Charge-transporting varnish

Patent metadata

Field	Value
Publication number	US-9853217-B2
Application number	US-201415026543-A
Country	US
Kind code	B2
Filing date	Sep 26, 2014
Priority date	Oct 1, 2013
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

A charge-transporting varnish which contains a charge-transporting substance containing fluorine atoms, a charge-transporting substance containing no fluorine atoms, a dopant substance composed of a heteropolyacid, and an organic solvent. The charge-transporting substance containing fluorine atoms is a polymer which is obtained by condensing a triaryl amine compound, an arylaldehyde compound containing fluorine atoms, a fluorene derivative having a carbonyl group and a carbazole derivative having an alkyl group or an alkyl group containing an ether structure in the N-position, and which has a weight average molecular weight of 1,000-200,000. The charge-transporting substance containing no fluorine atoms is an oligoaniline compound. A thin film formed from this charge-transporting varnish is capable of providing an organic EL element having excellent luminance characteristics and durability even in cases where the thin film is used as a single layer between a positive electrode and a light emitting layer in such a manner that the thin film is in contact with the positive electrode and the light emitting layer.

First claim

The invention claimed is:

1. A charge-transporting varnish comprising:
a charge-transporting substance containing a fluorine atom;
a charge-transporting substance containing no fluorine atom;
a dopant substance of heteropolyacid; and
an organic solvent,
wherein said charge-transporting substance containing the fluorine atom is a polymer having a weight-average molecular weight of 1,000 to 200,000 which is obtained by condensation from a triarylamine compound, arylaldehyde compound containing a fluorine atom, fluorene derivative having a carbonyl group, and carbazole derivative having at the N-position an alkyl group or an alkyl group having an ether structure,
said charge-transporting substance containing no fluorine atom is an oligoaniline compound.

2. The charge-transporting varnish of claim 1 ,
wherein the charge-transporting substance containing the fluorine atom is a polymer which is obtained by condensation from a triarylamine compound represented by Formula (1), an arylaldehyde compound containing a fluorine atom represented by Formula (2), a fluorene derivative having a carbonyl group represented by Formula (3) or (4), and a carbazole derivative represented by Formula (5):

wherein Ar 1 to Ar 3 mutually independently represent an aryl group having 6 to 20 carbon atoms with an optional substituent Z 1 , with each aryl group being composed of carbon atoms at least one of which has no substituent;
Ar 4 represents an aryl group having 6 to 20 carbon atoms with at least one substituent Z 3 and an optional substituent Z 4 ;
R 1 to R 8 mutually independently represent a hydrogen atom, halogen atom, nitro group, cyano group or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 2 ;
R 9 and R 10 mutually independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, (poly)ethyleneoxide group having 2 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 2 or alkyl group having 1 to 20 carbon atoms, a substituent of ethenyl group or ethynyl group and an optional substituent Z 2 ;
R 11 represents an alkyl group having 1 to 20 carbon atoms or alkyl group having 2 to 20 carbon atoms and having the ether structure, both having an optional substituent Z 2 ;
Z 1 represents a halogen atom, nitro group, or cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 2 ;
Z 2 represents a halogen atom, nitro group, or cyano group;
Z 3 represents a fluorine atom, fluorinated alkyl group having 1 to 20 carbon atoms, or fluorinated aryl group having 6 to 20 carbon atoms;
Z 4 represents a chlorine atom, bromine atom, iodine atom, nitro group, or cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 5 ; and
Z 5 represents a chlorine atom, bromine atom, iodine atom, nitro group, or cyano group.

3. The charge-transporting varnish of claim 2 ,
wherein said triarylamine compound is a triphenylamine derivative represented by Formula (6):

wherein R 12 to R 23 mutually independently represent a hydrogen atom, halogen atom, nitro group, or cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 2 .

4. The charge-transporting varnish of claim 2 or 3 ,
wherein said arylaldehyde compound is a benzaldehyde derivative represented by Formula (7) or (8):

wherein R 24 represents a fluorine atom or fluorinated alkyl group having 1 to 20 carbon atoms;
R 25 to R 28 mutually independently represent a hydrogen atom, nitro group, cyano group, or an alkyl group having 1 to 20 carbon atoms optionally substituted with a nitro group or cyano group; and
R 29 to R 33 mutually independently represent a fluorine atom or fluorinated alkyl group having 1 to 20 carbon atoms.

5. The charge-transporting varnish of claim 1 ,
wherein said oligoaniline compound is one represented by Formula (9):

wherein R 34 to R 39 mutually independently represent a hydrogen atom, halogen atom other than fluorine atom, nitro group, or cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 6 , or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms, each having an optional substituent Z 7 , or —NHY 2 , —NY 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 group;
Y 2 to Y 13 mutually independently represent an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 6 , or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms, each having an optional substituent Z 7 ;
X 1 represents —NY 1 —, —O—, —S—, —(CR 40 R 41 ) k —, or a single bond wherein R 40 and R 41 are identical with the R 34 mentioned above;
letter k represents an integer of 1 to 20;
Y 1 represents independently a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 6 , or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms, each having an optional substituent Z 7 ;
Z 6 represents a halogen atom other than fluorine atom, nitro group, or cyano group, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms, each having an optional substituent Z 8 ;
Z 7 represents a halogen atom other than fluorine atom, nitro group, or cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, or alkynyl group having 2 to 20 carbon atoms, each having an optional substituent Z 8 ;
Z 8 represents a halogen atom other than fluorine atom, nitro group, or cyano group; and
letters m and n mutually independently represent an integer of 1 to 10, with m+n≦10.

6. The charge-transporting varnish of claim 1 ,
wherein said heteropolyacid is phosphotungstic acid.

7. The charge-transporting varnish of claim 1 , further comprising a curing agent.

8. The charge-transporting varnish of claim 7 ,
wherein said curing agent is a curing agent of acrylate type.

9. A charge-transporting thin film prepared from the charge-transporting varnish of claim 1 .

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

11. An organic electroluminescence element having the charge-transporting thin film of claim 9 .

12. An organic electroluminescence element including

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Otani Naoki

Classifications

• H01L51/5024

  Electricity · mapped topic

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• H01L51/5206

  Electricity · mapped topic

• H01L51/506

  Electricity · mapped topic

• C09D5/24

  Electrically-conducting paints {(conductive materials H01B1/00)} · CPC title