KR20190125282A - Fluorine atom-containing polymer and its use - Google Patents

Abstract

The fluorine atom containing polymer represented by following formula (1) or (2) is provided. (In formula, A <^1> -A <^3> respectively independently represents a C1-C6 fluoroalkyynyl group; X <^1> -X <^4> respectively independently represents a crosslinkable group; Ar <^1> -Ar <^3> is respectively independently substituted An arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and each of Y ¹ to Y ⁴ independently represents a single bond or an arylene group having 6 to 20 carbon atoms; R ¹ to R ¹⁰ Are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group, alkenyl group, alkynyl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryl group, heteroaryl group, aryloxy group or Heteroaryloxy group.)

Description

Fluorine atom-containing polymer and its use

The present invention relates to fluorine atom-containing polymers and their use.

In the organic electroluminescent (EL) device, a charge transporting thin film made of an organic compound is used as a light emitting layer or a charge injection layer. In particular, the hole injection layer is responsible for the transfer of charges between the anode, 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.

The method of forming the hole injection layer is largely classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coat method. In comparison with each of these processes, the wet process effectively produces a thin film having a high flatness in a large area. can do. For this reason, the hole injection layer which can be formed by a wet process is desired in the present large area of organic electroluminescent display.

In view of such circumstances, the inventors of the present invention can apply to various wet processes and, when applied to the hole injection layer of an organic EL device, provide a charge transporting material that provides a thin film capable of realizing excellent organic EL device characteristics, and Compounds having good solubility in organic solvents have been developed (see, for example, Patent Documents 1 to 4). However, regarding the wet process material for a hole injection layer, improvement is always required, especially the wet process material which gives a thin film excellent in charge transport property is calculated | required.

International Publication No. 2008/032616 International Publication No. 2008/129947 International Publication No. 2006/025342 International Publication No. 2010/058777

This invention is made | formed in view of the said situation, and an object of this invention is to provide the charge transport varnish which gives reproducibly the charge transport thin film excellent in charge transport property, flatness, and uniformity, and the compound used as a material of this charge transport varnish.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, the predetermined | prescribed fluorine atom containing polymer is excellent in the solubility to an organic solvent, and contains the charge transport material, the dopant, and the organic solvent which consist of this fluorine atom containing polymer. The thin film obtained from the charge-transporting varnish mentioned above was excellent in charge transportability, flatness, and uniformity, and by using this thin film as a hole injection layer, the organic electroluminescent element of the outstanding brightness characteristic was obtained, and the present invention was completed.

That is, this invention provides the following fluorine atom containing polymer and its use.

1. The fluorine atom containing polymer represented by following formula (1) or (2).

(In formula, A <^1> -A <^3> respectively independently represents a C1-C6 fluoro alkyidayl group;

Ar ¹ to Ar ³ each independently represent an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and each having 1 to 2 carbon atoms which may be substituted with a halogen atom, a nitro group or a cyano group, or Z ¹ ; 20 alkyl group, is optionally substituted with a heteroaryl group having 2 to 20 carbon atoms alkenyl or 2 to 20 carbon atoms and an alkynyl group, or an aryl group having from 6 to 20 carbon atoms optionally substituted by Z ² or 2 to 20 carbon atoms of, and Each Ar ¹ , each Ar ² and each Ar ³ may be the same as or different from each other;

X ¹ to X ⁴ each independently represent a crosslinkable group;

Y ¹ to Y ⁴ each independently represent a single bond or an arylene group having 6 to 20 carbon atoms, and each Y ¹ , each Y ² , each Y ³ and each Y ⁴ may be the same as or different from each other;

R ¹ to R ¹⁰ are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. , a heteroaryl group having 1 to 20 carbon atoms an alkoxy group, having from 2 to 20 carbon atoms alkenyloxy group or 2 to 20 carbon atoms and an alkynyl group, or an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms in the Group, a C6-C20 aryloxy group, or a C2-C20 heteroaryloxy group, and when two or more R <^1> -R <^10> exists, each R <^1> -R <^10> may mutually be same or different;

Z ¹ is a C6-C20 aryl group, a C2-C20 heteroaryl group, a C1-C20 alkoxy group, or a C2-C20 that may be substituted with a halogen atom, a nitro group or a cyano group, or Z ³ A 20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group;

Z ² is a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and having 1 to 20 carbon atoms. An alkoxy group, a C2-C20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group;

Z ³ represents a halogen atom, a nitro group or a cyano group;

p, q, t, u, w and x each independently represent an integer of 0 to 4;

r, s, y and z each independently represent an integer of 0 to 4;

m and n represent a positive number satisfying 0 ≦ m ≦ 1, 0 <n ≦ 1 and m + n = 1;

k represents an integer of 1 or more.)

2. A fluorine atom-containing polymer of 1 having a weight average molecular weight of 1,000 to 1,000,000.

3. A is a perfluoromethanediyl group, a perfluoroethane-1,2-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-2,2-diyl group, 1 or 2 fluorine atom-containing polymer, which is a perfluorobutane-1,4-diyl group, a perfluoropentane-1,5-diyl group, or a perfluorohexane-1,6-diyl group.

4. The fluorine atom-containing polymer of any one of 1 to 3, wherein Ar ¹ to Ar ³ are groups derived from fluorene, benzene, naphthalene, biphenyl or derivatives thereof.

5. The fluorine atom containing polymer of 4 whose Ar <^1> -Ar <^3> is group represented by following formula (3).

(In formula, R <^11> and R <^12> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, or C2 A heteroaryl group of ˜20;

R ¹³ and R ¹⁴ are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms. Or a C6-C20 aryl group or C2-C20 heteroaryl group which may be substituted by Z <^2>;

a and b represent the integer of 0-3 each independently.)

6. A fluorine atom-containing polymer of 5 wherein R ¹¹ and R ¹² together are an alkyl group.

7. The fluorine atom-containing polymer according to any one of 1 to 6, wherein the crosslinkable group is a group containing a polymerizable carbon carbon double bond, an oxysilane ring or an oxetane ring.

8. Charge transport material which consists of a fluorine atom containing polymer in any one of 1-7.

9. A charge transport varnish comprising a charge transport material of 8, a dopant and an organic solvent.

10. A charge transport thin film fabricated using the charge transport varnish of 10. 9.

11. An electronic device having a charge transport thin film of 10.

12. An organic EL device comprising the charge transporting thin film of 10.

By using the charge transport varnish containing the fluorine atom containing polymer of this invention, the charge transport thin film excellent in charge transport property, flatness, and uniformity is obtained. Moreover, the charge-transporting thin film which has such a characteristic can be used suitably as thin film for electronic devices including organic electroluminescent element. In particular, by applying the thin film to the hole injection layer of the organic EL device, an organic EL device having a low driving voltage can be obtained. In addition, since the charge transport varnish of the present invention can produce a thin film having excellent charge transport properties with good reproducibility even when various wet processes capable of forming a film in a large area such as a spin coat method or a slit coat method are used, the field of organic EL devices has recently been developed. It can fully cope with the progress.

The charge-transporting thin film of the present invention can also be used as an antistatic film, an anode buffer layer of an organic thin film solar cell, or the like.

[Fluorine atom-containing polymer]

The fluorine atom containing polymer of this invention is represented by following formula (1) or (2).

In formulas (1) and (2), the nitrogen atom is preferably bonded to the meta position or the para position with respect to the bonding position of A ¹ to A ^{3 in} the benzene ring.

In Formula (1) and (2), A <^1> -A <^3> represents a C1-C6 fluoro alkyindayl group. The fluoroalkyindayl group is not particularly limited as long as some or all of the hydrogen atoms bonded to the carbon atoms of the alkenidayl group are substituted with fluorine atoms.

As a specific example of a fluoro alkanediyl group, a monofluoro methane diyl group, a perfluoro methane diyl group, a 2,2, 2- trifluoro ethane- 1, 1- diyl group, a perfluoro ethane 1, 1 -Diyl group, perfluoroethane-1,2-diyl group, 3-fluoropropane-1,2-diyl group, 3,3,3-trifluoropropane-1,1-diyl group, 1 , 1-difluoropropane-1,3-diyl group, perfluoropropane-1,1-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-1, 3-diyl group, perfluoropropane-2,2-diyl group, 2-methyl-2-fluoropropane-1,3-diyl group, 3,4,4-trifluorobutane-1, 2-diyl group, 4,4,4-trifluorobutane-1,3-diyl group, 2,2,3,3-tetrafluorobutane-1,4-diyl group, perfluorobutane -1,1-diyl group, perfluorobutane-1,2-diyl group, perfluorobutane-1,3-diyl group, perfluorobutane-1,4-da Diary, 1-fluoropentane-1,1-diyl group, 4,5,5-trifluoropentane-1,5-diyl group, 2,2,3,3,4,4-hexafluoro Pentane-1,5-diyl group, perfluoropentane-1,1-diyl group, perfluoropentane-1,2-diyl group, perfluoropentane-1,3-diyl group, purple Luopentane-1,4-diyl group, perfluoropentane-1,5-diyl group, 2,2,3,3,4,4,5,5-octafluorohexane-1,6 -Diyl group, perfluorohexane-1,1-diyl group, perfluorohexane-1,2-diyl group, perfluorohexane-1,3-diyl group, perfluorohexane-1 , 4-diyl group, perfluorohexane-1,5-diyl group, perfluorohexane-1,6-diyl group, etc. are mentioned.

As the fluoroalkenyl yl group, a perfluoro alkenyl yl group having 1 to 6 carbon atoms (that is, all of hydrogen atoms bonded to a carbon atom of an alkenyl yl group is substituted with a fluorine atom) is preferred. In particular, perfluoro methane Diyl group, perfluoroethane-1,2-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-2,2-diyl group, perfluorobutane-1,4 -Diyl group, perfluoropentane-1,5-diyl group, perfluorohexane-1,6-diyl group, etc. are preferable.

In Formulas (1) and (2), Ar ¹ to Ar ³ each independently represent an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms. These groups are substituted with an alkynyl group, or Z ² of a halogen atom, a group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ^1, having from 2 to 20 carbon atoms alkenyl or 2 to 20 carbon atoms and the nitro, It may be substituted by the C6-C20 aryl group or C2-C20 heteroaryl group which may be sufficient. In addition, although each Ar <^1> , each Ar <^2> and Ar <^3> may mutually be same or different, it is preferable that it is the same group from a viewpoint of the ease of the synthesis | combination of a polymer.

As Ar ¹ to Ar ³ , groups derived from fluorene, benzene, naphthalene, biphenyl or derivatives thereof are preferable. Especially as Ar <^1> -Ar <^3>, group represented by following formula (3) is preferable.

In formula (3), R <^11> and R <^12> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, or C2-C20 heteroaryl group is shown. Among these, it is preferable that R <^11> and R <^12> together are an alkyl group from a viewpoint of the solubility to the solvent used for a varnish. Especially as said alkyl group, it is preferable that it is C4-C10.

R ¹³ and R ¹⁴ are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms. Or a C6-C20 aryl group or C2-C20 heteroaryl group which may be substituted by Z <^2> . Moreover, when two or more R <^13> and R <^14> respectively exist, each R <^13> and R <^14> may mutually be same or different.

In Formula (3), although a and b respectively independently represent the integer of 0-3, 0-2 are preferable from a viewpoint of improving the availability of a raw material compound, the solubility of the polymer of this invention, charge transport property, etc., and 0 Or 1 is more preferred and 0 is optimal. In particular, it is preferable that a and b together are zero.

In Formulas (1) and (2), X ¹ to X ⁴ each independently represent a crosslinkable group. As the crosslinkable group, a group containing a polymerizable carbon carbon double bond, an oxysilane ring or an oxetane ring is preferable. It is preferable to specifically select from the group represented by a following formula.

In the formula, R ^a represents a hydrogen atom or a methyl group. R ^b and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a methyl group and an ethyl group are preferable. R ^c , R ^e and R ^f each independently represent an alkylene group having 1 to 8 carbon atoms that may contain an oxygen atom, a sulfur atom or a nitrogen atom. As R <^c> , R <^e> and R <^f>, the C1-C8 alkylene group which may contain the oxygen atom is preferable. The dashed line indicates the bond.

In Formulas (1) and (2), Y ¹ to Y ⁴ each independently represent a single bond or an arylene group having 6 to 20 carbon atoms. Examples of the arylene group include 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 2,6-naphthylene group, 4,4'-biphenylylene group etc. are mentioned. Among these, as Y ¹ to Y ⁴ , a single bond, a 1,3-phenylene group, and a 1,4-phenylene group are preferable. Moreover, although each Y <^1> , each Y <^2> , each Y <^3>, and each Y <^4> may mutually be same or different, it is preferable that it is the same group from a viewpoint of the ease of synthesis of a monomer.

In formulas (1) and (2), R ¹ to R ¹⁰ each independently represent a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , and a C 2 to 20 carbon group. alkenyl group of 2 to 20 carbon atoms alkynyl group, having 1 to 20 alkoxy groups, 2 to 20 carbon atoms alkenyloxy group or 2 to 20 carbon atoms and an alkynyl group, or a 6 to 20 carbon atoms which may be substituted with Z ² of the An aryl group, a C2-C20 heteroaryl group, a C6-C20 aryloxy group, or a C2-C20 heteroaryloxy group is shown. In addition, when two or more R <^1> -R <^10> exists, respectively, each R <^1> -R <^10> may mutually be same or different.

Z ¹ is a C6-C20 aryl group, a C2-C20 heteroaryl group, a C1-C20 alkoxy group, or a C2-C20 that may be substituted with a halogen atom, a nitro group or a cyano group, or Z ³ A 20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group is shown.

Z ² is a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and having 1 to 20 carbon atoms. An alkoxy group, a C2-C20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group is shown.

Z ³ represents a halogen atom, a nitro group or a cyano group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, C1-C20 linear or branched alkyl groups, such as a t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl 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 C3-C20 cyclic alkyl groups, such as a methyl group, a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group, are mentioned.

The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group and n- 1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1- A propenyl group, a 1-methyl- 2-propenyl group, n-1-pentenyl group, n-1-decenyl group, n-1- ecosenyl group, etc. are mentioned.

The alkynyl group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butylynyl group and n- 2-butylyn group, n-3-butylynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1 -Methyl-n-butylyl group, 2-methyl-n-butylyl group, 3-methyl-n-butylyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decyl And a n-1-pentadisinyl group, an n-1-ecosinyl group, and the like.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, and 2-phenanthryl Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc. are mentioned.

Specific examples of the heteroaryl group having 2 to 20 carbon atoms include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3 -Isoxazolyl group, 4-isooxazolyl group, 5-isooxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl Group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc. are mentioned.

The 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, isobutoxy group and s C1-C20, such as a butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. Linear or branched alkoxy group of; Cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group, bicyclobutyloxy group, bicyclopentyl octa C3-C20 cyclic alkoxy groups, such as a time period, a bicyclohexyloxy group, a bicycloheptyloxy group, a bicyclooctyloxy group, a bicyclononyloxy group, a bicyclodecyloxy group, are mentioned.

The alkenyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethenyloxy group, n-1-propenyloxy group, n-2-propenyloxy group and 1-methyl. Ethenyloxy group, n-1-butenyloxy group, n-2-butenyloxy group, n-3-butenyloxy group, 2-methyl-1-propenyloxy group, 2-methyl-2-propenyloxy group , 1-ethylethenyloxy group, 1-methyl-1-propenyloxy group, 1-methyl-2-propenyloxy group, n-1-pentenyloxy group, n-1-decenyloxy group, n- 1-eicosenyloxy group etc. are mentioned.

The alkynyloxy group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include an ethynyloxy group, n-1-propynyloxy group, n-2-propynyloxy group, and n-1-beauty. Nyloxy group, n-2-butylynoxy group, n-3-butylynyloxy group, 1-methyl-2-propynyloxy group, n-1-pentynyloxy group, n-2-pentynyloxy group, n-3-pentiene Neyloxy group, n-4-pentynyloxy group, 1-methyl-n- butynyloxy group, 2-methyl-n- butynyloxy group, 3-methyl-n- butynyloxy group, 1, 1- dimethyl-n- A propynyloxy group, n-1-hexynyloxy group, n-1-decynyloxy group, n-1-pentadedecyloxy group, n-1-ecosinyloxy group, etc. are mentioned.

Specific examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group and 1- Phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 4-phenanthryloxy group, 9-phenanthryloxy group, etc. are mentioned.

Specific examples of the heteroaryloxy group having 2 to 20 carbon atoms include 2-thienyloxy group, 3-thienyloxy group, 2-furanyloxy group, 3-furanyloxy group, 2-oxazolyloxy group, 4-oxazolyloxy group, 5-oxazolyloxy group, 3-isoxazolyloxy group, 4-isoxazolyloxy group, 5-isoxazolyloxy group, 2-thiazolyloxy group, 4-thiazolyloxy group, 5-thiazolyl jade Period, 3-isothiazolyloxy group, 4-isothiazolyloxy group, 5-isothiazolyloxy group, 2-imidazolyloxy group, 4-imidazolyloxy group, 2-pyridyloxy group, 3- Pyridyloxy group, 4-pyridyloxy group, etc. are mentioned.

As R <^1> -R <^10> , a C1-C6 alkyl group is preferable and a methyl group and an ethyl group are more preferable.

In formulas (1) and (2), p, q, t, u, w and x each independently represent an integer of 0 to 4, and r, s, y and z each independently represent an integer of 0 to 5; Although it shows, from a viewpoint of improving the availability of a raw material compound, the solubility of the polymer of this invention, charge transport property, etc., 0-2 are preferable and 0 or 1 is more preferable.

In formula (1), m and n represent the composition ratio of the left repeating unit (henceforth a repeating unit m) and the right repeating unit (henceforth a repeating unit n) in Formula (1), respectively, and 0 <= m≤1 and 0 <n≤1 also represent a positive number satisfying m + n = 1. The fluorine atom containing polymer represented by Formula (1) may contain repeating unit n as an essential unit, may include only repeating unit n, and may include both repeating units m and n. When the fluorine atom containing polymer represented by Formula (1) contains both repeating units m and n, it is preferable that m and n satisfy | fill 0.1 <= m <1 and 0 <n <0.9, and 0.5 <= m <= It is more preferable to satisfy 0.99, 0.01 ≦ n ≦ 0.5, and even more preferably 0.8 ≦ m ≦ 0.99 and 0.01 ≦ n ≦ 0.2.

In formula (2), k represents an integer of 1 or more. k or less is preferable, 100 or less are more preferable, and 50 or less are further more preferable.

The lower limit of the weight average molecular weight (Mw) of the fluorine atom-containing polymer of the present invention is preferably 1,000, more preferably 3,000, even more preferably 5,000 from the viewpoint of improving the charge transportability of the polymer. From the viewpoint of improving the solubility of the polymer, it is preferably 500,000, more preferably 100,000, and even more preferably 50,000. In addition, in this invention, Mw is the polystyrene conversion measured value by gel permeation chromatography (GPC).

[Synthesis method of fluorine atom-containing polymer]

As a method for synthesizing the fluorine atom-containing polymer represented by formula (1), when Y ¹ and Y ² are arylene groups, condensation polymerization using a coupling reaction is suitable. It does not specifically limit as said coupling reaction. For example, when synthesize | combining by Suzuki-Miyaura coupling reaction, it is represented by the amine derivative represented by Formula (4), the amine derivative represented by Formula (5), and Formula (6), as shown by following Scheme A. The method of making an aromatic compound to react in presence of a catalyst is mentioned.

In the formula, A ¹ , A ² , Ar ¹ , X ¹ , X ² , Y ¹ , Y ² , R ¹ to R ⁶ , p, q, r, s, t and u are the same as above. X ^A and X ^B each independently represent a halogen atom or a similar halogen group. Each X ^C independently represents a group represented by the following formula (7) or (8).

(In formula, A <^11> and A <^12> respectively independently represent a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group. ^A13 is a C1-C20 alkenidayl group or C6-C20 Arylene group.)

As a specific example of a halogen atom, an alkyl group, and an aryl group, the thing similar to what was mentioned above is mentioned.

Examples of the pseudo halogen group include fluoroalkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group, and nonafluorobutanesulfonyloxy group; Aromatic sulfonyloxy groups, such as a benzene sulfonyloxy group and a toluene sulfonyloxy group, etc. are mentioned.

Examples of the alkenylyl group having 1 to 20 carbon atoms represented by A ¹³ include ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3 -Diyl group, 2-ethyl-2-methylpropane-1,3-diyl group, 2,2-diethylpropane-1,3-diyl group, 2-methyl-2-propylpropane-1,3 -Diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,4-diyl group, 2-methylbutane-2,3-diyl group, 2,3 -Dimethylbutane-2,3-diyl group, pentane-1,3-diyl group, pentane-1,5-diyl group, pentane-2,3-diyl group, pentane-2,4- Diyl group, 2-methylpentane-2,3-diyl group, 3-methylpentane-2,3-diyl group, 4-methylpentane-2,3-diyl group, 2,3-dimethylpentane -2,3-diyl group, 3-methylpentane-2,4-diyl group, 3-ethylpentane-2,4-diyl group, 3,3-dimethylpentane-2,4-diyl group, 3,3-dimethylpentane-2,4-diyl group, 2,4-dimethylpentane-2,4-diyl group, hexane-1,6-diyl , Hexane-1,2-diyl group, hexane-1,3-diyl group, hexane-2,3-diyl group, hexane-2,4-diyl group, hexane-2,5-diyl group , 2-methylhexane-2,3-diyl group, 4-methylhexane-2,3-diyl group, 3-methylhexane-2,4-diyl group, 2,3-dimethylhexane-2 , 4-diyl group, 2,4-dimethylhexane-2,4-diyl group, 2,5-dimethylhexane-2,4-diyl group, 2-methylhexane-2,5-diyl group , 3-methylhexane-2,5-diyl group, 2,5-dimethylhexane-2,5-diyl group, and the like.

As the arylene group having 6 to 20 carbon atoms, 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group, 1,2-anthylene group, 2,3 -Anthylene groups, 1,2-phenanthryl groups, 3,4-phenanthryl groups, 9,10-phenanthryl groups and the like.

Although reaction of Scheme A can be performed even without a solvent, it is usually performed using a solvent. As the solvent, any solvent can be used as long as it does not inhibit the reaction. Examples thereof include cyclic ethers such as tetrahydrofuran and 1,4-dioxane; Amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); Ketones such as methyl isobutyl ketone and cyclohexanone; Halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; Aromatic hydrocarbons, such as benzene, toluene, and xylene, are mentioned. These solvent can be used individually by 1 type or in mixture of 2 or more types. Among these, 1, 4- dioxane, toluene, xylene, etc. are preferable.

As a catalyst used in the reaction, [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 ( Palladium catalysts such as Pd ₂ (dba) ₃ ), bis (trit-butylphosphine) palladium (Pd (Pt-Bu ₃ ) ₂ ), palladium acetate (II) (Pd (OAc) ₂ ), and the like. .

As for the introduction ratio of the aromatic compound represented by Formula (6), 0.83-1.2 are suitable as molar ratio with respect to the sum total of the amine derivative represented by Formula (4), and the amine derivative represented by Formula (5). Moreover, what is necessary is just to set suitably the introduction ratio of the amine derivative represented by Formula (4) and the amine derivative represented by Formula (5) so that the composition ratio of repeating units m and n may become the above-mentioned range.

The reaction temperature of the said reaction is 40-200 degreeC normally. Although reaction time is set suitably according to reaction temperature, it is about 30 minutes-about 50 hours normally.

The amine derivative represented by the formula (4) is condensed with the amine compound represented by the formula (9) and the halogenated compound represented by the formula (10) in the presence of a catalyst, as represented by the following scheme B. After condensation reaction with the halogenated compound represented by the formula (11) and the halogenated compound represented by the formula (12) to synthesize an amine derivative represented by the formula (4-1), the resulting amine derivative is reacted with a known halogenating agent. It can synthesize | combine by making it.

(Wherein A ¹ , R ¹ to R ⁴ , Y ¹ , X ^A , p, q, r and s are the same as above. Y ¹ ′ represents an aryl group having 6 to 20 carbon atoms. Hal represents a halogen atom or A pseudo halogen group.)

Moreover, the amine derivative represented by Formula (4) catalyzes the halogenated compound represented by Formula (13), the amine compound represented by Formula (14), and the amine compound represented by Formula (15), as shown by Scheme C below. It can also be synthesize | combined by making condensation reaction in presence and synthesize | combining the amine derivative represented by Formula (4-1), and then making the obtained amine derivative react with a well-known halogenating agent.

(Wherein A ¹ , R ¹ to R ⁴ , Y ¹ , Y ¹ ′, X ^A , p, q, r and s are the same as above).

The introduction ratio of the amine compound and the halogenated compound may be made to be equal to or more than the total Hal group of the total halogenated compound relative to the amount of substances in the total NH groups of the total amine compound, but about 1 to 1.5 equivalents are suitable.

As a catalyst, For example, Copper catalysts, such as a copper chloride, copper bromide, and copper iodide; Palladium catalysts such as Pd (PPh ₃ ) ₄ , Pd (PPh ₃ ) ₂ Cl ₂ , Pd (dba) ₂ , Pd ₂ (dba) ₃ , Pd (Pt-Bu ₃ ) ₂ , Pd (OAc) ₂ , and the like. Can be. These catalysts may be used alone, or may be used in combination of two or more thereof. Moreover, you may use these catalysts together with a well-known suitable ligand.

The amount of the catalyst to be used may be 0.0001 to 0.5 mol with respect to 1 mol of the halogenated compound, and about 0.001 to 0.1 mol is suitable. Moreover, when using a ligand, the usage-amount can be 0.5-50 equivalent with respect to the metal complex to be used, 1-10 equivalent is suitable.

As a halogenating agent, a well-known thing can be used and N-bromosuccinimide etc. are mentioned specifically ,.

As for the usage-amount of a halogenating agent, about 4-6 mol is suitable with respect to 1 mol of compounds represented by Formula (4-1).

You may perform each reaction shown by the schemes B and C in a solvent. In the case of using a solvent, the kind is not particularly limited as long as it does not adversely affect the reaction. Among these, specific examples of the solvent that can be suitably used in the condensation reaction include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane). Phosphorus, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), ethers (diethyl ether, diiso) Propylether, t-butylmethylether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), amide (N, N-dimethylform Amide (DMF), N, N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), urea derivatives (N, N-dimethylimidazolidinone, tetra Methylurea, etc.), sulfoxide (dimethylsulfoxide, sulfolane, etc.), nitrile (acetonitrile, propionitrile, Butyronitrile etc.) etc. are mentioned. Specific examples of the solvent that can be suitably used in the reaction with the halogenating agent include halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, in addition to those exemplified as solvents usable in the condensation reaction). , p-dichlorobenzene and the like). In addition, a solvent may be used individually by 1 type and may mix and use 2 or more types.

What is necessary is just to set reaction temperature suitably in the range from the melting point of a solvent to boiling point, about 0-200 degreeC is especially preferable, and its 20-150 degreeC is more preferable.

After completion | finish of reaction, it can post-process in accordance with a conventional method, and can obtain the target amine derivative.

The amine derivative represented by formula (5) is a catalyst having an amine compound represented by formula (16), a halogenated compound represented by formula (17), and a halogenated compound represented by formula (18) as shown in Scheme D below. The resulting compound is reacted with the halogenated compound represented by the formula (10) to synthesize the amine derivative represented by the formula (5-1), and then the obtained amine derivative is reacted with a known halogenating agent. can do.

(In the ^{formula, A 2, R 5, R} 6, X 1, X 2, Y 2, X A, Hal, t and u are as defined above. Y ² 'is an aryl group of 6 to 20 carbon atoms.)

The introduction ratio of the amine compound and the halogenated compound may be made to be equal to or more than the total Hal group of the total halogenated compound relative to the amount of substances in the total NH groups of the total amine compound, but about 1 to 1.5 equivalents are suitable.

The catalysts, solvents and halogenating agents that can be used in the reaction represented by scheme D, the amounts of use thereof, and reaction conditions are the same as those described in the description of schemes B and C.

The aromatic compound represented by Formula (6) can be synthesize | combined by a conventionally well-known method.

In the fluorine atom-containing polymer represented by formula (1), when Y ¹ and Y ² are single bonds, for example, an amine derivative represented by formula (4 ') as represented by Scheme E below, formula (5) And a method of reacting the amine derivative represented by ') and the aromatic compound represented by the formula (6') in the presence of a catalyst.

(Wherein A ¹ , A ² , Ar ¹ , X ¹ , X ² , R ¹ to R ⁶ , p, q, r, s, t and u are the same as above. X ^D is each independently a halogen atom) Or a pseudo halogen group.)

The amine derivative represented by formula (4 ') can be synthesized according to the methods shown in Schemes B and C. The phenylamine derivative represented by formula (5 ') can be synthesized according to the method shown in Scheme D. The compound represented by Formula (6 ') can be synthesize | combined by a conventionally well-known method.

The catalyst, the solvent and the halogenating agent which can be used in the reaction represented by scheme E, the amount of use thereof, and the reaction conditions are the same as those described in the description of scheme A.

The fluorine atom-containing polymer represented by the formula (2) is, for example, in the presence of a catalyst containing the amine derivative represented by the formula (4 '') and the aromatic compound represented by the formula (6 ''), as represented by Scheme F below. The polymer obtained by condensation polymerization under the following reaction can be synthesized by reacting with the compounds represented by formulas (9) and (10) to seal the ends.

(Wherein R ⁷ to R ¹⁰ , A ³ , Ar ³ , X ³ , X ⁴ , Y ³ , Y ⁴ , X ^A , X ^C , w, x, y and z are the same as above).

In the reaction represented by the scheme F, the condensation polymerization and the reaction with the compounds represented by the formulas (9) and (10) can proceed under the same conditions as those described for the reaction represented by the scheme A.

[Charge transport material]

The fluorine atom-containing polymer of the present invention can be suitably used as a charge transporting substance. In the present invention, the charge transportability is the same as the conductivity and the hole transportability. The charge transporting material may be charge transporting itself, or may be charge transporting when used with a dopant. The charge-transporting varnish may itself be charge-transporting, or the solid film obtained thereby may be charge-transporting.

[Charge transport varnish]

The charge transport varnish of the present invention contains a charge transport material, a dopant, and an organic solvent composed of the fluorine atom-containing polymer.

As for content of the charge transport material which consists of the said fluorine atom containing polymer, about 0.1-20 mass% is preferable in a varnish from a viewpoint of suppressing precipitation of a charge transport material.

[Dopant]

Although the said dopant will not be specifically limited if it melt | dissolves in the organic solvent mentioned later, The ionic compound represented by following formula (9) is suitable.

In formula (9), E represents a Group 13 element of the long-period periodic table, and Ar ¹⁰¹ to Ar ¹⁰⁴ each independently represent an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, and a fluorine atom and chlorine It may be substituted by halogen atoms, such as an atom and a bromine atom, a C2-C12 acyl group, such as a cyano group, a nitro group, and an acetyl group, or a C1-C10 halogenated alkyl group, such as a trifluoromethyl group.

As said group 13 element, a boron atom, an aluminum atom, and a gallium atom are preferable, and a boron atom is more preferable. Examples of the aryl group having 6 to 20 carbon atoms and the heteroaryl group having 2 to 20 carbon atoms include those similar to those described above.

In formula (9), M <^+> represents onium ion. Examples of the onium ions include iodonium ions, sulfonium ions, ammonium ions, phosphonium ions, and the like, and particularly, iodonium ions represented by the following formula (10) are preferable.

In formula (10), R <^101> and R <^102> are respectively independently a C1-C12 alkyl group, a C2-C12 alkenyl group, a C2-C12 alkynyl group, a C6-C20 aryl group, or a C2-C20 A heteroaryl group, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or 2 carbon atoms It may be substituted by the heteroaryl group of ˜20.

A commercial item can be used as an ionic compound represented by Formula (9).

In consideration of device characteristics, the content of the dopant is preferably 0.01 to 10, more preferably 0.05 to 5, and even more preferably 0.1 to 3 with respect to the charge transporting material.

[Charge transport material not containing fluorine atom]

The charge transport varnish of the present invention may contain a charge transport material containing no fluorine atom as necessary. Examples of such charge transport materials include charge transport oligomers such as aniline derivatives, thiophene derivatives, and pyrrole derivatives. Although the molecular weight of a charge-transporting oligomer is 200-5,000 normally, from a viewpoint of preparing the varnish which gives a thin film with high charge transportability, Preferably it is 300 or more, More preferably, it is 400 or more, More preferably, it is 500 or more, and flatness is From a viewpoint of preparing the uniform varnish which gives a high thin film, Preferably it is 4,000 or less, More preferably, it is 3,000 or less, More preferably, it is 2,000 or less.

Of the above charge transporting oligomers, aniline derivatives are preferred in view of the balance between solubility in an organic solvent and charge transportability of the resulting thin film. Examples of aniline derivatives include oligoaniline derivatives disclosed in Japanese Patent Application Laid-Open No. 2002-151272, oligoaniline compounds disclosed in International Publication No. 2004/105446, oligoaniline compounds disclosed in International Publication No. 2008/032617, and International Publication No. 2008/032616. The oligoaniline compound described, the aryldiamine compound etc. of international publication 2013/042623, etc. are mentioned. And aniline derivatives described in International Publication No. 2016/006674.

In the case of using a charge transport material containing no fluorine atom, the ratio of the charge transport material made of the fluorine atom-containing polymer of the present invention to the charge transport material containing no fluorine atom is indicative of the luminance characteristics of the organic EL device obtained. Considering the height is higher, the charge transport material made of the fluorine atom-containing polymer of the present invention in a mass ratio with respect to the charge transport material not containing fluorine atoms is preferably about 0.1 to 5, more preferably about 0.5 to 3, further More preferably, it is about 0.5-1.

[Organic Solvent]

As an organic solvent used when preparing a charge transporting varnish, a high solubility solvent capable of dissolving a charge transporting material and a dopant can be used. Since the fluorine atom containing polymer of this invention has high solubility with respect to a low polar solvent, it is possible to use a low polar solvent as a solid solution solvent.

Examples of the low polar solvent in the high solubility solvent include cyclohexanone, anisole, chloroform, chlorobenzene, toluene, xylene, tetralin, cyclohexylbenzene, 3-phenoxytoluene, methyl benzoate, and the like. . As the polar solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. . These solvent can be used individually by 1 type or in mixture of 2 or more types, The usage-amount can be 5-100 mass% in the whole solvent used for a varnish.

In addition, it is preferable that both the charge-transporting substance and the dopant are completely dissolved in the solvent.

In the present invention, the varnish has a viscosity of 10 to 200 mPa · s, in particular 35 to 150 mPa · s at 25 ° C., and a high viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C., at normal pressure (atmospheric pressure). Species can be contained. By adding such a solvent, adjustment of the viscosity of a varnish becomes easy, and varnish preparation by the coating method to be used which gives a high flatness thin film reproducibly is attained.

As a high viscosity organic solvent, for example, cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene Glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, etc. It may be, but is not limited to these.

When using a high viscosity organic solvent, it is preferable that the content exists in the range which solid does not precipitate, and unless the solid precipitates, 5-90 mass% is preferable in all the solvent used for a varnish.

In addition, for the purpose of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, and the like, 1 to 90% by mass of the total solvent using other solvents, preferably 1 to 50 You may mix in mass% ratio.

As such a solvent, for example, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol Although lycol monoethyl ether, diacetone alcohol, (gamma) -butyrolactone, ethyl lactate, n-hexyl acetate, etc. are mentioned, It is not limited to these. These solvent can be used individually by 1 type or in mixture of 2 or more types.

Although the viscosity of the varnish of this invention is suitably set according to the thickness etc. and solid content concentration of the thin film to produce, it is 1-50 mPa * s at 25 degreeC normally. In addition, the solid content concentration of the charge-transporting varnish in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, and the like, and is usually about 0.1 to 10.0% by mass, thereby improving the applicability of the varnish. When considering what is made to make it, Preferably it is 0.5-5.0 mass%, More preferably, it is 1.0-3.0 mass%. In addition, solid content means what removed the organic solvent among the components of a varnish.

[Charge Transport Thin Film]

By apply | coating and baking the charge-transporting varnish of this invention on a base material, a charge-transporting thin film can be formed on a base material.

Examples of the varnish coating method include a dip method, spin coating method, transfer printing method, roll coating method, brushing, inkjet method, spray method, slit coating method, and the like. It is preferable to adjust the viscosity and surface tension of the varnish according to the application method.

Moreover, when using the varnish of this invention, a baking atmosphere is not specifically limited, either, In addition to an atmospheric atmosphere, even if it is inert gas, such as nitrogen, or in vacuum, the thin film which has a uniform film forming surface and high charge transport property can be obtained.

The firing temperature is appropriately set within the range of approximately 100 to 260 ° C. in consideration of the use of the thin film to be obtained, the degree of charge transportability imparted to the thin film to be obtained, and the like. Degree C is preferable, and about 150-230 degreeC is more preferable.

In particular, the varnish of the present invention is characterized by being calcinable at a low temperature of less than 200 ° C. Even thin films produced under such firing conditions have high flatness and high charge transportability.

In addition, at the time of baking, in order to express higher uniform film-forming property or to advance reaction on a base material, you may provide two or more temperature changes. Heating may be performed using a suitable apparatus, such as a hotplate or oven.

Although the film thickness of a charge-transporting thin film is not specifically limited, When using in an organic electroluminescent element, it can be about 5-200 nm, Especially when using as a hole injection transport layer, 10-100 nm is preferable and 20-50 nm is more preferable. 25-45 nm is further more preferable. As a method of changing a film thickness, the method of changing solid content concentration in a varnish, changing the amount of solution on a board | substrate at the time of application | coating, etc. are mentioned.

[Organic EL element]

The organic electroluminescent element of this invention has a pair of electrode, and has the charge-transporting thin film of this invention mentioned above between these electrodes.

Although the following (a)-(f) is mentioned as a typical structure of organic electroluminescent element, It is not limited to these. Moreover, in the following structure, an electron blocking layer etc. can be provided between a light emitting layer and an anode, and a hole (hole) block layer etc. can be provided between a light emitting layer and a cathode as needed. In addition, the hole injection layer, the hole transport layer, or the hole injection transport layer may have a function as an electron block layer or the like, and the electron injection layer, an electron transport layer or an electron injection transport layer may have a function as a hole (hole) block layer or the like.

(a) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(b) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / cathode

(c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode

(e) Anode / hole injection layer / hole transport layer / light emitting layer / cathode

(f) anode / hole injection transport layer / light emitting layer / cathode

The "hole injection layer", the "hole transporting layer" and the "hole injection transporting layer" are layers formed between the light emitting layer and the anode, and have a function of transporting holes from the anode to the light emitting layer. When only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a "hole injection transporting layer", and when two or more layers of hole transporting material are provided between the light emitting layer and the anode, the layer close to the anode is "hole Injection layer ", and the other layer is a" hole transport layer ". In particular, the hole injection layer and the hole injection transport layer may be formed using a thin film having excellent hole acceptability from the anode as well as hole injection properties into the hole transport layer and the light emitting layer, respectively.

The "electron injection layer", "electron transport layer" and "electron injection transport layer" are layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer. When only one layer of the electron transporting material is provided between the light emitting layer and the cathode, it is the "electron injection transport layer", and when two or more layers of the electron transporting material are provided between the light emitting layer and the cathode, the layer close to the cathode is "electron Injection layer ”, and the other layer is an“ electron transport layer ”.

The "light emitting layer" is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is employed. At this time, the host material mainly promotes recombination of electrons and holes, traps excitons in the light emitting layer, and the dopant material functions to efficiently emit excitons obtained by recombination. In the case of a phosphorescent device, the host material mainly has a function of confining excitons generated in the dopant in the light emitting layer.

Although the following are mentioned as a material and manufacturing method at the time of manufacturing an organic electroluminescent element using the charge-transporting varnish of this invention, It is not limited to these.

It is preferable to clean the electrode substrate to be used by cleaning the liquid with detergent, alcohol, pure water, or the like beforehand. For example, the positive electrode substrate is preferably subjected to surface treatment such as UV ozone treatment, oxygen-plasma treatment, etc. immediately before use. . However, when the positive electrode material mainly contains an organic substance, the surface treatment may not be performed.

An example of the manufacturing method of the organic electroluminescent element of this invention when the thin film obtained from the charge-transporting varnish of this invention is a hole injection layer is as follows.

By the method mentioned above, the charge-transporting varnish of this invention is apply | coated and baked on an anode board | substrate, and a hole injection layer is produced on an electrode. On this hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order. The hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be formed by any one of a vapor deposition method and a coating method (wet process), depending on the characteristics of the material to be used.

Examples of the anode material include a transparent electrode represented by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode composed of a metal represented by aluminum, an alloy thereof, and the like, and a planarization treatment is preferable. . Polythiophene derivatives or polyaniline derivatives having high charge transporting properties can also be used.

Other metals constituting the metal anode include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, Cadmium, indium, scandium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, thallium, tungsten, rhenium, osmium, iridium, platinum, Although gold, titanium, lead, bismuth, these alloys, etc. are mentioned, It is not limited to these.

Examples of the material for forming the hole transport layer include a (triphenylamine) dimer derivative, a [(triphenylamine) dimer] spirodimer, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -Benzidine (α-NPD), N, N'-bis (naphthalen-2-yl) -N, N'-bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N ' -Bis (phenyl) -benzidine, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9-spirobifluorene, N, N'-bis (naphthalene-1 -Yl) -N, N'-bis (phenyl) -9,9-spirobifluorene, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) -9,9- Dimethyl-fluorene, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -9,9-dimethyl-fluorene, N, N'-bis (3-methylphenyl ) -N, N'-bis (phenyl) -9,9-diphenyl-fluorene, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -9,9- Diphenyl-fluorene, N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -2,2'-dimethylbenzidine, 2,2 ', 7,7'-tetra Keith (N, N-diphenylamino) -9,9-spirobiflu Orene, 9,9-bis [4- (N, N-bis-biphenyl-4-yl-amino) phenyl] -9H-fluorene, 9,9-bis [4- (N, N-bis-naphthalene -2-yl-amino) phenyl] -9H-fluorene, 9,9-bis [4- (N-naphthalen-1-yl-N-phenylamino) -phenyl] -9H-fluorene, 2,2 ' , 7,7'-tetrakis [N-naphthalenyl (phenyl) -amino] -9,9-spirobifluorene, N, N'-bis (phenanthrene-9-yl) -N, N'- Bis (phenyl) -benzidine, 2,2'-bis [N, N-bis (biphenyl-4-yl) amino] -9,9-spirobifluorene, 2,2'-bis (N, N -Diphenylamino) -9,9-spirobifluorene, di- [4- (N, N-di (p-tolyl) amino) -phenyl] cyclohexane, 2,2 ', 7,7' Tetra (N, N-di (p-tolyl) amino) -9,9-spirobifluorene, N, N, N ', N'-tetra-naphthalen-2-yl-benzidine, N, N, N ', N'-tetra- (3-methylphenyl) -3,3'-dimethylbenzidine, N, N'-di (naphthalenyl) -N, N'-di (naphthalen-2-yl) -benzidine, N, N, N ', N'-tetra (naphthalenyl) -benzidine, N, N'-di (naphthalen-2-yl) -N, N '-Diphenylbenzidine-1,4-diamine, N ¹ , N ⁴ -diphenyl-N ¹ , N ⁴ -di (m-tolyl) benzene-1,4-diamine, N ² , N ² , N ⁶ , N ⁶ -tetraphenylnaphthalene-2,6-diamine, tris (4- (quinolin-8-yl) phenyl) amine, 2,2'-bis (3- (N, N-di (p-tolyl) ) Amino) phenyl) biphenyl, 4,4 ', 4''-tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4', 4 ''-tris [1-naph Triarylamines, such as methyl (phenyl) amino] triphenylamine (1-TNATA), 5,5 ''-bis- {4- [bis (4-methylphenyl) amino] phenyl} -2,2 ': 5' Hole-transporting low molecular weight materials, such as oligothiophenes, such as a 2 "-terthiophene (BMA-3T), etc. are mentioned.

Examples of the material for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq ₃ ), bis (8-quinolinolato) zinc (II) (Znq ₂ ), and bis (2-methyl-8- Quinolinolato) -4- (p-phenylphenolato) aluminum (III) (BAlq), 4,4'-bis (2,2-diphenylvinyl) biphenyl, 9,10-di (naphthalene-2 -Yl) anthracene, 2-t-butyl-9,10-di (naphthalen-2-yl) anthracene, 2,7-bis [9,9-di (4-methylphenyl) -fluoren-2-yl]- 9,9-di (4-methylphenyl) fluorene, 2-methyl-9,10-bis (naphthalen-2-yl) anthracene, 2- (9,9-spirobifluoren-2-yl) -9 , 9-spirobifluorene, 2,7-bis (9,9-spirobifluoren-2-yl) -9,9-spirobifluorene, 2- [9,9-di (4 -Methylphenyl) -fluoren-2-yl] -9,9-di (4-methylphenyl) fluorene, 2,2'-dipyrenyl-9,9-spirobifluorene, 1,3,5- Tris (pyren-1-yl) benzene, 9,9-bis [4- (pyrenyl) phenyl] -9H-fluorene, 2,2'-bi (9,10-diphenylanthracene), 2,7- Daffy Lenyl-9,9-spirobifluorene, 1,4-di (pyren-1-yl) benzene, 1,3-di (pyren-1-yl) benzene, 6,13-di (biphenyl-4 -Yl) pentacene, 3,9-di (naphthalen-2-yl) perylene, 3,10-di (naphthalen-2-yl) perylene, tris [4- (pyrenyl) -phenyl] amine, 10 , 10'-di (biphenyl-4-yl) -9,9'-bianthracene, N, N'-di (naphthalen-1-yl) -N, N'-diphenyl- [1,1 ': 4 ', 1'':4'',1'''-quaterphenyl] -4,4 '''-diamine,4,4'-di [10- (naphthalen-1-yl) anthracene-9- Il] biphenyl, dibenzo {[f, f ']-4,4', 7,7'-tetraphenyl} diindeno [1,2,3-cd: 1 ', 2', 3'-lm ] Perylene, 1- (7- (9,9'-bianthracene-10-yl) -9,9-dimethyl-9H-fluoren-2-yl) pyrene, 1- (7- (9,9) '-Bianthracene-10-yl) -9,9-dihexyl-9H-fluoren-2-yl) pyrene, 1,3-bis (carbazol-9-yl) benzene, 1,3,5-tris (Carbazol-9-yl) benzene, 4,4 ', 4''-tris (carbazol-9-yl) triphenylamine, 4,4'-bis (carbazol-9-yl) biphenyl (CBP ), 4,4'-bis (carbazol-9-yl) -2,2'-dimethylbar Phenyl, 2,7-bis (carbazol-9-yl) -9,9-dimethylfluorene, 2,2 ', 7,7'-tetrakis (carbazol-9-yl) -9,9- Spirobifluorene, 2,7-bis (carbazol-9-yl) -9,9-di (p-tolyl) fluorene, 9,9-bis [4- (carbazol-9-yl)- Phenyl] fluorene, 2,7-bis (carbazol-9-yl) -9,9-spirobifluorene, 1,4-bis (triphenylsilyl) benzene, 1,3-bis (triphenylsilyl ) Benzene, bis (4-N, N-diethylamino-2-methylphenyl) -4-methylphenylmethane, 2,7-bis (carbazol-9-yl) -9,9-dioctylfluorene, 4 , 4 ''-di (triphenylsilyl) -p-terphenyl, 4,4'-di (triphenylsilyl) biphenyl, 9- (4-t-butylphenyl) -3,6-bis (triphenyl Silyl) -9H-carbazole, 9- (4-t-butylphenyl) -3,6-ditrityl-9H-carbazole, 9- (4-t-butylphenyl) -3,6-bis (9 -(4-methoxyphenyl) -9H-fluoren-9-yl) -9H-carbazole, 2,6-bis (3- (9H-carbazol-9-yl) phenyl) pyridine, triphenyl (4 -(9-phenyl-9H-fluoren-9-yl) phenyl) silane, 9,9-dimethyl-N, N-da Phenyl-7- (4- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -9H-fluoren-2-amine, 3,5-bis (3- (9H-carbazole -9-yl) phenyl) pyridine, 9,9-spirobifluoren-2-yl-diphenyl-phosphineoxide, 9,9 '-(5- (triphenylsilyl) -1,3-phenylene ) Bis (9H-carbazole), 3- (2,7-bis (diphenylphosphoryl) -9-phenyl-9H-fluoren-9-yl) -9-phenyl-9H-carbazole, 4,4 , 8,8,12,12-hexa (p-tolyl) -4H-8H-12H-12C-azadibenzo [cd, mn] pyrene, 4,7-di (9H-carbazol-9-yl)- 1,10-phenanthroline, 2,2'-bis (4- (carbazol-9-yl) phenyl) biphenyl, 2,8-bis (diphenylphosphoryl) dibenzo [b, d] thiophene , Bis (2-methylphenyl) diphenylsilane, bis [3,5-di (9H-carbazol-9-yl) phenyl] diphenylsilane, 3,6-bis (carbazol-9-yl)- 9- (2-ethyl-hexyl) -9H-carbazole, 3- (diphenylphosphoryl) -9- (4- (diphenylphosphoryl) phenyl) -9H-carbazole, 3,6-bis [( 3,5-diphenyl) phenyl] -9-phenylcarbazole, etc. are mentioned. You may form a light emitting layer by co-depositing these materials and a luminescent dopant.

As the luminescent dopant, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- 10- (2-benzothiazolyl) quinolidino [9,9a, 1gh] coumarin, quinacridone, N, N'-dimethyl-quinacridone, tris (2-phenylpyridine) iridium (III) (Ir (ppy) ₃ ), bis (2-phenylpyridine) (acetylacetonate) iridium (III) (Ir (ppy) ₂ (acac)), tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) ₃ ), 9,10-bis [N, N-di (p-tolyl) amino] anthracene, 9,10-bis [phenyl (m-tolyl) amino] anthracene, bis [2- (2-hydro Oxyphenyl) benzothiazolato] zinc (II), N ¹⁰ , N ¹⁰ , N ¹⁰ , N ¹⁰ -tetra (p-tolyl) -9,9'-bianthracene-10,10'-diamine, N ^{10 , N 10, N 10, N} 10 - tetraphenyl -9,9'- bi anthracene -10,10'- diamine, N ^10, N ¹⁰ - diphenyl -N ^10, N ¹⁰ - dimethyl naphthalene 1-9, 9'-bianthracene-10,10'-diamine, 4,4'-bis (9-ethyl-3-carbazovinylene) -1,1'-biphenyl, peryl Ethylene, 2,5,8,11-tetra-t-butylperylene, 1,4-bis [2- (3-N-ethylcarbazolyl) vinyl] benzene, 4,4'-bis [4- (di -p-tolylamino) styryl] biphenyl, 4- (di-p-tolylamino) -4 '-[(di-p-tolylamino) styryl] stilbene, bis [3,5-difluoro -2- (2-pyridyl) phenyl- (2-carboxypyridyl)] iridium (III), 4,4'-bis [4- (diphenylamino) styryl] biphenyl, bis (2,4- Difluorophenylpyridinato) tetrakis (1-pyrazolyl) borateiridium (III), N, N'-bis (naphthalen-2-yl) -N, N'-bis (phenyl) -tris (9, 9-dimethylfluorenylene), 2,7-bis {2- [phenyl (m-tolyl) amino] -9,9-dimethyl-fluoren-7-yl} -9,9-dimethyl-flu Orene, N- (4-((E) -2- (6 ((E) -4- (diphenylamino) styryl) naphthalen-2-yl) vinyl) phenyl) -N-phenylbenzeneamine, fac- Iridium (III) tris (1-phenyl-3-methylbenzimidazolin-2-iriden-C, C ² ), mer-iridium (III) tris (1-phenyl-3-methylbenzimidazolin-2 -Wolf Den-C, C ² ), 2,7-bis [4- (diphenylamino) styryl] -9,9-spirobifluorene, 6-methyl-2- (4- (9- (4- (6-methylbenzo [d] thiazol-2-yl) phenyl) anthracene-10-yl) phenyl) benzo [d] thiazole, 1,4-di [4- (N, N-diphenyl) amino] Styrylbenzene, 1,4-bis (4- (9H-carbazol-9-yl) styryl) benzene, (E) -6- (4- (diphenylamino) styryl) -N, N-di Phenylnaphthalen-2-amine, bis (2,4-difluorophenylpyridinato) (5- (pyridin-2-yl) -1H-tetrazolate) iridium (III), bis (3-trifluoro Methyl-5- (2-pyridyl) pyrazole) ((2,4-difluorobenzyl) diphenylphosphinate) iridium (III), bis (3-trifluoromethyl-5- (2-pyri Dill) pyrazolate) (benzyldiphenylphosphinate) iridium (III), bis (1- (2,4-difluorobenzyl) -3-methylbenzimidazolum) (3- (trifluoromethyl ) -5- (2-pyridyl) -1,2,4-triazolate) iridium (III), bis (3-trifluoromethyl-5- (2-pyri) ) Pyrazolate) (4 ', 6'-difluorophenylpyridinate) iridium (III), bis (4', 6'-difluorophenylpyridinato) (3,5-bis (trifluoro) Rhomethyl) -2- (2'-pyridyl) pyrrolate) iridium (III), bis (4 ', 6'-difluorophenylpyridinato) (3- (trifluoromethyl) -5- ( 2-pyridyl) -1,2,4-triazolate) iridium (III), (Z) -6-mesityl-N- (6-methylquinoline-2 (1H) -iridene) quinoline-2 -Amine-BF ₂ , (E) -2- (2- (4- (dimethylamino) styryl) -6-methyl-4H-pyran-4-iridene) malononitrile, 4- (disai Aminomethylene) -2-methyl-6-zulolidil-9-enyl-4H-pyran, 4- (dicyanomethylene) -2-methyl-6- (1,1,7,7-tetramethylzololy Dyl-9-enyl) -4H-pyran, 4- (diicyanomethylene) -2-t-butyl-6- (1,1,7,7-tetramethylzulolidin-4-yl-vinyl)- 4H-pyran, tris (dibenzoylmethane) phenanthroline europium (III), 5,6,11,12-tetraphenylnaphthacene, bis (2-benzo [b] thiophen-2-yl-pyridine) (Acetylacetonate) iridium (III), tris (1-phenylisoquinoline) iridium (III), bis (1-phenylisoquinoline) (acetylacetonate) iridium (III), bis [1- (9,9- Dimethyl-9H-fluoren-2-yl) -isoquinoline] (acetylacetonate) iridium (III), bis [2- (9,9-dimethyl-9H-fluoren-2-yl) quinoline] ( Acetylacetonate) iridium (III), tris [4,4'-di-t-butyl- (2,2 ')-bipyridine] ruthenium (III) -bis (hexafluorophosphate), tris (2-phenyl Quinoline) iridium (III), bis (2-phenylquinoline) (acetylacetonate) iridium (III), 2,8-di-t-butyl-5,11-bis (4-t-butylphenyl) -6, 12-diphenyltetracene, bis (2-phenylbenzothiazolato) (acetylacetonate) iridium (III), 5,10,15,20-tetraphenyltetrabenzoporphyrin platinum, osmium (II) bis (3- Trifluoromethyl-5- (2-pyridine) -pyrazolate) dimethylphenylphosphine, osmium (II) bis (3- (trifluoro Methyl) -5- (4-t-butylpyridyl) -1,2,4-triazolate) diphenylmethylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (2 -Pyridyl) -1,2,4-triazole) dimethylphenylphosphine, osmium (II) bis (3- (trifluoromethyl) -5- (4-t-butylpyridyl) -1,2, 4-triazolate) dimethylphenylphosphine, bis [2- (4-n-hexylphenyl) quinoline] (acetylacetonate) iridium (III), tris [2- (4-n-hexylphenyl) quinoline] iridium (III), tris [2-phenyl-4-methylquinoline] iridium (III), bis (2-phenylquinoline) (2- (3-methylphenyl) pyridinate) iridium (III), bis (2- (9 , 9-diethyl-fluoren-2-yl) -1-phenyl-1H-benzo [d] imidazolato) (acetylacetonate) iridium (III), bis (2-phenylpyridine) (3- ( Pyridin-2-yl) -2H-chromen-2-onate) iridium (III), bis (2-phenylquinoline) (2,2,6,6-tetramethylheptane-3,5-dionate) Iridium (III), bis (phenylisoquinoline) (2,2,6,6-tetramethylhepte Phosphorus-3,5-dionate) iridium (III), iridium (III) bis (4-phenylthieno [3,2-c] pyridinato-N, C ² ) acetylacetonate, (E) -2 -(2-t-butyl-6- (2- (2,6,6-trimethyl-2,4,5,6-tetrahydro-1H-pyrrolo [3,2,1-ij] quinoline-8 -Yl) vinyl) -4H-pyran-4-iriden) malononitrile, bis (3-trifluoromethyl-5- (1-isoquinolyl) pyrazolate) (methyldiphenylphosphine) ruthenium , Bis [(4-n-hexylphenyl) isoquinoline] (acetylacetonate) iridium (III), platinum (II) octaethylphosphine, bis (2-methyldibenzo [f, h] quinoxaline) (acetylaceto Nate) iridium (III), tris [(4-n-hexylphenyl) isoquinoline] iridium (III), etc. are mentioned.

As a material for forming the electron transporting layer, 8-hydroxyquinolinolate-lithium, 2,2 ', 2' '-(1,3,5-benzintriyl) -tris (1-phenyl-1-H-benz Imidazole), 2- (4-biphenyl) 5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10 -Phenanthroline, 4,7-diphenyl-1,10-phenanthroline, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum, 1,3-bis [2 -(2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] benzene, 6,6'-bis [5- (biphenyl-4-yl) -1 , 3,4-oxadiazo-2-yl] -2,2'-bipyridine, 3- (4-biphenyl) -4-phenyl-5-t-butylphenyl-1,2,4-triazole , 4- (naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole, 2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1 , 10-phenanthroline, 2,7-bis [2- (2,2'-bipyridin-6-yl) -1,3,4-oxadiazo-5-yl] -9,9-dimethyl Fluorene, 1,3-bis [2- (4-t-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene, tris (2,4,6-trimethyl-3- ( blood Ridin-3-yl) phenyl) borane, 1-methyl-2- (4- (naphthalen-2-yl) phenyl) -1H-imidazo [4,5f] [1,10] phenanthroline, 2- (Naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline, phenyl-dipyrenylphosphineoxide, 3,3 ', 5,5'-tetra [(m-pyridyl) -Phen-3-yl] biphenyl, 1,3,5-tris [(3-pyridyl) -phen-3-yl] benzene, 4,4'-bis (4,6-diphenyl-1,3 , 5-triazin-2-yl) biphenyl, 1,3-bis [3,5-di (pyridin-3-yl) phenyl] benzene, bis (10-hydroxybenzo [h] quinolinato) beryllium , Diphenylbis (4- (pyridin-3-yl) phenyl) silane, 3,5-di (pyren-1-yl) pyridine and the like.

Materials for forming the electron injection layer include lithium oxide (Li ₂ O), magnesium oxide (MgO), alumina (Al ₂ O ₃ ), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF ₂ ), and fluoride Cesium (CsF), strontium fluoride (SrF ₂ ), molybdenum trioxide (MoO ₃ ), aluminum, lithium acetylacetonate (Li (acac)), lithium acetate, lithium benzoate and the like.

Examples of the negative electrode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.

Moreover, the other example of the manufacturing method of the organic electroluminescent element of this invention when the thin film obtained from the charge-transporting varnish of this invention is a hole injection layer is as follows.

In the above-described organic EL device fabrication method, the charge formed by the charge transport varnish of the present invention is formed by sequentially forming the hole transport layer and the light emitting layer, instead of performing the vacuum deposition operation of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer. An organic EL device having a transport thin film can be produced. Specifically, the charge-transporting varnish of the present invention is applied onto the anode substrate to form a hole injection layer by the above-described method, a hole transport layer and a light emitting layer are sequentially formed thereon, and further a cathode material is deposited to form an organic EL device. do.

As the negative electrode and the positive electrode material to be used, those similar to those described above can be used, and the same cleaning treatment and surface treatment can be performed.

As a method for forming the hole transporting layer and the light emitting layer, a solvent is added to the hole transporting polymer material, the light emitting polymer material, or the material to which the dopant is added, or the particles are uniformly dispersed and coated on the hole injection layer or the hole transporting layer, and then fired. The film forming method can be mentioned.

As the hole-transporting polymer material, 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] -end capped with polysilses Quoxane, poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 '-(N- (p-butylphenyl)) diphenylamine)] and the like Can be mentioned.

As the light emitting polymer material, polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylenevinyl Polyphenylene vinylene derivatives such as ethylene) (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), polyvinylcarbazole (PVCz) and the like.

Toluene, xylene, chloroform, etc. are mentioned as a solvent. As a dissolution or uniform dispersion method, methods, such as stirring, heating stirring, and ultrasonic dispersion, are mentioned.

It does not specifically limit as a coating method, The inkjet method, the spray method, the dip method, the spin coat method, the transfer printing method, the roll coating method, the brushing etc. are mentioned. In addition, it is preferable to perform application | coating under inert gas, such as nitrogen and argon.

As a baking method, the method of heating in oven or a hotplate under inert gas or vacuum is mentioned.

An example of the manufacturing method of the organic electroluminescent element of this invention when the thin film obtained from the charge-transporting varnish of this invention is a hole injection transport layer is as follows.

A hole injection transport layer is formed on the anode substrate, and a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order on the hole injection transport layer. As a formation method and a specific example of a light emitting layer, an electron carrying layer, and an electron injection layer, the thing similar to what was mentioned above is mentioned.

As the material for forming the anode material, the light emitting layer, the luminescent dopant, the electron transporting layer and the electron blocking layer, and the cathode material, those similar to those described above may be mentioned.

In addition, a hole block layer, an electron block layer, or the like may be provided between the electrodes and any of the above layers as necessary. For example, tris (phenylpyrazole) iridium etc. are mentioned as a material which forms an electron block layer.

Since the material constituting the anode and cathode and the layer formed therebetween differs depending on which of the bottom emission structure and the top emission structure is manufactured, the material is appropriately selected in consideration of the point.

In general, a transparent anode is used on a substrate side in a device having a bottom emission structure, and a reflective anode made of a metal is used in a device in a top emission structure, while a light anode is taken out from the substrate side. Light is taken out from the (cathode) side. Therefore, for example, in the case of an anode material, a transparent anode such as ITO is used when producing a device having a bottom emission structure, and a reflective anode such as Al / Nd is used when producing a device having a top emission structure.

The organic EL device of the present invention may be sealed with a catcher or the like according to the conventional method in order to prevent deterioration of properties.

(Example)

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following. Moreover, the apparatus used is as follows.

(1) 1H-NMR: manufactured by Bruker, Ascend 500

(2) LC / MS: made by Waters, ZQ 2000

(3) Substrate cleaning: Choshu Sangyo Co., Ltd., substrate cleaning device (pressurized plasma method)

(4) Application of varnish: Mikasa Co., Ltd., spin coater MS-A100

(5) Film thickness measurement: Kosaka Kenkyu Sho Co., Ltd., fine shape measuring instrument surf coder ET-4000

(6) Weight average molecular weight (Mw) and number average molecular weight (Mn) measurement: Shimadzu Seisakusho Co., Ltd. (column: SHODEX GPC KF-803l + GPC KF-804L, column temperature: 40 degreeC, detector: UV detector ( 254 nm) and RI detector, eluent: THF, column flow rate: 1.0 mL / min.)

(7) Fabrication of organic EL device: Choshu Sangyo Co., Ltd., multi-functional deposition apparatus system C-E2L1G1-N

(8) Measurement of luminance and the like of organic EL elements: multichannel IVL measuring apparatus manufactured by HI C.

(9) Measurement of Lifetime of Organic EL Device: Organic EL Luminance Lifetime Evaluation System PEL-105S

[1] synthesis of monomers

Synthesis Example 1 Synthesis of Monomer 1

Synthesis Example 1-1 Synthesis of Intermediate 1-1

Xyl of 2,2-bis (3-amino-4-methylphenyl) -1,1,1,3,3,3-hexafluoropropane (7.25 g, 20 mmol) and iodobenzene (8.16 g, 40 mmol) Pd (PPh ₃ ) ₄ (1.16 g, 1 mmol) and t-BuONa (5.77 g, 60 mmol) were added to the styrene suspension (145 mL), and the mixture was heated to reflux for 4 hours after nitrogen substitution. After the reaction was completed, the mixture was allowed to cool to room temperature, water (70 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and then celite filtered. The crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain intermediate 1-1 as a brown liquid (amount 8.66 g, yield 84%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 1-2 Synthesis of Intermediate 1-2

In a toluene suspension (150 mL) of intermediate 1-1 (7.60 g, 14.8 mmol) and 4-iodotoluene (7.09 g, 32.5 mmol), Pd (dba) ₂ (340 mg, 0.6 mmol), [(t-Bu) ₃ PH] BF ₄ (344 mg, 1.18 mmol) and t-BuONa (4.27 g, 44.4 mmol) were added and reacted at 80 ° C for 3 hours. After the reaction was completed, the mixture was allowed to cool to room temperature, and water (75 mL) was added to wash the organic layer. The organic layer was dried over sodium sulfate and then celite filtered. The crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (eluate: toluene), and the oil containing Intermediate 1-2 was concentrated. Methanol was added thereto, and the precipitated solid was collected by filtration and methanol washed to obtain Intermediate 1-2 as a white solid (amount 6.04 g, yield 59%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 1-3 Synthesis of Monomer 1

DMF (45 mL) and THF (20 mL) were added to Intermediate 1-2 (6.01 g, 8.7 mmol), the solution was cooled to 0 ° C., and N-bromosuccinimide (3.00 g, 16.9 mmol) was added. . Then, it stirred at room temperature for 1 hour, and after cooling to 0 degreeC, water (60 mL) was dripped. The precipitated solid was collected by filtration and washed with water and methanol in this order to obtain monomer 1 as a white solid (amount 7.25 g, yield 98%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 2 Synthesis of Monomer 2

Synthesis Example 2-1 Synthesis of Intermediate 2-1

A dimethylformamide solution (45 mL) of 3-ethyl-3-hydroxymethyloxetane (2.32 g, 20 mmol) and 4-bromobenzylbromide (5.00 g, 20 mmol) was cooled to 0 ° C., and sodium hydride ( 0.96 g, 24 mmol) was added. It stirred at room temperature for 2 hours, and after cooling to 0 degreeC, water (90 mL) was dripped and extracted with ethyl acetate. After drying the organic layer with sodium sulfate, the crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give the intermediate 2-1 as a colorless liquid (amount 5.32 g, yield 93%). Obtained as. The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 2-2 Synthesis of Monomer 2

Of 2,2-bis (3-amino-4-methylphenyl) -1,1,1,3,3,3-hexafluoropropane (1.09 g, 3 mmol) and intermediate 2-1 (1.71 g, 6 mmol) Pd (dba) ₂ (34.5 mg, 0.06 mmol) and t-BuONa (0.69 g, 7.2 mmol) were added to the toluene suspension (22 mL), and reacted at 80 degreeC for 3 hours. After the reaction was completed, the mixture was allowed to cool to room temperature, water (20 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and then celite filtered. The crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give monomer 2 as a brown liquid (amount 1.99 g, yield 86%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 3 Synthesis of Monomer 3

Synthesis Example 3-1 Synthesis of Intermediate 3-1

Toluene suspension (40 mL) of monomer 2 (1.99 g, 2.6 mmol) and iodobenzene (1.16 g, 5.7 mmol) was added to Pd (dba) ₂ (148 mg, 0.26 mmol), [(t-Bu) ₃ PH] BF ₄ (150 mg, 0.52 mmol) and t-BuONa (0.74 g, 7.8 mmol) were added and heated to reflux for 1 hour after nitrogen substitution. After the reaction was completed, the mixture was allowed to cool to room temperature, water (40 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and then celite filtered. The crude product obtained by concentrating the filtrate was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give intermediate 3-1 as a brown liquid (amount 2.18 g, yield 91%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 3-2 Synthesis of Monomer 3

DMF (22 mL) was added to intermediate 3-1 (2.18 g, 2.4 mmol), the solution was cooled to 0 ° C., and N-bromosuccinimide (0.84 g, 4.8 mmol) was added thereto. Then, it stirred at room temperature for 1 hour, and water (40 mL) was dripped. The precipitated solid was collected by filtration and purified by silica gel column chromatography (eluate: hexane / ethyl acetate) to obtain monomer 3 as a pale yellow solid (amount 2.37 g, yield 93%). The measurement results of ¹ H-NMR and LC / MS are shown below.

Synthesis Example 4 Synthesis of Monomer 4

1,4-dioxane solution (48 mL) of 2,7-dibromo-9,9-dioctyl-9H-fluorene (4.80 g, 8.8 mmol) and bis (pinacolato) diboron (5.33 g, 21 mmol) ) Was added potassium acetate (3.45 g, 35 mmol) and dichloromethane adduct (287 mg, 0.35 mmol) of PdCl ₂ (dppf), followed by heating at 100 ° C. for 3 hours after nitrogen substitution. After the completion of the reaction, the product was filtered through celite, the filtrate was concentrated, and the crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to obtain monomer 4 as a white solid (2.64 g, 47% yield). . The measurement result of <^1> H-NMR is shown below.

[2] polymer synthesis

Example 1 Synthesis of Polymer 1

Methyltri-n-octylammonium chloride (182 mg, 0.45 mmol) in toluene solution (32 mL) of monomer 1 (1.38 g, 1.62 mmol), monomer 3 (0.19 g, 0.18 mmol) and monomer 4 (0.96 g, 1.5 mmol) , Pd (PPh ₃ ) ₄ (21 mg, 18 μmol) and 2 mol / L aqueous sodium carbonate solution (3.6 mL, 7.2 mmol) were added and heated to reflux for 16 hours. Phenylboronic acid (219 mg, 1.8 mmol) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. After completion of the reaction, the organic layer was washed with 1 mol / L hydrochloric acid and dried over sodium sulfate. After celite filtration, the organic layer was concentrated until the volume became 1/4 and added dropwise to methanol (320 mL). After stirring for 1 hour at room temperature, the precipitated solid was collected by filtration. This solid was dissolved in THF (20 mL), added dropwise to methanol (320 mL), stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration to obtain Polymer 1 as a pale yellow solid (1.47 g). The measurement result of Mw and Mn by GPC is shown below.

Mw = 6,400

Mn = 3,900

Mw / Mn = 1.64

Example 2 Synthesis of Polymer 2

Toluene solution (32 mL) of Monomer 3 (1.62 g, 1.5 mmol) and Monomer 4 (0.8 g, 1.25 mmol) in methyltri-n-octylammonium chloride (152 mg, 0.38 mmol), Pd (PPh ₃ ) ₄ (87 mg, 75 µmol) and 2 mol / L aqueous sodium carbonate solution (3 mL, 6 mmol) were added, and the mixture was heated to reflux for 24 hours. Phenylboronic acid (183 mg, 1.5 mmol) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. After completion of the reaction, the organic layer was washed with 1 mol / L hydrochloric acid and dried over sodium sulfate. After celite filtration, the organic layer was concentrated until the volume became 1/4 and added dropwise to methanol (320 mL). After stirring for 1 hour at room temperature, the precipitated solid was collected by filtration. This solid was dissolved in THF (10 mL), added dropwise to methanol (320 mL), stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration to obtain Polymer 2 as a colorless solid (1.02 g). The measurement result of Mw and Mn by GPC is shown below.

Mw = 7,800

Mn = 4,900

Mw / Mn = 1.59

Example 3 Synthesis of Polymer 3

Pd (dba) ₂ (115 mg, 0.2) in toluene solution (30 mL) of monomer 2 (1.54 g, 2 mmol) and 2,7-dibromo-9,9-dioctyl-9H-fluorene (1.11 g, 2.02 mmol) mmol), [(t-Bu) ₃ PH] BF ₄ (116 mg, 0.4 mmol) and t-BuONa (0.58 g, 6 mmol) were added and heated to reflux for 3 hours. Diphenylamine (338 mg, 2 mmol) was added to the reaction solution, and the mixture was further heated to reflux for 3 hours. After completion of the reaction, the organic layer was washed with 1 mol / L hydrochloric acid and dried over sodium sulfate. After celite filtration, the organic layer was concentrated until the volume became 1/4 and added dropwise to methanol (200 mL). After stirring for 1 hour at room temperature, the precipitated solid was collected by filtration. This solid was dissolved in toluene (10 mL), added dropwise to methanol (100 mL), stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration to obtain Polymer 3 as a yellow solid (0.44 g). The measurement result of Mw and Mn by GPC is shown below.

Mw = 5,700

Mn = 4,400

Mw / Mn = 1.30

Example 4 Synthesis of Polymer 4

Toluene solution (27 mL) of Monomer 1 (1.36 g, 1.6 mmol) and Monomer 4 (1.29 g, 2.0 mmol) in methyltri-n-octylammonium chloride (162 mg, 0.4 mmol), Pd (PPh ₃ ) ₄ (92 mg, 80 mol) and 2 mol / L aqueous sodium carbonate solution (3.2 mL, 6.4 mmol) were added, and the mixture was heated to reflux for 21 hours. Intermediate 2-1 (0.46 g, 1.6 mmol) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. After completion of the reaction, the organic layer was washed with 1 mol / L hydrochloric acid and dried over sodium sulfate. After celite filtration, the organic layer was concentrated until the volume became 1/4 and added dropwise to methanol (270 mL). After stirring for 1 hour at room temperature, the precipitated solid was collected by filtration. This solid was dissolved in THF (20 mL), added dropwise to methanol (270 mL), stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration to obtain Polymer 4 as a white solid (1.46 g). The measurement result of Mw and Mn by GPC is shown below.

Mw = 6,400

Mn = 4,100

Mw / Mn = 1.55

[3] preparation of charge-transporting varnishes

Example 5 Preparation of Charge Transport Varnish A

P-1 (Tokyo Kasei Co., Ltd.) (0.026 mg) represented by the following formula as a polymer 1 (0.129 mg) and a dopant was added to a mixed solvent of cyclohexanone (4.0 g) and anisole (1.0 g), The mixture was heated and stirred at 400 rpm for 50 minutes for 5 minutes. The obtained solution was filtered using a PTFE filter having a pore size of 0.2 μm to obtain a charge transport varnish A.

Example 6 Preparation of Charge Transport Varnish B

A charge-transporting varnish B was obtained in the same manner as in Example 5 except that Polymer 1 was changed to Polymer 2 (0.129 mg).

Example 7 Preparation of Charge Transport Varnish C

A charge-transporting varnish B was obtained in the same manner as in Example 5 except that Polymer 1 was changed to Polymer 3 (0.129 mg).

Example 8 Preparation of Charge Transport Varnish D

A charge-transporting varnish B was obtained in the same manner as in Example 5 except that Polymer 1 was changed to Polymer 4 (0.129 mg).

[4] fabrication of organic EL device and evaluation of its characteristics

As a substrate for evaluating the electrical properties, a 25 mm × 25 mm × 0.7 t glass substrate (hereinafter referred to as an ITO substrate) in which indium tin oxide was patterned at a film thickness of 150 nm on the surface was used. The ITO substrate was used after removing impurities on the surface by using an O ₂ plasma cleaning apparatus (150 W, 30 seconds).

Example 9 Fabrication of Organic EL Device Using Charge-Transport Varnish A

The charge-transporting varnish A prepared in Example 5 was applied to an ITO substrate using a spin coater, and then fired at 150 ° C. for 10 minutes in an air atmosphere to form a 50 nm uniform thin film on the ITO substrate.

Subsequently, 30 nm of (alpha) -NPD was formed into 0.2 nm / sec using the vapor deposition apparatus (vacuum degree 1.0x10 <^-5> Pa) with respect to the ITO board | substrate which formed the thin film. CBP and Ir (PPy) ₃ were then co-deposited. Co-deposition was carried out by controlling the deposition rate so that the Ir (PPy) ₃ concentration of 6% was stacked 40nm. Subsequently, thin films of Alq ₃ , lithium fluoride and aluminum were sequentially laminated to obtain an organic EL device. At this time, the deposition rates were performed under conditions of 0.2 nm / sec for Alq ₃ and aluminum and 0.02 nm / sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.

Moreover, in order to prevent the characteristic deterioration by the influence of oxygen, water, etc. in air, after sealing with an sealing substrate, the organic electroluminescent element evaluated the characteristic. Sealing was performed in the following procedures. The organic EL element was sandwiched between sealing substrates in a nitrogen atmosphere having an oxygen concentration of 2 ppm or less and a dew point of −85 ° C. or less, and the sealing substrate was bonded with an adhesive (Moreco Moisture Cut WB90US (P) manufactured by MORESCO Co., Ltd.). At this time, a catcher (manufactured by Dynec Co., Ltd., HD-071010W-40) was put together with the organic EL device into the sealing substrate. The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm ² ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.

Example 10 Fabrication of Organic EL Device Using Charge-Transport Varnish B

An organic EL device was fabricated in the same manner as in Example 9 except that a charge transport varnish B was used instead of a charge transport varnish A.

Example 11 Fabrication of Organic EL Device Using Charge-Transport Varnish C

An organic EL device was fabricated in the same manner as in Example 9 except that a charge transport varnish C was used instead of a charge transport varnish A.

Example 12 Fabrication of Organic EL Device Using Charge-Transport Varnish D

An organic EL device was fabricated in the same manner as in Example 9 except that the charge transport varnish D was used instead of the charge transport varnish A.

Example 9 - voltage, current density at a luminance 5,000cd / m ² with respect to the prepared organic EL element 12, and current efficiency, luminous efficiency and external quantum efficiency (EQE), and half-life (initial luminance of 5,000cd / m ² ) Was measured. The results are shown in Table 1.

Charge transport varnish Voltage
(V) Current density
(mA / cm ² ) Current efficiency
(cd / A) Luminous efficiency
(lm / W) EQE
(%) Half-life
(h) Example 9 A 8.9 27.9 17.9 6.3 5.2 386 Example 10 B 10.3 28.1 17.8 5.4 5.2 346 Example 11 C 10.4 28.3 17.7 5.3 5.1 358 Example 12 D 8.8 28.7 17.4 6.2 5.1 368

Claims (12)

The fluorine atom containing polymer represented by following formula (1) or (2).

(In formula, A <^1> -A <^3> respectively independently represents a C1-C6 fluoro alkyidayl group;
Ar ¹ to Ar ³ each independently represent an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and each having 1 to 2 carbon atoms which may be substituted with a halogen atom, a nitro group or a cyano group, or Z ¹ ; 20 alkyl group, is optionally substituted with a heteroaryl group having 2 to 20 carbon atoms alkenyl or 2 to 20 carbon atoms and an alkynyl group, or an aryl group having from 6 to 20 carbon atoms optionally substituted by Z ² or 2 to 20 carbon atoms of, and Each Ar ¹ , each Ar ² and each Ar ³ may be the same as or different from each other;
X ¹ to X ⁴ each independently represent a crosslinkable group;
Y ¹ to Y ⁴ each independently represent a single bond or an arylene group having 6 to 20 carbon atoms, and each Y ¹ , each Y ² , each Y ³ and each Y ⁴ may be the same as or different from each other;
R ¹ to R ¹⁰ are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. , a heteroaryl group having 1 to 20 carbon atoms an alkoxy group, having from 2 to 20 carbon atoms alkenyloxy group or 2 to 20 carbon atoms and an alkynyl group, or an aryl group having from 6 to 20 carbon atoms which may be substituted with Z ^2, 2 to 20 carbon atoms in the Group, a C6-C20 aryloxy group, or a C2-C20 heteroaryloxy group, and when two or more R <^1> -R <^10> exists, each R <^1> -R <^10> may mutually be same or different;
Z ¹ is a C6-C20 aryl group, a C2-C20 heteroaryl group, a C1-C20 alkoxy group, or a C2-C20 that may be substituted with a halogen atom, a nitro group or a cyano group, or Z ³ A 20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group;
Z ² is a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ³ , an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and having 1 to 20 carbon atoms. An alkoxy group, a C2-C20 alkenyloxy group, a C2-C20 alkynyloxy group, a C6-C20 aryl group, or a C2-C20 heteroaryl group;
Z ³ represents a halogen atom, a nitro group or a cyano group;
p, q, t, u, w and x each independently represent an integer of 0 to 4;
r, s, y and z each independently represent an integer of 0 to 4;
m and n represent a positive number satisfying 0 ≦ m ≦ 1, 0 <n ≦ 1 and m + n = 1;
k represents an integer of 1 or more.) The fluorine atom-containing polymer according to claim 1, wherein the weight average molecular weight is 1,000 to 1,000,000. The method according to claim 1 or 2, wherein A is a perfluoromethanediyl group, a perfluoroethane-1,2-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane Characterized in that it is a -2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluoropentane-1,5-diyl group or a perfluorohexane-1,6-diyl group A fluorine atom containing polymer. The fluorine atom-containing polymer according to any one of claims ¹ to ³ , wherein Ar ¹ to Ar ³ are derived from fluorene, benzene, naphthalene, biphenyl or derivatives thereof. The fluorine atom-containing polymer according to claim 4, wherein Ar ¹ to Ar ³ are a group represented by the following formula (3).

(In formula, R <^11> and R <^12> is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, or C2 A heteroaryl group of ˜20;
R ¹³ and R ¹⁴ are each independently a halogen atom, a nitro group or a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z ¹ , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms. Or a C6-C20 aryl group or C2-C20 heteroaryl group which may be substituted by Z <^2>;
a and b represent the integer of 0-3 each independently.) 6. A fluorine atom-containing polymer according to claim 5, wherein R ¹¹ and R ¹² together are an alkyl group. The fluorine atom-containing polymer according to any one of claims 1 to 6, wherein the crosslinkable group is a group containing a polymerizable carbon carbon double bond, an oxysilane ring or an oxetane ring. The charge-transporting material which consists of a fluorine atom containing polymer in any one of Claims 1-7. A charge transport varnish comprising the charge transport material, dopant and an organic solvent according to claim 8. The charge-transporting thin film manufactured using the charge-transporting varnish of Claim 9. An electronic device comprising the charge transporting thin film according to claim 10. An organic electroluminescent device comprising the charge transporting thin film according to claim 10.