Charge-transporting varnish

Patent metadata

Field	Value
Publication number	US-10158081-B2
Application number	US-201414771099-A
Country	US
Kind code	B2
Filing date	Feb 24, 2014
Priority date	Feb 28, 2013
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

Provided is a charge-transporting varnish which includes a charge-transporting material including fluorine atoms, a charge-transporting material not including fluorine atoms, a dopant material comprising heteropoly acid, and an organic solvent, said charge-transporting material including fluorine atoms being a polymer of weight-average 1,000 to 200,000 molecular weight obtained by condensing a triarylamine compound, an aryl aldehyde compound including fluorine atoms, and a fluorine derivative having a carbonyl group, and said charge-transporting material not including fluorine atoms being an oligoaniline compound. The charge-transporting varnish provides a thin film which, even in a case of being used as a single layer in contact with and in between an anode and a luminescent layer, is capable of achieving an organic EL element having superior luminance characteristics and durability.

First claim

The invention claimed is:

1. A charge-transporting varnish characterized by comprising a charge-transporting material containing fluorine atoms, a charge-transporting material not containing fluorine atoms, a dopant material composed of a heteropolyacid, and an organic solvent,
wherein the charge-transporting material containing fluorine atoms is a polymer having a weight-average molecular weight of from 1,000 to 200,000 which is obtained by condensation of a triarylamine compound, a fluorine atom-containing arylaldehyde compound, and a carbonyl group-bearing fluorene derivative, and
the charge-transporting material not containing fluorine atoms is an oligoaniline compound.

2. The charge-transporting varnish according to claim 1 , wherein the charge-transporting material containing fluorine atoms is a polymer obtained by condensation of a triarylamine compound of formula (1), a fluorine atom-containing arylaldehyde compound of formula (2), and a carbonyl group-bearing fluorene derivative of formula (3) or formula (4)

(wherein Ar 1 to Ar 3 are each independently an aryl group of 6 to 20 carbons which may be substituted with Z 1 , with at least one constituent carbon atom in each aryl group being unsubstituted;
Ar 4 is an aryl group of 6 to 20 carbons which is substituted with at least one Z 3 and may also be substituted with Z 4 ;
R 1 to R 8 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 2 ;
R 9 and R 10 are each independently a hydrogen atom, an alkyl group of 1 to 20 carbons, (poly)ethylene oxide group of 2 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 2 , or an alkyl group of 1 to 20 carbons which is substituted with an ethenyl or ethynyl group and may also be substituted with Z 2 ;
Z 1 is a halogen atom, a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 2 ;
Z 2 is a halogen atom, a nitro group or a cyano group;
Z 3 is a fluorine atom, a fluorinated alkyl group of 1 to 20 carbons, or a fluorinated aryl group of 6 to 20 carbons;
Z 4 is a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 5 ; and
Z 5 is a chlorine atom, a bromine atom, an iodine atom, a nitro group or a cyano group).

3. The charge-transporting varnish according to claim 2 , wherein the triarylamine compound is a triphenylamine derivative of formula (5)

(wherein R 11 to R 22 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 2 , Z 2 being the same as defined above).

4. The charge-transporting varnish according to claim 2 or 3 , wherein the arylaldehyde compound is a benzaldehyde derivative of formula (6) or formula (7)

(wherein R 23 is a fluorine atom or a fluorinated alkyl group of 1 to 20 carbons;
R 24 to R 27 are each independently a hydrogen atom, a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons which may be substituted with a nitro or cyano group; and
R 28 to R 32 are each independently a fluorine atom or a fluorinated alkyl group of 1 to 20 carbons).

5. The charge-transporting varnish according to claim 1 , wherein the oligoaniline compound has formula (8)

(wherein R 33 to R 38 are each independently a hydrogen atom, a halogen atom (exclusive of a fluorine atom), a nitro group, a cyano group, an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 6 , an aryl group of 6 to 20 carbons or heteroaryl group of 2 to 20 carbons which may be substituted with Z 7 , —NHY 2 , —NHY 3 Y 4 , —C(O)Y 5 , —OY 6 , —SY 7 , —SO 3 Y 8 , —C(O)OY 9 , —OC(O)Y 10 , —C(O)NHY 11 or —C(O)NY 12 Y 13 ;
Y 2 to Y 13 are each independently an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 6 , or an aryl group of 6 to 20 carbons or heteroaryl group of 2 to 20 carbons which may be substituted with Z 7 ;
X 1 is —NY 1 —, —O—, —S—CR 39 R 40 ) l — or a single bond, with R 39 and R 40 being the same as defined for R 33 ;
l is an integer from 1 to 20;
Y 1 is independently at each occurrence a hydrogen atom, an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 6 , or an aryl group of 6 to 20 carbons or heteroaryl group of 2 to 20 carbons which may be substituted with Z 7 ;
Z 6 is a halogen atom (exclusive of a fluorine atom), a nitro group, a cyano group, or an aryl group of 6 to 20 carbons or heteroaryl group of 2 to 20 carbons which may be substituted with Z 8 ;
Z 7 is a halogen atom (exclusive of a fluorine atom), a nitro group, a cyano group, or an alkyl group of 1 to 20 carbons, alkenyl group of 2 to 20 carbons or alkynyl group of 2 to 20 carbons which may be substituted with Z 8 ;
Z 8 is a halogen atom (exclusive of a fluorine atom), a nitro group or a cyano group; and
m and n are each independently an integer from 1 to 10 and together satisfy the condition m+n≤10).

6. The charge-transporting varnish according to claim 1 , wherein the heteropolyacid compound is phosphotungstic acid.

7. The charge-transporting varnish according to claim 1 , which further comprises a curing agent.

8. The charge-transporting varnish according to claim 7 , wherein the curing agent is an acrylate curing agent.

9. A charge-transporting film produced using the charge-transporting varnish of claim 1 .

10. An electronic device comprising the charge-transporting thin-film of claim 9 .

11. An organic electroluminescence device comprising the charge-transporting thin-film of claim 9 .

12. An organic electroluminescence device comprising at least a positive electrode, a negative electrode, an emissive layer and the charge-transporting thin-film of claim 9 ,
which device includes the charge-transporting thin-film between the positive electrode and the emissive layer in a form that contacts each of these layers.

13. A method of producing a charge-transporting thin-film, characterized by coating the charge-transporting varnish of claim 1 onto a substrate and evaporating off the solvent.

14. A method of producing an organic electroluminescence device using the charge-transporting thin-film of claim 9 .

15. A polymer characterized by being obtained by condensation of a triarylamine compound of formula (1), a fluorine atom-containing arylaldehyde compound of formula (2), and a carbonyl group-bearing fluorene derivative of formula (3) or formula (4), and by having a weight-average molecular weight of from 1,000 to 200,000

Assignees

• Nissan Chemical Ind Ltd
• Nissan Chemical Industires Ltd

Inventors

• Otani Naoki

Classifications

• C09D161/00

  Coating compositions based on condensation polymers of aldehydes or ketones (with polyalcohols C09D159/00; with polynitriles C09D177/00); Coating compositions based on derivatives of such polymers · CPC title

• C09K2211/1416

  Condensed systems · CPC title

• C08G2261/3142

  fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene · CPC title

• C09D179/02

  Polyamines · CPC title

• C08L79/02

  Polyamines · CPC title