Charge-transporting varnishes
Provided are charge-transporting varnishes that can form satisfactory thin films and can provide organic EL elements that can exhibit excellent emission efficiency and luminance characteristics when used for EL elements that have a structure on a substrate. The charge-transporting varnishes comprise quinone diimine derivatives represented by general formula (1) that are oligoaniline derivatives or oxides thereof, electron-accepting dopant substances or hole-accepting dopant substances, and at least one kind of silane compound. [In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, etc. A and B each independently represents a divalent group represented by general formula (2) or (3). (In the formulas, R 4 -R 11 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, etc.) m and n are each independently integers of 1 or greater and satisfy m+n≦20.]
1. A charge-transporting varnish comprising an oligoaniline derivative represented by the general formula (1) or a quinonediimide derivative that is an oxidized product thereof, an electron-accepting dopant substance or a hole accepting dopant substance, a silane compound, and a solvent
wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphoric group, a phosphoric ester group, an ester group, a thioester group, an amide group, a nitro group, a monovalent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group or a sulfonic group, A and B are each independently a divalent group represented by the general formula (2) or (3):
wherein R 4 -R 11 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphoric group, a phosphoric ester group, an ester group, a thioester group, an amide group, a nitro group, a monovalent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group or a sulfonic group, and m and n are each independently an integer of 1 or over with the proviso that m+n≦20,
wherein said silane compound is at least one selected from the group consisting of dialkoxysilane compounds, trialkoxysilane compounds, tetraalkoxysilane compounds and silicone compounds.
2. The charge-transporting varnish of claim 1 , wherein said oligoaniline derivative or quinonediimine derivative that is an oxidized product thereof is an oligoaniline derivative represented by the general formula (4) or an quinonediimine derivative that is an oxidized product thereof,
wherein R 1 -R 7 , m and n are as defined above.
3. The charge-transporting varnish of claim 1 , wherein said electron-accepting dopant substance is an arylsulfonic acid derivative represent by the formula (5):
wherein X is O, S or NH, A is a naphthalene ring or anthracene ring that may have a substituent other than X and n is the number of SO 3 H groups, B is an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group or an unsubstituted or substituted group represented by the following group (6) or (7):
wherein W 1 and W 2 are each independently O, S, S(O), S(O 2 ), or unsubstituted or substituent group-bonded N, Si, P or P(O), n is the number of sulfonic acid groups bonded to A with the proviso that n is an integer satisfying 1≦n≦4, and q is the bond number between B and X with the proviso that q is an integer satisfying 1≦q.
4. The charge-transporting varnish of claim 1 , wherein said solvent is an organic solvent.
5. The charge-transporting varnish of claim 4 , which comprises 0.0001 to 10 wt % of water relative to said organic solvent.
6. The charge-transporting varnish of claim 1 , wherein a proportion of silane compound is in the range of 1 to 50 wt % relative to the total weight of solids in said charge-transporting varnish.
7. A charge transporting thin film prepared from the charge-transporting varnish of any one of claims 1 to 6 .
8. An organic electroluminescence element having the charge transporting thin film of claim 7 .
9. The charge-transporting varnish of claim 1 , wherein said silane compound is at least two selected from the group consisting of dialkoxysilane compounds, trialkoxysilane compounds, tetraalkoxysilane compounds and silicone compounds.
10. The charge-transporting varnish of claim 1 , wherein said silane compound is at least one selected from the group consisting of dialkoxysilane compounds, trialkoxysilane compounds and tetraalkoxysilane compounds.
11. The charge-transporting varnish of claim 10 , wherein said silane compound is at least one selected from the group consisting of trialkoxysilane compound represented by the formula (9), dialkoxysilane compound represented by the formula (10), and tetraalkoxysilane compound represented by the formula (11):
Y 1 Si(OY 2 ) 3 (9)
Y 3 Y 4 Si(OY 5 ) 2 (10)
Si(OY 6 ) 4 (11)
wherein Y 1 is a halogen atom, a hydrogen atom, or 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 or a heteroaryl group, each of which may be substituted with Z,
Y 2 is an alkyl group having 1 to 12 carbon atoms,
Y 3 and Y 4 are each independently a halogen atom, or 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 or a heteroaryl group, each of which may be substituted with Z,
Y 5 is an alkyl group having 1 to 12 carbon atoms,
Y 6 is an alkyl group having 1 to 12 carbon atoms, and
Z is a halogen atom, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atom, a hydroxyl group, a mercapto group, an amino group, a haloalkoxy group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a haloalkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a haloalkynyl group having 2 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, an alkenylcarbonyl group having 3 to 12 carbon atoms, an alkynylcarbonyl group having 3 to 12 carbon atoms, an alkylcarbonyloxy group having 2 to 12 carbon atoms, an alkenylcarbonyloxy group having 3 to 12 carbon atoms, an alkynylcarbonyloxy group having 3 to 12 carbon atoms, an aryl group, a halogenated aryl group, a heteroaryl group, or a halogenated heteroaryl group.
12. The charge-transporting varnish of claim 11 , wherein said silane compound is at least two selected from the group consisting of trialkoxysilane compound represented by the formula (9), dialkoxysilane compound represented by the formula (10), and tetraalkoxysilane compound represented by the formula (11).