by esterifying a predetermined arylsulfonic acid halide using a predetermined alcohol compound, for example, International Publication No. 2020/218316 (Patent Document 7) The method disclosed in can be adopted.

[3] Charge-transporting varnish The charge-transporting varnish of the present invention contains a charge-transporting substance made of the above-mentioned polymer and a solvent.
In addition, in this invention, charge transport property is synonymous with electroconductivity, and is synonymous with hole transport property. The charge-transporting varnish may be one that itself has charge-transporting properties, or the solid film obtained therefrom may have charge-transporting properties.

The content of the above polymer in the charge transporting varnish of the present invention is preferably 0.1 to 100% by mass, more preferably 10 to 100% by mass, based on the solid content, from the viewpoint of the electrical properties and solvent resistance of the obtained thin film. Even more preferably, it is 20 to 100% by mass. The upper limit of the content of the polymer is usually 100% by mass or less, but when it contains optional components such as thiophene derivatives and arylamine derivatives described below, it is preferably 99.95% by mass or less, more preferably 99.95% by mass or less. .90% by mass or less.

The present invention may further contain charge transporting substances other than the above-mentioned polymers. The other charge-transporting substances mentioned above are not particularly limited, and may be appropriately selected from charge-transporting compounds, charge-transporting oligomers, charge-transporting polymers, etc. used in the fields of organic EL and quantum dot EL. Can be used.
Specific examples include arylamine derivatives such as oligoaniline derivatives, N,N'-diarylbenzidine derivatives, N,N,N',N'-tetraarylbenzidine derivatives (excluding the above polymers); oligothiophene derivatives , thiophene derivatives such as thienothiophene derivatives, thienobenzothiophene derivatives; various charge transport compounds such as pyrrole derivatives such as oligopyrrole; charge transport polymers such as charge transport oligomers, polythiophene derivatives, polyaniline derivatives, polypyrrole derivatives, etc. Among these, polythiophene derivatives and arylamine derivatives are preferred.

In addition, for example, a charge transporting compound (low molecular weight compound) or a charge transporting oligomer such as an arylamine compound represented by the formula (T2) or (T3) described below is useful from the viewpoint of producing a thin film with high flatness. Therefore, it is preferably monodisperse (that is, the molecular weight distribution is 1). In this case, the molecular weight of the charge transporting substance is usually about 200 to 9,000 from the viewpoint of preparing a uniform varnish that provides a thin film with high flatness, but from the viewpoint of obtaining a thin film with even better charge transportability, It is preferably 300 or more, more preferably 400 or more, and from the viewpoint of preparing a uniform varnish that provides a highly flat thin film with good reproducibility, it is preferably 8,000 or less, more preferably 7,000 or less, and 6,000 or less. is even more preferable, and even more preferably 5,000 or less.

Other charge transporting substances include, for example, JP2002-151272A, WO2004/105446, WO2005/043962, WO2008/032617, and WO2008/032616. , International Publication No. 2013/042623, International Publication No. 2014/141998, International Publication No. 2014/185208, International Publication No. 2015/050253, International Publication No. 2015/137391, International Publication No. 2015/137395, International Publication No. Examples include those disclosed in Publication No. 2015/146912, International Publication No. 2015/146965, International Publication No. 2016/190326, International Publication No. 2016/136544, International Publication No. 2016/204079, etc.

In a preferred embodiment, the other charge transporting substance is a polythiophene derivative containing a repeating unit represented by formula (T1) or an amine adduct thereof.

In the formula, R ^1t and R ^2t each independently represent 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, or a C 1 to 40 alkoxy group. is a fluoroalkoxy group, an aryloxy group having 6 to 20 carbon atoms, -O-[Z-O] _h -R ^e , or a sulfo group, or -O- formed by combining R ^1t and R ^2t YO-, Y is an alkylene group having 1 to 40 carbon atoms which may contain an ether bond and may be substituted with a sulfo group, and Z may be substituted with a halogen atom. A good alkylene group having 1 to 40 carbon atoms, h 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 a carbon It is an aryl group of number 6 to 20.

The alkyl group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and 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, tetracontyl groups and the like. In the present invention, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

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 the specific Examples include fluoromethyl, difluoromethyl, perfluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,2-difluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1,2 -Trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,2,2,2-tetrafluoroethyl, perfluoroethyl Fluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 1,2-difluoropropyl, 1,3-difluoropropyl, 2,2-difluoropropyl, 2,3- Difluoropropyl, 3,3-difluoropropyl, 1,1,2-trifluoropropyl, 1,1,3-trifluoropropyl, 1,2,3-trifluoropropyl, 1,3,3-trifluoropropyl, 2,2,3-trifluoropropyl, 2,3,3-trifluoropropyl, 3,3,3-trifluoropropyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,3- Tetrafluoropropyl, 1,2,2,3-tetrafluoropropyl, 1,3,3,3-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,3,3,3-tetrafluoro Propyl, 1,1,2,2,3-pentafluoropropyl, 1,2,2,3,3-pentafluoropropyl, 1,1,3,3,3-pentafluoropropyl, 1,2,3, Examples include 3,3-pentafluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl group, etc. .

As the alkoxy group having 1 to 40 carbon atoms, the alkyl group therein may be linear, branched, or cyclic, and specific examples include methoxy, ethoxy, n-propoxy, i-propoxy, c -Propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy , n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyl An example is an oxy group.

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 the specific Examples include fluoromethoxy, difluoromethoxy, perfluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 1,2-difluoroethoxy, 1,1-difluoroethoxy, 2,2-difluoroethoxy, 1,1,2 -Trifluoroethoxy, 1,2,2-trifluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 1,2,2,2-tetrafluoroethoxy, perfluoroethoxy, Fluoroethoxy, 1-fluoropropoxy, 2-fluoropropoxy, 3-fluoropropoxy, 1,1-difluoropropoxy, 1,2-difluoropropoxy, 1,3-difluoropropoxy, 2,2-difluoropropoxy, 2,3- Difluoropropoxy, 3,3-difluoropropoxy, 1,1,2-trifluoropropoxy, 1,1,3-trifluoropropoxy, 1,2,3-trifluoropropoxy, 1,3,3-trifluoropropoxy, 2,2,3-trifluoropropoxy, 2,3,3-trifluoropropoxy, 3,3,3-trifluoropropoxy, 1,1,2,2-tetrafluoropropoxy, 1,1,2,3- Tetrafluoropropoxy, 1,2,2,3-tetrafluoropropoxy, 1,3,3,3-tetrafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 2,3,3,3-tetrafluoro Propoxy, 1,1,2,2,3-pentafluoropropoxy, 1,2,2,3,3-pentafluoropropoxy, 1,1,3,3,3-pentafluoropropoxy, 1,2,3, Examples include 3,3-pentafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, and perfluoropropoxy groups.

The alkylene group having 1 to 40 carbon atoms may be linear, branched, or cyclic, and specific examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. , octamethylene, nonamethylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosanylene groups, and the like.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, Examples include 4-phenanthryl and 9-phenanthryl groups, with phenyl, tolyl and naphthyl groups being preferred.
Specific examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy, anthracenoxy, naphthoxy, phenanthrenoxy, and fluorenoxy groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In the above formula (T1), R ^1t and R ^2t each independently represent a hydrogen atom, a fluoroalkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, -O[C(R ^a R ^b ) -C(R ^c R ^d )-O] _h -R ^e , -OR ^f , or a sulfo group, or -O-Y-O- formed by combining R ^1t and R ^2t is preferred.
R ^a to R ^d each independently represent 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; Examples include the same groups as listed above.
Among these, R ^a to 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.
R ^e is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and preferably a hydrogen atom, a methyl group, a propyl group, or a butyl group.
h is preferably 1 to 5, more preferably 1, 2 or 3.

R ^f 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; A fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group is preferred, and -CH ₂ CF ₃ is more preferred.

The above R ^1t is preferably a hydrogen atom or a sulfo group, more preferably a sulfo group, and R ^2t is preferably an alkoxy group having 1 to 40 carbon atoms or -O-[Z-O] _h -R ^e , more preferably -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e or -OR ^f , even more preferably -O[C(R ^a R ^b )-C (R ^c R ^d )-O] _h -R ^e , -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -OH or -O-CH ₂ CH ₂ -OH, or -O-Y-O- formed by combining R ^1t and R ^2t with each other.

For example, the polythiophene derivative according to a preferred embodiment of the present invention contains a repeating unit in which R ^1t is a sulfo group and R ^2t is other than a sulfo group, or is formed by combining R ^1t and R ^2t . -O-Y-O-.
Preferably, the polythiophene derivative contains a repeating unit in which R ^1t is a sulfo group and R ^2t is an alkoxy group having 1 to 40 carbon atoms or -O-[Z-O] _h -R ^e , Or it includes a repeating unit that is -O-Y-O- formed by combining R ^1t and R ^2t .
More preferably, in the polythiophene derivative, R ^1t is a sulfo group, and R ^2t is -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e or -OR Contains a repeating unit that is ^f .
Even more preferably, in the polythiophene derivative, R ^1t is a sulfo group, and R ^2t is -O[C(R ^a R ^b )-C(R ^c R ^d )-O] _h -R ^e It contains a repeating unit, or it contains a repeating unit which is -O-Y-O- formed by combining R ^1t and R ^2t .
More preferably, in the polythiophene derivative, R ^1t is a sulfo group, and R ^2t is -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ - Contains a repeating unit that is O-CH ₂ CH ₂ -OH or -O-CH ₂ CH ₂ -OH, or R ^1t and R ^2t are bonded to each other and are represented by the following formulas (Y1) and (Y2). Contains repeating units that are groups.

Preferred specific examples of the polythiophene derivatives include polythiophenes containing at least one type of repeating unit represented by the following formulas (T1-1) to (T1-5).

Further, as a preferable structure of the polythiophene derivative, for example, a polythiophene derivative having a structure represented by the following formula (T1a) can be mentioned. In addition, in the following formula, each unit may be bonded randomly or may be bonded as a block polymer.

In the formula, a to d represent the molar ratio of each unit, and 0≦a≦1, 0≦b≦1, 0<a+b≦1, 0≦c<1, 0≦d<1, a+b+c+d=1. be satisfied.

Furthermore, the polythiophene derivatives may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers). For polymers comprising monomer A and monomer B, block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) _k -multiblock copolymers. Polythiophenes also contain repeating units derived from other types of monomers, such as thienothiophenes, selenophenes, pyrroles, furans, tellurophenes, anilines, arylamines, and arylenes (such as phenylene, phenylene vinylene, and fluorene). May contain.

The content of the repeating unit represented by formula (T1) in the polythiophene derivative is preferably more than 50 mol%, more preferably 80 mol% or more, and more preferably 90 mol% or more, based on all the repeating units contained in the polythiophene derivative. It is more preferably 95 mol% or more, and most preferably 100 mol%.

The above polythiophene derivative may contain repeating units derived from impurities, depending on the purity of the starting monomer used for polymerization. The term "homopolymer" above refers to a polymer containing repeat units derived from one type of monomer, but may also contain repeat units derived from impurities. The polythiophene derivative is preferably a polymer in which basically all of the repeating units are repeating units represented by the above formula (T1), and the polythiophene derivative is preferably a polymer in which basically all repeating units are repeating units represented by the above formula (T1-1) to (T1-5). More preferably, it is a polymer containing at least one repeating unit.

When the above-mentioned polythiophene derivative contains a repeating unit having a sulfo group, from the viewpoint of further improving solubility and dispersibility in organic solvents, the polythiophene derivative has an amine compound added to at least a part of the sulfo group contained therein. Amine adducts are preferred.

Amine compounds that can be used to form amine adducts 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-penta Monoalkylamine compounds such as decylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosanylamine; aniline, tolylamine, 1-naphthylamine, 2-naphthylamine, 1- Anthrylamine, 2-anthrylamine, 9-anthrylamine, 1-phenanthrylamine, 2-phenanthrylamine, 3-phenanthrylamine, 4-phenanthrylamine, 9-phenanthrylamine Primary amine compounds such as monoarylamine compounds such as; N-ethylmethylamine, N-methyl-n-propylamine, N-methylisopropylamine, N-methyl-n-butylamine, N-methyl-s-butylamine, -Methyl-t-butylamine, N-methylisobutylamine, diethylamine, N-ethyl-n-propylamine, N-ethylisopropylamine, N-ethyl-n-butylamine, N-ethyl-s-butylamine, N-ethyl- t-Butylamine, dipropylamine, Nn-propylisopropylamine, Nn-propyl-n-butylamine, Nn-bropyl-s-butylamine, diisopropylamine, Nn-butylisopropylamine, Nt -Butylisopropylamine, di(n-butyl)amine, di(s-butyl)amine, diisobutylamine, aziridine (ethyleneimine), 2-methylaziridine (propyleneimine), 2,2-dimethylaziridine, azetidine (trimethylene) imine), 2-methylazetidine, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 2,2,6, Dialkylamine compounds such as 6-tetramethylpiperidine, hexamethyleneimine, heptamethyleneimine, octamethyleneimine; diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1,1'-dinaphthylamine, 2 , 2'-dinaphthylamine, 1,2'-dinaphthylamine, carbazole, 7H-benzo[c]carbazole, 11H-benzo[a]carbazole, 7H-dibenzo[c,g]carbazole, 13H-dibenzo[a,i ] Diarylamine compounds such as carbazole; N-methylaniline, N-ethylaniline, Nn-propylaniline, N-isopropylaniline, Nn-butylaniline, Ns-butylaniline, N-isobutylaniline, N- -Methyl-1-naphthylamine, N-ethyl-1-naphthylamine, Nn-propyl-1-naphthylamine, indoline, isoindoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydro Secondary amine compounds such as alkylarylamine compounds such as isoquinoline; 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-methyldiisopropyl Amine, N-methyldi(n-butyl)amine, N-methyldiisobutylamine, triethylamine, N,N-diethyl-n-butylamine, N,N-diisopropylethylamine, N,N-di(n-butyl)ethylamine, triethylamine, Trialkyl such as (n-propyl)amine, tri(i-propyl)amine, tri(n-butyl)amine, tri(i-butyl)amine, 1-methylacetidine, 1-methylpyrrolidine, 1-methylpiperidine, etc. Amine compounds; triarylamine compounds such as triphenylamine; alkyldiarylamine compounds such as N-methyldiphenylamine, N-ethyldiphenylamine, 9-methylcarbazole, 9-ethylcarbazole; N,N-diethylaniline, N,N- Examples include tertiary amine compounds such as dialkylarylamine compounds such as di(n-propyl)aniline, N,N-di(i-propyl)aniline, and N,N-di(n-butyl)aniline; Considering the balance of solubility in the body, charge transportability of the resulting organic functional film, etc., 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 its solution and stirring well.

Moreover, the above-mentioned polythiophene derivative or its amine adduct may be treated with a reducing agent.
In polythiophene derivatives or their amine adducts, some of their constituent repeating units may have an oxidized chemical structure called a "quinoid structure." The term ``quinoid structure'' is used for the term ``benzenoid structure.'' The latter is a structure containing an aromatic ring, whereas the former is a structure in which the double bond within the aromatic ring moves outside the ring (its (As a result, the aromatic ring disappears), meaning a structure in which two extracyclic double bonds are formed that are conjugated with other double bonds remaining in the ring. For those skilled in the art, the relationship between these two structures can be easily understood from the relationship between the structures of benzoquinone and hydroquinone. Quinoid structures for the repeat 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 (T1) is shown in the following formula (T1').

(In the formula, R ^1t and R ^2t are as defined in the above formula (T1).)

This quinoid structure is produced by a process in which a polythiophene derivative containing the repeating unit represented by the above formula (T1) undergoes an oxidation reaction with a dopant, a so-called doping reaction, and a "polaron structure" and " It forms part of a structure called "bipolaron structure". These structures are known. In the production of organic EL devices and quantum dot EL devices, it is essential to introduce a “polaron structure” and/or a “bipolaron structure”. This is achieved by intentionally causing the above doping reaction when the formed thin film is subjected to a firing process. The reason why the polythiophene derivative contains a quinoid structure before undergoing this doping reaction is that the polythiophene derivative undergoes an unintended oxidation reaction equivalent to the doping reaction during its manufacturing process (especially in the sulfonation step). This is thought to be due to the

There is a correlation between the amount of quinoid structure contained in the above polythiophene derivative and the solubility and dispersibility of the polythiophene derivative in organic solvents, and as the amount of quinoid structure increases, the solubility and dispersibility tend to decrease. be. Therefore, the introduction of the quinoid structure after a thin film is formed from the charge-transporting varnish does not cause any problem, but if the quinoid structure is excessively introduced into the polythiophene derivative due to the unintended oxidation reaction described above, the charge It may interfere with the production of transportable varnish. It is known that polythiophene derivatives vary in their solubility and dispersibility in organic solvents, and one of the reasons for this is that the amount of quinoid structure introduced into polythiophene due to the above-mentioned unintended oxidation reaction is This is thought to vary depending on differences in the manufacturing conditions of each polythiophene derivative.
Therefore, when the above polythiophene derivative is subjected to a reduction treatment using a reducing agent, even if an excessive amount of quinoid structure is introduced into the polythiophene derivative, the reduction reduces the quinoid structure, improving the solubility and dispersibility of the polythiophene derivative in organic solvents. As a result, it becomes possible to stably produce a varnish with good charge transport properties that provides a thin film with excellent homogeneity.

The conditions for the reduction treatment are such that the quinoid structure is reduced and appropriately converted to a non-oxidized structure, that is, the benzenoid structure (for example, in a polythiophene derivative containing a repeating unit represented by the above formula (T1), There is no particular restriction as long as the quinoid structure represented by the above formula (T1') can be converted into the structure represented by the above formula (T1), but for example, in the presence of a suitable solvent or This treatment can be carried out simply by contacting the polythiophene derivative or amine adduct with a reducing agent in the absence of the reducing agent.
Such a reducing agent is not particularly limited as long as the reduction is carried out appropriately, but suitable examples include aqueous ammonia, hydrazine, etc., which are easily available commercially.
Furthermore, the amount of the reducing agent cannot be unconditionally defined as it varies depending on the amount of the reducing agent used, but from the viewpoint that the reduction is usually appropriate for 100 parts by mass of the polythiophene derivative or amine adduct to be treated, The content is 0.1 parts by mass or more, and from the viewpoint of preventing excessive reducing agent from remaining, the content is 10 parts by mass or less.

As a specific example of the reduction treatment method, a polythiophene derivative or an amine adduct is stirred in 28% ammonia water at room temperature overnight. The reduction treatment under such relatively mild conditions sufficiently improves the solubility and dispersibility of the polythiophene derivative and amine adduct in organic solvents.

When using an amine adduct of a polythiophene derivative in the charge transporting varnish of the present invention, the above reduction treatment may be performed before or after forming the amine adduct.

Note that as a result of this reduction treatment, the solubility and dispersibility of the polythiophene derivative or its amine adduct in the solvent changes, and as a result, the polythiophene derivative or its amine adduct that was not dissolved in the reaction system at the start of the treatment is Sometimes it is dissolved. In such cases, an organic solvent that is incompatible with the polythiophene derivative or its amine adduct (for sulfonated polythiophene, acetone, 2-propanol, etc.) is added to the reaction system to dissolve the polythiophene derivative or its amine adduct. The polythiophene derivative or its amine adduct can be recovered by a method such as precipitation and filtration.

The weight average molecular weight of the polythiophene derivative containing the repeating unit represented by formula (T1) or its amine adduct is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 100,000, Even more preferred is about 10,000 to about 50,000. By setting the weight average molecular weight to be at least the lower limit, good conductivity can be obtained with good reproducibility, and by setting the weight average molecular weight to be at most the upper limit, solubility in a solvent is improved. Note that this weight average molecular weight is a polystyrene equivalent value determined by GPC.

The polythiophene derivative or its amine adduct contained in the charge-transporting varnish used in the present invention may be only one type of polythiophene derivative or its amine adduct containing the repeating unit represented by formula (T1), or may be two types. It may be more than that.
Further, the polythiophene derivative containing the repeating unit represented by formula (T1) may be a commercially available product or one polymerized by a known method using a thiophene derivative as a starting material, but in either case, It is also preferable to use one purified by a method such as reprecipitation or ion exchange. By using a purified product, the characteristics of an organic EL device or a quantum dot EL device including a thin film obtained from the charge transporting varnish of the present invention can be further improved.

Sulfonation of conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in Seshadri et al., US Pat. No. 8,017,241. Moreover, sulfonated polythiophene is described in International Publication No. 2008/073149 and International Publication No. 2016/171935.

Note that at least a portion of the polythiophene derivative containing the repeating unit represented by the above formula (T1) or its amine adduct is dissolved in the below-mentioned solvent.

In the present invention, when a polythiophene derivative or an amine adduct thereof containing a repeating unit represented by formula (T1) is used, the polythiophene derivative or an amine adduct thereof and another charge transporting compound are used as charge transporting substances. Although a charge transporting substance consisting of the following may be used in combination, it is preferable that only a polythiophene derivative containing a repeating unit represented by formula (T1) or an amine adduct thereof is included.

When using a polythiophene derivative containing a repeating unit represented by the above formula (T1) or an amine adduct thereof, the content is usually 0.05% in the solid content, taking into consideration the desired film thickness and viscosity of the varnish. It is preferably determined in the range of 0.1 to 35% by weight, more preferably 0.1 to 35% by weight.

Other preferable embodiments of the above-mentioned other charge transporting substances include those represented by the following formulas (T2) and (T3).

Note that the aniline derivative represented by formula (T2) may be an oxidized aniline derivative (quinone diimine derivative) having a quinone diimine structure represented by the following formula in its molecule. Examples of the method of oxidizing an aniline derivative to obtain a quinone diimine derivative include the methods described in International Publication No. 2008/010474 and International Publication No. 2014/119782.

In formula (T2), R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z ¹ . group, an alkenyl group having 2 to 20 carbon atoms or 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, which may be substituted with Z ² , - NHY ¹ , -NY ² Y ³ , -OY ⁴ , or -SY ⁵ group, and Y ¹ to Y ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, which may be substituted with Z ¹ group, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, which may be substituted with Z ² . and 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 a halogen atom, nitro group, cyano group, amino group, or Z ³ , Z ² is a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, which may be substituted with Z ³ represents an alkynyl group, Z ³ represents a halogen atom, a nitro group, a cyano group, or an amino group, and k and l are each independently an integer of 1 to 5.

In formula (T3), R ⁷ to R ¹⁰ are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxy group, or a Z ¹ an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, 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; , represents ^an aryl ^group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to ²⁰ carbon atoms, which may be substituted with hydrogen atom, phenyl group, naphthyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, furanyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thienyl group (these groups include halogen atom, nitro group, Cyano group, hydroxyl group, thiol group, phosphoric acid group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms 20 haloalkyl group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, or acyl group having 1 to 20 carbon atoms. ) or a group represented by formula (T3a) (however, at least one of R ¹¹ to R ¹⁴ is a hydrogen atom), m is an integer of 2 to 5. represent. Z ¹ and Z ² have the same meanings as above.

In formula (T3a), R ¹⁵ to R ¹⁸ are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxy group, or a Z ¹ an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, 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; , represents an aryl ^group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or ^an acyl group having 1 to ²⁰ carbon atoms, which may be substituted with phenyl group, naphthyl group, anthryl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, furanyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thienyl group (these groups are bonded to each other to form a ring). A halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfo group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms. , alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms (Optionally substituted with 20 aralkyl groups or acyl groups having 1 to 20 carbon atoms.) Z ¹ and Z ² have the same meanings as above.

In each of the above formulas, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl. , n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and other linear or branched alkyl groups having 1 to 20 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, and other cyclic alkyl groups having 3 to 20 carbon atoms.

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, n- Examples include 1-eicosenyl group.

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- Examples include butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, n-1-eicosynyl and the like.

Specific examples of aryl groups 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- Examples include phenanthryl and 9-phenanthryl groups.

Specific examples of aralkyl groups having 7 to 20 carbon atoms include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl groups, and the like.

Specific examples of heteroaryl groups having 2 to 20 carbon atoms include 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, 4-pyridyl group, etc. can be mentioned.

Examples of the haloalkyl group having 1 to 20 carbon atoms include those in which at least one hydrogen atom of the above alkyl group having 1 to 20 carbon atoms has been replaced with a halogen atom. Among them, a fluoroalkyl group is preferred, and a perfluoro Alkyl groups are more preferred.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2, 2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, nonafluorobutyl, 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2 , 3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3, 3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3, Examples include 4,4,5,5,6,6,6-nonafluorohexyl group.

Specific examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy , n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyloxy and the like.

Specific examples of thioalkoxy (alkylthio) groups having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, n- hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, n-tridecylthio, n-tetradecylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio, Examples include n-octadecylthio, n-nonadecylthio, and n-eicosanylthio groups.

Specific examples of the acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and benzoyl groups.

In formula (T2), R ¹ to R ⁶ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , or an alkyl group having 6 to 20 carbon atoms which may be substituted with Z ² 20 aryl groups, -NHY ¹ , -NY ² Y ³ , -OY ⁴ , or -SY ⁵ are preferred, and in this case, Y ¹ to Y ⁵ have 1 to 1 carbon atoms, which may be substituted with Z ¹ 10 alkyl group or an aryl group having 6 to 10 carbon atoms which may be substituted with Z ² is preferable, and an alkyl group having 1 to 6 carbon atoms which may be substituted with Z ¹ or an aryl group having 6 to 6 carbon atoms which may be substituted with Z ² is preferable. A phenyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms or a phenyl group is even more preferred.
In particular, R ¹ to R ⁶ are more preferably a hydrogen atom, a fluorine atom, a methyl group, a phenyl group, or a diphenylamino group (-NY ² Y ³ in which Y ² and Y ³ are phenyl groups), and R ¹ to R ⁴ is a hydrogen atom, and it is even more preferable that R ⁵ and R ⁶ are both hydrogen atoms or diphenylamino groups.

In particular, in R ¹ to R ⁶ and Y ¹ to Y ⁵ , Z ¹ is preferably a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted with Z ³ , and more preferably a fluorine atom or a phenyl group. Preferably, it is not present (that is, it is an unsubstituted group), and Z ² is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z ³ . A fluorine atom or an alkyl group having 1 to 6 carbon atoms is more preferred, and its absence (ie, an unsubstituted group) is even more preferred.
Furthermore, Z ³ is preferably a halogen atom, more preferably a fluorine atom, and even more preferably absent (that is, an unsubstituted group).
From the viewpoint of increasing the solubility of the aniline derivative represented by formula (H2), k and l preferably satisfy k+l≦8, and more preferably k+l≦5.

In formula (T3), R ⁷ to R ¹⁰ are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Hydrogen atoms are more preferred.
Further, in consideration of increasing the solubility of the aniline derivative represented by formula (T3) in a solvent and increasing the uniformity of the obtained thin film, it is preferable that R ¹¹ and R ¹³ are both hydrogen atoms.
In particular, R ¹¹ and R ¹³ are both hydrogen atoms, and R ¹² and R ¹⁴ are each independently a phenyl group (this phenyl group can be a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, group, sulfo group, carboxy group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms may be substituted with an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms.) or a group represented by the above formula (T3a), R ¹¹ and R ¹³ are both hydrogen atoms, and R ¹² and R ¹⁴ are each independently a phenyl group, or R ^19' and More preferably, it is a group represented by the following formula (T3a') in which both R ^20' are phenyl groups, R ¹¹ and R ¹³ are both hydrogen atoms, and R ¹² and R ¹⁴ are both phenyl groups. It is even more preferable that
In addition, m is preferably 2 to 4 in consideration of the ease of obtaining the compound, ease of production, cost, etc., and more preferably 2 or 3 in consideration of increasing the solubility in the solvent. Considering the balance of availability, ease of manufacture, manufacturing cost, solubility in solvents, transparency of the obtained thin film, etc., 2 is optimal.

The aniline derivatives represented by formulas (T2) and (T3) may be commercially available products or those produced by known methods such as those described in the above publications; In this case, it is preferable to use a varnish purified by recrystallization, vapor deposition, etc. before preparing the charge transporting varnish. By using a purified varnish, the characteristics of an electronic device including a thin film obtained from the varnish can be further improved. When purifying by recrystallization, for example, 1,4-dioxane, tetrahydrofuran, etc. can be used as the solvent.

In the present invention, the charge transport substance represented by formulas (T2) and (T3) is one type of compound selected from the compounds represented by formulas (T2) and (T3) (i.e., the dispersity of molecular weight distribution 1) may be used alone or in combination of two or more compounds.

Specific examples of charge transporting substances represented by formulas (T2) and (T3) that can be suitably used in the present invention include, but are not limited to, the following.

(In the formula, DPA represents a diphenylamino group.)

When using the aniline derivative represented by the above formula (T2) and the aniline derivative represented by the formula (T3), the content thereof is usually determined in consideration of the desired film thickness, viscosity of the varnish, etc. in the solid content. It is preferably 0.05 to 90% by mass, more preferably 0.1 to 75% by mass, determined as appropriate.

Note that the charge transporting varnish of the present invention may contain a known organic dopant substance or inorganic dopant substance.

As the solvent used in preparing the charge transporting varnish of the present invention, a highly polar solvent that can satisfactorily dissolve the charge transporting substance, dopant substance, etc. to be used can be used. Furthermore, if necessary, a low polarity solvent may be used because it has better process compatibility than a highly polar solvent. In the present invention, a low polar solvent is defined as one having a dielectric constant of less than 7 at a frequency of 100 kHz, and a high polar solvent is defined as one having a dielectric constant of 7 or more at a frequency of 100 kHz.

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

In addition, as highly polar solvents, for example,
Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone;
Ketone solvents such as methyl ethyl 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, 2,3-butanediol;
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 monohydric alcohol solvent;
Examples include sulfoxide solvents such as dimethyl sulfoxide.

Furthermore, the charge transporting varnish of the present invention may contain one or more metal oxide nanoparticles. Nanoparticles refer to fine particles whose average primary particle diameter is on the order of nanometers (typically 500 nm or less). Metal oxide nanoparticles refer to metal oxides shaped into nanoparticles.
The primary particle diameter of the metal oxide nanoparticles is not particularly limited as long as it is nanosized, but is preferably from 2 to 150 nm, more preferably from 3 to 100 nm, and even more preferably from 5 to 50 nm. Note that the particle diameter is a value measured using a nitrogen adsorption isotherm according to the BET method.

The metal constituting the metal oxide nanoparticles includes not only metals in the usual sense but also metalloids.
Metals in the usual sense include, but are not limited to, tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum ( It is preferable to use one or more selected from the group consisting of Ta) and W (tungsten).
On the other hand, metalloid means an element whose chemical and/or physical properties are intermediate between metals and nonmetals. Although a universal definition of semimetals has not been established, in the present invention, a total of six metalloids are used: boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te). The element is a metalloid. These metalloids may be used alone or in combination of two or more types, or may be used in combination with metals in the usual sense.

In particular, metal oxide nanoparticles include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum It is preferable that the metal oxide contains one or more metal oxides selected from (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten). Note that when the metals are a combination of two or more types, the metal oxide may be a mixture of oxides of individual metals, or may be a composite oxide containing a plurality of metals.

Specific examples of metal oxides include B ₂ O ₃ , B ₂ O, SiO ₂ , SiO, GeO ₂ , GeO, As ₂ O ₄ , As ₂ O ₃ , As ₂ O ₅ , Sb ₂ O ₃ , Sb ₂ Examples include O ₅ , TeO ₂ , SnO ₂ , SnO, ZrO ₂ , Al ₂ O ₃ , ZnO, etc., but B ₂ O ₃ , B ₂ O, SiO ₂ , SiO, GeO ₂ , GeO, As ₂ O ₄ , As ₂ O ₃ , As ₂ O ₅ , SnO ₂ , SnO, Sb ₂ O ₃ , TeO ₂ and mixtures thereof are preferred, and SiO ₂ is more preferred.

The amount of metal oxide nanoparticles is not particularly limited, but from the viewpoint of improving the transparency of the thin film obtained and the uniformity of the film, the lower limit of the amount of metal oxide nanoparticles in the solid content is usually 50%. It is preferably 60% by mass, more preferably 65% by mass, and its upper limit is usually 95% by mass, preferably 90% by mass.

In particular, in the present invention, it is preferable to use silica sol in which SiO ₂ nanoparticles are dispersed in a dispersion medium as the metal oxide nanoparticles.
The silica sol is not particularly limited, and can be appropriately selected from known silica sols.
Commercially available silica sols are usually in the form of dispersions. Commercially available silica sols include _SiO2 nanoparticles in various solvents, such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, acetic acid. Examples include those dispersed in ethyl, toluene, propylene glycol monomethyl ether acetate, and the like.

Specific examples of commercially available silica sols include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40, ST-OL manufactured by Nissan Chemical Co., Ltd., and Silicadol 20 manufactured by Nippon Kagaku Kogyo Co., Ltd. , 30, 40, etc.; methanol silica sol manufactured by Nissan Chemical Co., Ltd., MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, EG- Examples include, but are not limited to, organosilica sols such as ST.
The solid content concentration of the silica sol is also not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass.

The amount of silica sol used is appropriately determined in consideration of its concentration so that the amount of silica ultimately contained in the charge transporting varnish corresponds to the amount of metal oxide nanoparticles described above.

In addition, when the obtained thin film is used as a hole injection layer of an organic EL device or a quantum dot EL device, the charge transporting varnish of the present invention improves the injection property to the hole transport layer and improves the life characteristics of the device. For this purpose, an organic silane compound may be included. Its content is usually about 1 to 30% by mass based on the total mass of the charge transport material and the dopant material.
Examples of the organic silane compound include dialkoxysilane compounds, trialkoxysilane compounds, and tetraalkoxysilane compounds.

The viscosity of the charge transporting varnish is determined appropriately depending on the thickness of the thin film to be produced and the solid content concentration, but it is usually 1 to 50 mPa·s at 25°C. In the present invention, the solid content refers to components other than the solvent contained in the charge transporting varnish.
In addition, the solid content concentration of the charge transporting varnish is determined as appropriate by taking into account the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but it is usually 0.1 to 20.0% by mass. %, and in consideration of improving the coatability of the varnish, it is preferably about 0.2 to 10.0% by mass, more preferably about 0.5 to 8.0% by mass.

The method for preparing the charge-transporting varnish is not particularly limited, but for example, a charge-transporting substance and a dopant substance are dissolved in a highly polar solvent, and a low-polar solvent and surface-treated metal oxide nanoparticles, etc. are added thereto. Examples include a method in which a highly polar solvent and a low polar solvent are mixed, a charge transporting substance and a dopant substance are dissolved therein, and further surface-treated metal oxide nanoparticles are added.

In particular, when preparing a charge-transporting varnish, from the viewpoint of obtaining a thin film with higher flatness with good reproducibility, after dissolving the charge-transporting substance, dopant substance, etc. in an organic solvent, a submicrometer-order filter, etc. It is desirable to use it after it has been filtered.

The charge-transporting varnish described above can be used to easily produce a charge-transporting thin film, and therefore can be suitably used in producing electronic devices, particularly organic EL devices and quantum dot EL devices.
In this case, the charge-transporting thin film can be formed by applying the above-described charge-transporting varnish onto a base material and baking it.
The varnish application method is not particularly limited, and examples include dip method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spray method, slit coating method, etc. It is preferable to adjust the viscosity and surface tension of the varnish accordingly.

Furthermore, the firing atmosphere of the charge transporting varnish after application is not particularly limited, and a thin film with a uniform coating surface and high charge transporting properties can be produced not only in the air but also in an inert gas such as nitrogen or in a vacuum. However, depending on the type of dopant material used, a thin film having charge transporting properties may be obtained with good reproducibility by firing the varnish in the atmosphere.

The firing temperature is determined as appropriate within the range of about 100 to 260°C, taking into account the purpose of the thin film to be obtained, the degree of charge transport property to be imparted to the thin film, the type and boiling point of the solvent, etc. When used as a hole injection layer of an organic EL device or a quantum dot EL device, the temperature is preferably about 140 to 250°C, more preferably about 145 to 240°C, but when the above-mentioned arylamine compound is used as a charge transporting substance, Even when firing at a low temperature of 200° C. or lower, a thin film having good charge transport properties can be obtained.
In addition, during firing, the temperature may be changed in two or more steps in order to develop more uniform film formation or to advance the reaction on the substrate, and the heating may be performed using, for example, a hot plate or This may be done using a suitable device such as an oven.

The thickness of the charge transporting thin film is not particularly limited, but it may be provided between an anode and a light emitting layer such as a hole injection layer, a hole transport layer, a hole injection transport layer, etc. of an organic EL element or a quantum dot EL element. When used as a functional layer, the thickness is preferably 5 to 300 nm. As a method for changing the film thickness, there are methods such as changing the solid content concentration in the varnish or changing the amount of solution on the substrate during coating.

[3] Organic EL device and quantum dot EL device When applying the above charge transporting thin film to an organic EL device or a quantum dot EL device, the above-mentioned It can be configured to include a charge transporting thin film.
Typical configurations of organic EL devices and quantum dot EL devices include (a) to (f) below, but are not limited to these. In addition, in the following structure, an electron blocking layer etc. can also be provided between a light emitting layer and an anode, and a hole (hole) blocking layer etc. can also be provided between a light emitting layer and a cathode as needed. Further, the hole injection layer, the hole transport layer, or the hole injection transport layer may also have a function as an electron blocking layer, etc., and the electron injection layer, the electron transport layer, or the electron injection transport layer may block holes. It may also have a function as a block layer or the like. Furthermore, it is also possible to provide an arbitrary functional layer 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/Positive Hole injection layer/hole transport layer/light emitting layer/cathode (f) anode/hole injection transport layer/light emitting layer/cathode

"Hole injection layer", "hole transport layer" and "hole injection transport layer" are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. If only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a "hole injection transport layer", and between the light emitting layer and the anode, When two or more layers of hole-transporting materials are provided, the layer close to the anode is the "hole-injection layer" and the other layers are the "hole-transporting layers." In particular, for the hole injection (transport) layer, a thin film is used 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.
"Electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between a light emitting layer and a cathode, and have the function of transporting electrons from the cathode to the light emitting layer. If only one layer of electron transport material is provided between the light emitting layer and the cathode, it is an "electron injection transport layer", and the layer of electron transport material is provided between the light emitting layer and the cathode. When two or more layers are provided, the layer close to the cathode is the "electron injection layer", and the other layers are the "electron transport layers".
The "light-emitting layer" is an organic layer having a light-emitting function, and may be an organic light-emitting layer or a quantum dot light-emitting layer. Correspondingly, when the light emitting layer is an EL device of an organic light emitting layer, it is an organic EL device, and when the light emitting layer is an EL device of a quantum dot light emitting layer, it is a quantum dot EL device. When a doping system is adopted, it includes a host material and a dopant material. At this time, the host material mainly has the function of promoting recombination of electrons and holes and confining excitons within the light emitting layer, and the dopant material makes the excitons obtained by recombination efficiently emit light. Has a function. In the case of a phosphorescent device, the host material mainly has the function of confining excitons generated by the dopant within the light emitting layer.

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

Examples of the materials used and the manufacturing method for manufacturing an EL device using the charge-transporting varnish of the present invention include, but are not limited to, the following.
An example of a method for producing an organic EL device or a quantum dot EL device having a hole injection layer made of a thin film obtained from the charge transporting varnish of the present invention is as follows. Note that it is preferable that the electrode is previously subjected to surface treatment such as cleaning with alcohol, pure water, etc., UV ozone treatment, oxygen-plasma treatment, etc. within a range that does not adversely affect the electrode.
A hole injection layer made of the charge transporting thin film of the present invention is formed on the anode substrate by the method described above. This is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light emitting layer, an electron transport layer/hole blocking layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, instead of forming the hole transport layer and the light emitting layer by vapor deposition in this method, a composition for forming a hole transport layer containing a hole transporting polymer and a composition for forming a light emitting layer containing a light emitting polymer may be used. These layers are formed using a wet process. Note that, if necessary, an electron blocking layer may be provided between the light emitting layer and the hole transport layer. In the above, an example (sequential structure) in which the anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer/hole blocking layer, electron injection layer, and cathode are laminated in this order has been described, but the present invention is not limited to this. , a cathode, an electron injection layer, an electron transport layer/hole blocking layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode may be laminated in this order (reverse structure).

Examples of anode materials include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and metal anodes made of metals typified by aluminum and their alloys. Preferably, the material has been subjected to chemical treatment. Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
Note that other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.

Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis (phenyl)-benzidine (α-NPD), 4,4',4"-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4"-tris[1 -Triarylamines such as naphthyl(phenyl)amino]triphenylamine (1-TNATA), 5,5''-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2': Examples include, but are not limited to, oligothiophenes such as 5',2''-terthiophene (BMA-3T).

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

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, pyrimidine derivatives, and the like.

Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (MgO), and alumina (Al ₂ O ₃ ), lithium fluoride (LiF), and sodium fluoride (NaF). metal fluorides, but are not limited to these.
Examples of the cathode material include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
Examples of the material for forming the electron block layer include tris(phenylpyrazole)iridium, but are not limited thereto.

Examples of hole-transporting polymers include poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid), 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)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)- benzidine]-endcapped with polysilcisquinoxane, poly[(9,9-didioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl)) diphenylamine)], but is not limited thereto.

Examples of luminescent polymers include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene) (MEH- Examples include, but are not limited to, polyphenylene vinylene derivatives such as PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

In the form in which the light emitting layer includes quantum dots (quantum dot EL device), the quantum dot material may include a II-VI group semiconductor, a III-V group semiconductor, an I-III-VI group semiconductor, a group IV semiconductor, and a semiconductor material. It can contain at least one semiconductor material selected from the group consisting of Group I-II-IV-VI semiconductors. Specific examples of the semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS , CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgST e, HgZnSeS, HgZnSeTe, HgZnSTe; GaN, GaP, GaAs, GaSb, 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, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, Pb SeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe , SnPbSeTe _, SnPbSTe; Si, Ge, SiC, SiGe, AgInSe ₂ , CuGaSe ₂ , CuInS 2 , CuGaS ₂ , CuInSe ₂ , AgInS ₂ , AgGaSe ₂ , AgGaS ₂ , C, Si and Ge. , to these Not limited.

As described above, the charge transporting varnish of the present invention can be used to connect an anode and a light emitting layer such as a hole injection layer, a hole transport layer, a hole injection transport layer, etc. of an organic EL device or a quantum dot EL device (quantum dot light emitting diode). Although it is suitably used to form a functional layer provided between, it is also used in addition to organic photoelectric conversion elements, organic thin film solar cells, organic perovskite photoelectric conversion elements, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, It can also be used to form charge-transporting thin films in electronic devices such as organic optical analyzers, organic photoreceptors, organic field quenchers, light-emitting electrochemical cells, quantum lasers, organic laser diodes, and organic plasmon light-emitting devices. .

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The equipment used is as follows.
(1) ^1H -NMR: Bruker nuclear magnetic resonance spectrometer AVANCE III HD500MHz
(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) measurement: Shimadzu Corporation (Column: SHODEX GPC KF-803L + GPC KF-804L, Column temperature: 40°C, Detector: UV detector (254 nm) ) and RI detector, eluent: THF, column flow rate: 1.0 mL/min.), standard sample: polystyrene (3) Substrate cleaning: Choshu Sangyo Co., Ltd., substrate cleaning device (low-pressure plasma method)
(4) Application of charge transporting varnish: Spin coater MS-A100 manufactured by Mikasa Co., Ltd.
(5) Film thickness measurement: Fine shape measuring device Surfcoder ET-4000 manufactured by Kosaka Institute Co., Ltd.
(6) Fabrication of organic EL element: Multifunctional vapor deposition system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
(7) Measurement of brightness, etc. of organic EL elements: Multi-channel IVL measuring device manufactured by EHC Co., Ltd.

[1] Synthesis of raw material compounds [Synthesis Example 1]

In a three-neck flask, add 10.0 g of sodium 1-naphthol-3,6-disulfonate (manufactured by Yamada Chemical Industries, Ltd.) and 2,3,4,5,6-pentafluorostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.). ), 5.02 g of sodium carbonate (manufactured by Kanto Kagaku Co., Ltd.), and 100 g of dimethyl sulfoxide (manufactured by Junsei Kagaku Co., Ltd., hereinafter the same) were added, and the mixture was stirred at 80° C. in a nitrogen atmosphere for 30 hours. After cooling the reaction solution to room temperature, 200 g of dimethyl sulfoxide was added and stirred at room temperature for 3 hours to dissolve the precipitated product. After filtering the obtained solution, the filtrate was depressurized to remove the solvent to obtain a crude product. The obtained crude product was added to 900 g of a mixed solvent (1/1 (w/w)) of 2-propanol (manufactured by Junsei Kagaku Co., Ltd.) and ethyl acetate (manufactured by Junsei Kagaku Co., Ltd., hereinafter the same), and the mixture was heated at room temperature. The mixture was stirred for 1 hour. The precipitated solid was collected by filtration, and the obtained solid was dried under reduced pressure to obtain Compound 1 (yield: 11.3 g, yield: 76%). The ¹ H-NMR spectrum of Compound 1 is shown below.
^1H -NMR (500MHz, DMSO): δ 5.87 (d, J = 11.5Hz, 1H), 6.12 (d, J = 18.0Hz, 1H), 6.72 (dd, J = 18 .0, 11.5Hz, 1H), 6.99 (s, 1H), 7.88 (dd, J=8.5, 1.5Hz, 1H), 7.97 (s, 1H), 8.21 (s, 1H), 8.25 (d, J=8.5Hz, 1H)

[Synthesis example 2]

Compound 1 (11.3 g) was dissolved in 56.5 g of water, and ion exchange was performed by column chromatography using a cation exchange resin Dowex Monosphere 650C (150 mL, extraction solvent: water). Fractions around pH 1 were collected and dried under reduced pressure to obtain Compound 2 (10.24 g, yield 98.8%).
Compound 3 and Compound 4 described below were synthesized sequentially according to the method described in patent document (International Publication No. 2020/218316). 122 mg of dimethylformamide (manufactured by Kanto Kagaku Co., Ltd.) and 12 g of thionyl chloride (manufactured by Kanto Kagaku Co., Ltd.) were added to a four-necked flask under a nitrogen atmosphere, and the mixture was stirred at 70° C. for 1 hour. Thereafter, a mixed solution of Compound 2 (4.0 g) and 12 g of 1,2-dimethoxyethane (Tokyo Kasei Kogyo Co., Ltd.) was slowly added dropwise, and the mixture was stirred at 70° C. for 4 hours. Thereafter, 200 g of hexane (manufactured by Kanto Kagaku Co., Ltd., hereinafter the same) was added, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was filtered, washed with 50 g of hexane, and then dried at 50° C. for 3 hours under reduced pressure to obtain pale yellow Compound 3 (2.4 g) (yield: 56%).

The ¹ H-NMR spectrum of Compound 3 is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 5.84 (d, J = 11.9 Hz, 1H), 6.22 (d, J = 18.0 Hz, 1H), 6.75 (dd, J = 11.9Hz, 18.0Hz, 1H), 7.35 (s, 1H), 8.37 (dd, J=9.0Hz, 1.9Hz, 1H), 8.57 (s, 1H), 8. 78 (d, J=9.0Hz, 1H), 8.84 (d, J=1.8Hz, 1H)

[Synthesis example 3]

Under a nitrogen atmosphere, compound 3 (2.4 g) and 7.68 g of 1-ethoxy-2-propanol (manufactured by Junsei Kagaku Co., Ltd., the same hereinafter) were added to a 20 mL two-necked flask, and stirred at 0 to 5 °C. . Thereafter, 1.3 g of N,N-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.2 g of dehydrated N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.), and 1-ethoxy-2-propanol ( A mixed solution of 2.4 g) was added dropwise, and the mixture was stirred at 0 to 5°C for 1 hour. Thereafter, 28 g of ethyl acetate was added, and the organic layer was washed by separating the layers using a 15% aqueous ammonium chloride solution, and 14 g of diisopropyl ether was added to the organic layer after the separation. Thereafter, the funnel was filled with 9.6 g of silica gel suspended in a solution of ethyl acetate: diisopropyl ether = 2:1 (mass ratio), and the separated solution was filtered. Thereafter, the silica gel was washed with a solution of ethyl acetate:diisopropyl ether=2:1 (mass ratio). The resulting solution was concentrated and added dropwise to 2-propanol under ice cooling. The precipitate was filtered off and dried under reduced pressure at room temperature for 4 hours to obtain 1.5 g of Compound 4 as a white powder (yield 49.5%).

The ¹ H-NMR spectrum of Compound 4 is shown below.
¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.96-0.94 (m, 6H), 1.31 (dd, J=6.5Hz, 0.8Hz, 3H), 1.38 (d, 6.5Hz, 3H), 3.50-3.27 (m, 8H), 4.78-4.73 (m, 1H), 4.88-4.82 (m, 1H), 5.81 ( d, J = 12.0Hz, 1H), 6.19 (d, 18.0Hz, 1H), 6.73 (dd, J = 18.0Hz, 12.0Hz, 1H), 7.20 (s, 1H ), 8.19 (dd, J = 8.9Hz, 1.7Hz, 1H), 8.39 (s, 1H), 8.61 (d, J = 8.9Hz, 1H), 8.66 (d , J=1.4Hz, 1H)

[Synthesis example 4]

In a 300 mL four-neck flask, 4.44 g of 4-vinylphenylboronic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd., the same applies hereinafter), and 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (manufactured by AGLAIA TECH). ) 11.97 g, tetrakistriphenylphosphine palladium (manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter the same) 0.90 g, sodium carbonate (manufactured by Junsei Kagaku Co., Ltd., the same hereinafter) 9.54 g, toluene (Junsei Kagaku Co., Ltd.) , hereinafter the same), ethanol (manufactured by Junsei Kagaku Co., Ltd., hereinafter the same), and water were added, and the mixture was reacted at 80° C. for 4 hours. The organic layer was washed with water through liquid separation, and the organic layer was concentrated. Methanol was added to the obtained solid, stirred for 30 minutes, and the solid was filtered and dried to obtain 10.27 g of Compound 5. In a 300 mL four-necked flask, compound 5 (9.06 g), 8.31 g of 2-(4-biphenylyl)amino-9,9-dimethylfluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), and bis(dibenzylideneacetone)palladium ( 0.397 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.400 g of tri-t-butylphosphonium tetrafluoroborate (manufactured by Fuji Film Wako Chemical Co., Ltd.), 2.43 g of sodium tert-butoxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) ) and tetrahydrofuran were added, and the mixture was reacted at 70°C for 3 hours. The organic layer was washed with water through liquid separation, and the organic layer was concentrated. The obtained solid was purified by silica gel chromatography to obtain 11.00 g (yield 68%) of Compound 6.

The ¹ H-NMR spectrum of compound 6 is shown below.
^1H -NMR (500MHz, THF-d8): δ 7.78-7.76 (m, 2H), 7.71-7.63 (m, 8H), 7.61 (d, J = 9.0Hz , 2H), 7.54 (d, J = 8.0Hz, 2H), 7.45-7.41 (m, 3H), 7.38 (t, J = 2.0Hz, 2H), 7.32 -7.27 (m, 5H), 7.14 (d, J = 8.0Hz, 2H), 6.80 (dd, J = 17.6, 10.9Hz, 1H), 5.84 (d, J = 17.7Hz, 1H), 5.25 (d, J = 11.1Hz, 1H), 1.51 (s, 6H), 1.45 (s, 6H)

[Synthesis example 5]

In a 300 mL four-necked flask, 4.44 g of 4-vinylphenylboronic acid, 8.68 g of 3-bromo-9-phenylcarbazole (manufactured by AGLAIA TECH), 0.104 g of tetrakistriphenylphosphine palladium, 11.97 g of sodium carbonate, and toluene. , ethanol, and water were added, and the mixture was reacted at 80° C. for 4 hours. The organic layer was washed with water through liquid separation, and the organic layer was concentrated. Methanol was added to the obtained solid, stirred for 30 minutes, and the solid was filtered and dried to obtain 7.04 g of Compound 7 (76% yield).

The ¹ H-NMR spectrum of Compound 7 is shown below.
^1H -NMR (500MHz, DMSO-d6): δ 8.62 (d, J = 1.5Hz, 1H), 8.37 (d, J = 7.5Hz, 1H), 7.80-7.76 (m, 3H), 7.72-7.69 (m, 2H), 7.66-7.65 (m, 2H), 7.60-7.54 (m, 3H), 7.47-7 .43 (m, 2H), 7.40 (d, J = 8.0Hz, 1H), 7.32 (t, J = 8.0Hz, 1H), 6.80 (dd, J = 17.5, 10.5Hz, 1H), 5.89 (d, J = 18.0Hz, 1H), 5.25 (d, J = 11.0Hz, 1H)

[2] Polymer synthesis [Example 1-1]

Under a nitrogen atmosphere, 200 mg (0.31 mmol) of Compound 6, 50 mg (0.08 mmol) of Compound 4, 6.3 mg of AIBN (manufactured by Kanto Kagaku Co., Ltd., the same applies hereinafter), and 2.5 g of degassed toluene were placed in a 10 mL two-necked flask. and stirred at 80°C for 24 hours. The solution after the reaction was added dropwise to 30 g of a mixed solvent of 2-propanol:ethyl acetate=1:3 (mass ratio), and the mixture was stirred at room temperature. The precipitated solid was filtered off and washed with a mixed solvent of 2-propanol:ethyl acetate=1:3 (mass ratio). The washed solid was dried at 40° C. for 5 hours under reduced pressure to obtain 60 mg of yellow powder polymer P1.
GPC: Mw=12,000, Mn=9,100, Mw/Mn=1.32

[Example 1-2]
Under a nitrogen atmosphere, 200 mg (0.31 mmol) of Compound 6, 100 mg (0.15 mmol) of Compound 4, 7.6 mg of AIBN, and 3.0 g of degassed toluene were added to a 10 mL two-necked flask and stirred at 80° C. for 25 hours. The solution after the reaction was added dropwise to 30 g of a mixed solvent of 2-propanol:ethyl acetate=1:1 (mass ratio), and the mixture was stirred at room temperature. The precipitated solid was filtered and washed with a mixed solvent of 2-propanol:ethyl acetate=1:1 (mass ratio). The washed solid was dried at 40° C. for 5 hours under reduced pressure to obtain 180 mg of yellow powder of polymer P2.
GPC: Mw=8,500, Mn=6,000, Mw/Mn=1.42

[Comparative example 1-1]

Under a nitrogen atmosphere, 1.5 g of Compound 7, 71.3 mg of AIBN, and 12 g of degassed toluene were added to a 30 mL two-necked flask, and the mixture was stirred at 80° C. for 10 hours. The solution after the reaction was added dropwise to 120 g of ethyl acetate, and the mixture was stirred at room temperature. The precipitated solid was filtered off and washed with ethyl acetate. The washed solid was dried under reduced pressure at 40° C. for 5 hours to obtain 720 mg of polymer P3 as a pale yellow powder.
GPC: Mw=8,300, Mn=5,900, Mw/Mn=1.41

[Comparative example 1-2]
When 200 mg (0.31 mmol) of compound 6, 73 mg (0.15 mmol) of compound 2, 6.3 mg of AIBN, and 2.5 g of degassed toluene were added to a 10 mL two-necked flask under a nitrogen atmosphere, compound 2 precipitated and polymerized. I couldn't react.

[Comparative example 1-3]

Under a nitrogen atmosphere, 1,014 mg (1.55 mmol) of Compound 6, 370 mg (0.77 mmol) of Compound 2, 38 mg of AIBN, and 13.8 g of degassed N,N-dimethylacetamide (manufactured by Kanto Kagaku Co., Ltd.) were added in 30 mL. The mixture was added to a neck flask and stirred at 80°C for 20 hours. The solution after the reaction was added dropwise to 70 g of a mixed solvent of ethyl acetate:methanol=3:1 (mass ratio), and the mixture was stirred at room temperature. The precipitated solid was separated by filtration and washed with a mixed solvent of ethyl acetate:methanol=3:1 (mass ratio). The washed solid was dried under reduced pressure at 40° C. for 5 hours to obtain 340 mg of polymer P4 as a yellowish brown powder.
GPC: Mw=65,500, Mn=12,400, Mw/Mn=5.28

[Comparative example 1-4]

Under a nitrogen atmosphere, 600 mg of Compound 4, 15 mg of AIBN, and 5.4 g of degassed toluene were added to the flask and stirred at 80° C. for 10 hours. Thereafter, a solution of 15 mg of AIBN dissolved in 1.0 g of toluene was added to the flask, and the mixture was further stirred at 80° C. for 10 hours. Since the resulting polymer had high solubility and purification by reprecipitation was difficult, the solvent was removed from the reaction solution using an evaporator and dried at 50°C for 5 hours to obtain yellow-white polymer P5 as a crude product. Obtained.
GPC: Mw=6,320, Mn=5,090, Mw/Mn=1.24

[3] Preparation of composition for preparing charge transporting varnish [Preparation Example 1-1]
100 g of methyl ethyl ketone (MEK) dispersed silica sol (MEK-EC-2130Y manufactured by Nissan Chemical Co., Ltd., solid content concentration 35.7% by mass) and 175 g of triethylene glycol butyl methyl ether (manufactured by Toho Chemical Co., Ltd., hereinafter the same) was placed in an eggplant flask, and the MEK contained in the MEK-dispersed silica sol was solvent-substituted with triethylene glycol butyl methyl ether using an evaporator to obtain triethylene glycol butyl methyl ether-dispersed silica sol (silica concentration 20.5% by mass). Ta.

[4] Preparation of charge transporting varnish [Example 2-1]
In a sample tube, 51 mg of P1 obtained in Example 1-1, 1.07 g of triethylene glycol butyl methyl ether, 0.64 g of butyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd., the same applies hereinafter), and dimethyl phthalate (Tokyo 0.43 g (manufactured by Kasei Kogyo Co., Ltd., hereinafter the same) was added, and the mixture was stirred for 30 minutes at room temperature using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 2.3% by mass).

[Example 2-2]
Add 60 mg of P2 obtained in Example 1-2, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate to a sample tube, and stir at room temperature for 30 minutes using a stirrer. Stirred. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).

[Example 2-3]
In a sample tube, 30 mg of P2 obtained in Example 1-2, 30 mg of arylsulfonic acid ester compound A of the following formula, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate. was added and stirred for 30 minutes at room temperature using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass). In addition, the following arylsulfonic acid ester compound was synthesized according to the method described in International Publication No. 2017/217457.

[Example 2-4]
In a sample tube, 36 mg of P2 obtained in Example 1-2, 0.12 g of silica sol dispersed in triethylene glycol butyl methyl ether obtained in Preparation Example 1-1, 0.88 g of triethylene glycol butyl methyl ether, and benzoic acid. 0.58 g of butyl and 0.39 g of dimethyl phthalate were added, and the mixture was stirred at room temperature for 30 minutes using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).

[Example 2-5]
In a sample tube, 18 mg of P2 obtained in Example 1-2, 18 mg of the above arylsulfonic acid ester compound A, 0.12 g of the triethylene glycol butyl methyl ether-dispersed silica sol obtained in Preparation Example 1-1, and triethylene glycol. 0.88 g of butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate were added, and the mixture was stirred at room temperature using a stirrer for 30 minutes. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).

[Comparative example 2-1]
48 mg of P3 obtained in Comparative Example 1-1, 12 mg of Compound 4, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate were added to a sample tube, and the mixture was stirred using a stirrer. Stirred at room temperature for 30 minutes. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).

[Comparative example 2-2]
In a sample tube, 48 mg of P3 obtained in Comparative Example 1-1, 12 mg of P5 obtained in Comparative Example 1-4, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.5 g of dimethyl phthalate. 39 g was added and stirred for 30 minutes at room temperature using a stirrer. Thereafter, it was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a charge transporting varnish (solid content concentration: 3.0% by mass).

[Comparative example 2-3]
Into a sample tube, 48 mg of P3 obtained in Comparative Example 1-1, 12 mg of arylsulfonic acid compound B of the following formula, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate were added. In addition, when the mixture was stirred for 30 minutes at room temperature using a stirrer, the arylsulfonic acid compound B was not dissolved and a uniform charge-transporting varnish could not be obtained. In addition, the following arylsulfonic acid ester compound was synthesized according to the method described in International Publication No. 2006/025342.

[Comparative example 2-4]
Add 60 mg of P4 obtained in Comparative Example 1-3, 0.97 g of triethylene glycol butyl methyl ether, 0.58 g of butyl benzoate, and 0.39 g of dimethyl phthalate to a sample tube, and stir at room temperature for 30 minutes using a stirrer. When the mixture was stirred, undissolved P4 remained, making it impossible to obtain a uniform charge-transporting varnish.

[6] Solvent resistance test After applying the charge transporting varnishes obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-2 to an ITO substrate using a spin coater, It was baked at 120°C for 1 minute. Next, it was baked in the atmosphere at 180° C. for 15 minutes to form a uniform charge-transporting thin film with a thickness of about 30 to 40 nm on the ITO substrate. The ITO substrate used was a 25 mm x 25 mm x 0.7 t glass substrate on which indium tin oxide (ITO) was patterned with a film thickness _of 50 nm. , 30 seconds) to remove impurities on the surface.

The thickness of the charge-transporting thin film of the ITO substrate with the charge-transporting thin film prepared above was measured using a stylus-type thin-film profilometer. Thereafter, the ITO substrate with the charge transporting thin film after the film thickness measurement was completely immersed in a petri dish filled with toluene solvent, and left to stand for 15 minutes. Thereafter, the substrate was pulled up, the solvent was removed by air blowing, and then the solvent was completely removed by heating and drying at 100° C. for 5 minutes. Thereafter, the thickness of the charge transporting thin film of each substrate was measured again using a stylus meter, and changes in the film thickness before and after immersion in toluene solvent were evaluated. Table 1 shows the results of the film thickness change rate (remaining film rate) before and after immersion in the solvent.

From the results in Table 1, it was confirmed that the charge transporting thin films produced in Examples 2-1 to 2-5 had a small rate of change in film thickness before and after immersion in toluene, and had solvent resistance to toluene. On the other hand, the charge transporting thin film prepared in Comparative Example 2-1 was approximately 17% thicker after immersion than before immersion, indicating that it lacked solvent resistance to toluene. Ta. This is thought to be due to the membrane swelling due to immersion in toluene. Further, the charge transporting thin film prepared in Comparative Example 2-2 showed film thinning after being immersed in toluene. It is assumed that the interaction between the charge transporting polymer and the dopant polymer was weak, and that solvent resistance could not be obtained. P1 and P2 used in the charge transporting varnishes of Examples 2-1 to 2-5 have an arylsulfonic acid ester moiety inside the polymer, so when the charge transporting thin film is fired, the sulfonic acid It is speculated that solvent resistance to toluene was developed by deprotecting the ester moiety and forming a sulfonic acid group. On the other hand, since Comparative Example 2-1 does not have an arylsulfonic acid ester moiety inside the polymer, it is presumed that the charge transporting thin film after firing lacked solvent resistance to toluene.

[7] Fabrication and characteristic evaluation of organic EL device [Example 3-1]
The charge transporting varnish obtained in Example 2-1 was applied to an ITO substrate using a spin coater, and then dried at 120° C. for 1 minute in the atmosphere. Next, the dried ITO substrate was baked at 180° C. for 15 minutes in an air atmosphere to form a uniform thin film of 50 nm on the ITO substrate. The ITO substrate used was a 25 mm x 25 mm x 0.7 t glass substrate with a patterned 150 nm thick ITO film formed on the surface, and the surface was cleaned using an O ₂ plasma cleaning device (150 W, 30 seconds) before use. The impurities above were removed. Next, α-NPD (N,N'-di(1- ^naphthyl )-N,N'- diphenylbenzidine) was formed into a 30 nm film at 0.2 nm/sec. Next, a 10 nm film of electronic block material HTEB-01 manufactured by Kanto Kagaku Co., Ltd. was formed. Next, a light-emitting layer host material NS60 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and a light-emitting layer dopant material Ir(ppy) ₃ were co-deposited. In co-evaporation, the deposition rate was controlled so that the concentration of Ir(ppy) ₃ was 6%, and the layers were stacked to a thickness of 40 nm. Next, thin films of Alq ₃ , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device. At this time, the deposition rate was 0.2 nm/sec for Alq ₃ and aluminum, and 0.02 nm/sec for lithium fluoride, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.

In addition, in order to prevent characteristic deterioration due to the influence of oxygen, water, etc. in the air, the organic EL element was sealed with a sealing substrate, and then its characteristics were evaluated. The sealing was performed according to the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the organic EL element is placed between the sealing substrates, and the sealing substrate is bonded with an adhesive (Moresco Moisture Cut WB90US (P) manufactured by MORESCO Co., Ltd.). It was pasted together. At this time, a water absorbing agent (manufactured by Dynic Co., Ltd., HD-071010W-40) was placed in the sealing substrate together with the organic EL element. The bonded sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm ² ) and then annealed at 80° C. for 1 hour to cure the adhesive.

[Example 3-2]
The procedure of Example 3-1 was repeated except that the charge-transporting varnish obtained in Example 2-2 was used instead of the charge-transporting varnish obtained in Example 2-1, and an organic EL element was manufactured. Obtained.

[Example 3-3]
The procedure of Example 3-1 was repeated except that the charge-transporting varnish obtained in Example 2-3 was used instead of the charge-transporting varnish obtained in Example 2-1, and an organic EL element was manufactured. Obtained.

[Example 3-4]
An organic EL element was obtained by repeating the procedure of Example 3-1, except that the charge transporting varnish obtained in Example 2-4 was used instead of the charge transporting varnish obtained in Example 2-1. Ta.

[Example 3-5]
An organic EL element was obtained by repeating the procedure of Example 3-1, except that the charge transporting varnish obtained in Example 2-5 was used instead of the charge transporting varnish obtained in Example 2-1. Ta.

For each of the organic EL elements produced in Examples 3-1 to 3-5, the driving voltage, current density, luminous efficiency, and luminance half-life (initial luminance of 10,000 cd/m ² ) when driven at a luminance of 10,000 cd/m 2 /m ² ) was measured. The results are shown in Table 2.

The organic EL devices produced in Examples 3-1 to 3-5 all exhibited good organic EL device characteristics. The results of Examples 3-1 and 3-2 show that polymers P1 and P2 have good charge transport properties even when used alone, that is, polymers P1 and P2 have aryl sulfonic acid esters inside the polymer. This indicates that the site functions as a dopant. It is inferred that by containing a dopant function inside the polymer, doping occurs smoothly in the charge transporting site made of arylamine, and the polymer exhibits good charge transporting properties.

Claims

A polymer characterized by containing a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (B1).

[{In formula (A1), R M is a hydrogen atom or a methyl group. R 1a and R 2a each independently represent a single bond or a phenylene group, and some or all of the hydrogen atoms of the phenylene group are a cyano group, a nitro group, a halogen atom, a vinyl group, a trifluorovinyl group, or an acryloyl group. may be substituted with a methacryloyl group, an oxetanyl group, an epoxy group, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
X 1a is -N(Ar 3a )-, -S- or -O-.
Ar 1a is a divalent group obtained by removing two hydrogen atoms on the aromatic ring of an arylene group having 6 to 20 carbon atoms, a heteroarylene group having 3 to 20 carbon atoms, or a dialkylfluorene represented by the following formula (A2). A group in which some or all of the hydrogen atoms on the aromatic rings of these groups are a cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, or epoxy group. , may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
Ar 2a and Ar 3a are each independently an aryl group having 6 to 20 carbon atoms or a monovalent group obtained by removing one hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2). Some or all of the hydrogen atoms on the aromatic ring of these groups are cyano group, nitro group, halogen atom, vinyl group, trifluorovinyl group, acryloyl group, methacryloyl group, oxetanyl group, epoxy group, carbon number It may be substituted with an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.
When X 1a is -N(Ar 3a )-, Ar 2a and Ar 3a may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.
When R 2a is a phenylene group, R 2a and Ar 2a may be bonded to each other to form a ring together with the nitrogen atom, sulfur atom or oxygen atom to which they are bonded.
However, at least one of Ar 1a to Ar 3a is a group obtained by removing the hydrogen atom on the aromatic ring of dialkylfluorene represented by the following formula (A2).

(In the formula, R 3a and R 4a are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms containing at least one ether structure. be.)}
(In formula (B1), Ar F represents a fluorinated arylene group, X 1b represents O, S, NH, CONH or NHCO, and Ar S represents at least one SO 3 D 1 D 2 on the ring. Represents an aryl group having D 3 group, D 1 represents a substituted or unsubstituted divalent hydrocarbon group, and D 2 represents a single bond, O, S, or a substituted or unsubstituted divalent amino group. , D 3 represents a substituted or unsubstituted monovalent hydrocarbon group, but if D 2 is a single bond, it may be a hydrogen atom.)
The polymer according to claim 1, wherein the repeating unit represented by the above formula (A1) is one represented by the following formula (A1-1).

(In the formula, R M , R 1a , R 2a and Ar 1a to Ar 3a represent the same meanings as above.)
The polymer according to claim 1, wherein R 1a is a single bond.
The polymer according to claim 1, wherein R 2a is a phenylene group.
The polymer according to claim 1, wherein the Ar 1a is a 9,9-dimethyl-9H-fluorene-2,7-diyl group.
The polymer according to claim 1, wherein the Ar F is a perfluoroarylene group.
7. The polymer according to claim 6, wherein the Ar F is a tetrafluorophenylene group.
The polymer according to claim 1, wherein the Ar S is an aryl group having two or more of the SO 3 D 1 D 2 D 3 groups on the ring.
The polymer according to claim 8, wherein the aryl group is a naphthyl group.
The polymer according to claim 1, wherein the X 1b is O.
A charge transporting substance comprising the polymer according to any one of claims 1 to 10.
A charge transporting varnish comprising the polymer according to claim 1 and a solvent.
The charge transporting varnish according to claim 12, further comprising a charge transporting substance other than the polymer according to claim 1.
The charge transporting varnish according to claim 13, wherein the other charge transporting substance is an arylamine derivative (excluding the polymer) or a thiophene derivative.
A charge transporting thin film obtained from the charge transporting varnish according to any one of claims 12 to 14.
An electronic device comprising the charge transporting thin film according to claim 15.
An organic electroluminescent device comprising the charge transporting thin film according to claim 15.
The organic electroluminescent device according to claim 17, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.
A quantum dot electroluminescent device comprising the charge transporting thin film according to claim 15.
The quantum dot electroluminescent device according to claim 19, wherein the charge transporting thin film is a hole injection layer or a hole transport layer.