Patent Application
20170117491
The present invention relates to a light emitting device and a composition used in the same.
Light emitting devices such as an organic electroluminescent device (organic EL device) can be suitably used for applications of displays and lightings and are recently attracting attention, because of high external quantum efficiency and low driving voltage. This light emitting device has organic layers such as a light emitting layer and a charge transporting layer.
Patent document 1 discloses a light emitting device in which a metal complex A1 and a low molecular weight compound A1 represented by the following formulae are used in a light emitting layer. Patent document 2 discloses a light emitting device in which a metal complex A2 and a low molecular weight compound A2 represented by the following formulae are used in a light emitting layer.
Patent document 1: International Publication WO2004/101707
Patent document 2: JP-A No. 2010-135467
The light emitting devices disclosed in Patent documents 1 and 2 described above, however, did not necessarily have sufficient external quantum efficiency.
Then, the present invention has an object of providing a light emitting device excellent in external quantum efficiency. Further, the present invention has an object of providing a composition which is useful for production of a light emitting device excellent in external quantum efficiency.
In a first aspect, the present invention provides a light emitting device comprising
an anode,
a cathode,
a first organic layer disposed between the anode and the cathode and
a second organic layer disposed between the anode and the cathode,
wherein the first organic layer is a layer obtained by using a composition comprising a compound represented by the formula (H-A) and a metal complex represented by the formula (1), and
the second organic layer is a layer obtained by using a polymer compound comprising a constitutional unit having a crosslinkable group:
[wherein,
ZA represents a group represented by —C(RZA)2—, a group represented by —Si(RZA)2, a group represented by —N(RZA)—, a group represented by —B(RZA)—, a group represented by —P(RZA)—, a group represented by —P(═O) (RZA)—, a sulfur atom or an oxygen atom. RZA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups each optionally have a substituent. When a plurality of RZA are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached.
Z1, Z2, Z3 and Z4 each independently represent a carbon atom or a nitrogen atom. At least one of Z1, Z2, Z3 and Z4 is a carbon atom.
RZ1, RZ2, RZ3 and RZ4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups each optionally have a substituent. RZ1 is not present when Z1 is a nitrogen atom. RZ2 is not present when Z2 is a nitrogen atom. RZ3 is not present when Z3 is a nitrogen atom. RZ4 is not present when Z4 is a nitrogen atom. At least one of RZ1, RZ2, RZ3 and RZ4 is a monovalent heterocyclic group represented by the formula (H-1).
The ring RHA represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings each optionally have a substituent. When a plurality of the substituents are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached.
RZ1 and RZ2, RZ2 and RZ3, RZ3 and RZ4, RZ1 and RZA, a substituent which the ring RHA optionally has and RZA, and a substituent which the ring RHA optionally has and RZ4 each may be combined together to form a ring together with the atoms to which they are attached.]
[wherein,
the ring RH1 and the ring RH2 each independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings each optionally have a substituent. When a plurality of the substituents are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached.]
(wherein,
M represents a ruthenium atom, a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
n1 represents an integer of 1 or more, n2 represents an integer of 0 or more, and n1+n2 is 2 or 3. n1+n2 is 3 when M is a ruthenium atom, a rhodium atom or an iridium atom, while n1+n2 is 2 when M is a palladium atom or a platinum atom.
E1A, E2A, E3A and E4A each independently represent a nitrogen atom or a carbon atom. Two of E1A, E2A, E3A and E4A are a nitrogen atom and the remaining two are a carbon atom. When a plurality of E1A, E2A, E3A and E4A are present, they may be the same or different at each occurrence.
E2 represents a carbon atom or a nitrogen atom. At least one of E1A and E2 is a carbon atom.
R2A, R3A and R4A each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups each optionally have a substituent. When a plurality of R2A, R3A and R4A are present, they may be the same or different at each occurrence. R2A and R3A, R3A and R4A, and a substituent which the ring RB optionally has and R2A each may be combined together to form a ring together with the atoms to which they are attached. R2A may be either present or not present when E2A is a nitrogen atom. R3A may be either present or not present when E3A is a nitrogen atom. R4A may be either present or not present when E4A is a nitrogen atom.
The ring R1A represents a triazole ring constituted of a nitrogen atom, E1A, E2A, E3A and E4A.
The ring RB represents a 5-membered or 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocyclic ring, and these rings each optionally have a substituent. When a plurality of the substituents are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached. When a plurality of the rings RBare present, they may be the same or different. E2 is a carbon atom when the ring RV is a 6-membered aromatic heterocyclic ring.
A1-G1-A2 represents an anionic bidentate ligand, and G1 represents an atomic group constituting a bidentate ligand together with A1 and A2. A1 and A2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms each may be a carbon atom, an oxygen atom or a nitrogen atom constituting a ring. When a plurality of A1-G1-A2 are present, they may be the same or different.].
In a second aspect, the present invention provides a composition comprising
a compound represented by the formula (H-B) and
at least one metal complex selected from the group consisting of a metal complex represented by the formula (1-A1) and a metal complex represented by the formula (1-A2):
[wherein,
Z1, Z2, Z3 and Z4 each independently represent a carbon atom or a nitrogen atom. At least one of Z1, Z2, Z3 and Z4 is a carbon atom.
RZ1, RZ2, RZ3 and RZ4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups each optionally have a substituent. RZ1 is not present when Z1 is a nitrogen atom. RZ2 is not present when Z2 is a nitrogen atom. RZ3 is not present when Z3 is a nitrogen atom. RZ4 is not present when Z4 is a nitrogen atom. At least one of RZ1, RZ2, RZ3 and RZ4 is a monovalent heterocyclic group represented by the formula (H-1).
The ring RHA represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings each optionally have a substituent. When a plurality of the substituents are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached.
RZ1 and RZ2, RZ2 and RZ3, RZ3 and RZ4, RZ1 and RZA, and a substituent which the ring RHA optionally has and RZ4 each may be combined together to form a ring together with the atoms to which they are attached.]
[wherein,
the ring RH1 and the ring RH2 each independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and these rings each optionally have a substituent. When a plurality of the substituents are present, they may be the same or different and may be combined together to form a ring together with the atoms to which they are attached.]
[wherein,
M1 represents an iridium atom or a platinum atom.
n1A represents an integer of 2 or 3, and n1A is 3 when M1 is iridium, while n1A is 2 when M1 is platinum.
R2A, R3A, R4A, R2B, R3B, R4B and R5B each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups each optionally have a substituent. When a plurality of R2A, R3A, R4A, R2B, R3B, R4B and R5B are present, they may be the same or different at each occurrence. R3A and R4A, R2A and R2B, R2B and R3B, R3B and R4B, and R4B and R5B each may be combined together to form a ring together with the atoms to which they are attached.].
The present invention can provide a light emitting device excellent in external quantum efficiency. Further, the present invention can provide a composition which is useful for production of a light emitting device excellent in external quantum efficiency.
Suitable embodiments of the present invention will be illustrated in detail below.
Terms commonly used in the present specification have the following meanings unless otherwise stated.
Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and t-Bu represents a tert-butyl group.
A hydrogen atom may be a light hydrogen atom or a heavy hydrogen atom.
A solid line representing a bond to a central metal in a formula representing a metal complex denotes a coordinate bond or a covalent bond.
“Polymer compound” denotes a polymer having molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1×103 to 1×110.
A polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer and a graft copolymer, and may also be another embodiment.
An end group of a polymer compound is preferably a stable group because if a polymerization active group remains intact at the end, when the polymer compound is used for fabrication of a light emitting device, the light emitting property or luminance life possibly becomes lower. This end group is preferably a group having a conjugated bond to the main chain, and includes, for example, groups bonding to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.
“Low molecular weight compound” denotes a compound having no molecular weight distribution and having a molecular weight of 1×104 or less.
“Constitutional unit” denotes a unit structure found once or more in a polymer compound.
“Alkyl group” may be any of linear or branched. The number of carbon atoms of the linear alkyl group is, not including the number of carbon atoms of a substituent, usually 1 to 50, preferably 3 to 30, more preferably 4 to 20. The number of carbon atoms of the branched alkyl groups is, not including the number of carbon atoms of a substituent, usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.
The alkyl group optionally has a substituent, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoamyl group, a 2-ethylbutyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 3-propylheptyl group, a decyl group, a 3,7-dimethyloctyl group, a 2-ethyloctyl group, a 2-hexyldecyl group and a dodecyl group, and groups obtained by substituting a hydrogen atom in these groups with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like, and the alkyl group having a substituent includes, for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, a 3-(4-methylphenyl)propyl group, a 3-(3,5-di-n-hexylphenyl) propyl group and a 6-ethyloxyhexyl group.
The number of carbon atoms of a cycloalkyl group is, not including the number of carbon atoms of a substituent, usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.
The cycloalkyl group optionally has a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group and a cyclohexylethyl group.
“Aryl group” denotes an atomic group remaining after removing from an aromatic hydrocarbon one hydrogen atom linked directly to a carbon atom constituting the ring. The number of carbon atoms of the aryl group is, not including the number of carbon atoms of a substituent, usually 6 to 60, preferably 6 to 20, more preferably 6 to 10.
The aryl group optionally has a substituent, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups obtained by substituting a hydrogen atom in these groups with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
“Alkoxy group” may be any of linear or branched. The number of carbon atoms of the linear alkoxy group is, not including the number of carbon atoms of a substituent, usually 1 to 40, preferably 4 to 10. The number of carbon atoms of the branched alkoxy group is, not including the number of carbon atoms of a substituent, usually 3 to 40, preferably 4 to 10.
The alkoxy group optionally has a substituent, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group, and groups obtained by substituting a hydrogen atom in these groups with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom or the like.
The number of carbon atoms of a cycloalkoxy group is, not including the number of carbon atoms of a substituent, usually 3 to 40, preferably 4 to 10.
The cycloalkoxy group optionally has a substituent, and examples thereof include a cyclohexyloxy group.
The number of carbon atoms of “Aryloxy group” is, not including the number of carbon atoms of a substituent, usually 6 to 60, preferably 7 to 48.
The aryloxy group optionally has a substituent, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups obtained by substituting a hydrogen atom in these groups with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or the like.
“p-Valent heterocyclic group” (p represents an integer of 1 or more) denotes an atomic group remaining after removing from a heterocyclic compound p hydrogen atoms among hydrogen atoms directly linked to a carbon atom or a hetero atom constituting the ring. Of p-valent heterocyclic groups, “p-valent aromatic heterocyclic groups” as an atomic group remaining after removing from an aromatic heterocyclic compound p hydrogen atoms among hydrogen atoms directly linked to a carbon atom or a hetero atom constituting the ring are preferable.
“Aromatic heterocyclic compound” denotes a compound in which the heterocyclic ring itself shows aromaticity such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole and dibenzophosphole, and a compound in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself shows no aromaticity such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole and benzopyran.
The number of carbon atoms of the monovalent heterocyclic group is, not including the number of carbon atoms of a substituent, usually 2 to 60, preferably 4 to 20.
The monovalent heterocyclic group optionally has a substituent, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, a triazinyl group, and groups obtained by substituting a hydrogen atom in these groups with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like.
“Halogen atom” denotes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
“Amino group” optionally has a substituent, and a substituted amino group is preferable. The substituent which an amino group has is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group.
The substituted amino group includes, for example, a dialkylamino group, a dicycloalkylamino group and a diarylamino group.
The amino group includes, for example, a dimethylamino group, a diethylamino group, a diphenylamino group, a bis(4-methylphenyl)amino group, a bis(4-tert-butylphenyl)amino group and a bis(3,5-di-tert-butylphenyl)amino group.
“Alkenyl group” may be any of linear or branched. The number of carbon atoms of the linear alkenyl group, not including the number of carbon atoms of the substituent, is usually 2 to 30, preferably 3 to 20. The number of carbon atoms of the branched alkenyl group, not including the number of carbon atoms of the substituent, is usually 3 to 30, preferably 4 to 20.
The number of carbon atoms of a cycloalkenyl group, not including the number of carbon atoms of the substituent, is usually 3 to 30, preferably 4 to 20.
The alkenyl group and cycloalkenyl group each optionally have a substituent, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and these groups having a substituent.
“Alkynyl group” may be any of linear or branched. The number of carbon atoms of the alkynyl group, not including the number of carbon atoms of the substituent, is usually 2 to 20, preferably 3 to 20. The number of carbon atoms of the branched alkynyl group, not including the number of carbon atoms of the substituent, is usually 4 to 30, preferably 4 to 20.
The number of carbon atoms of a cycloalkynyl group, not including the number of carbon atoms of the substituent, is usually 4 to 30, preferably 4 to 20.
The alkynyl group and cycloalkynyl group each optionally have a substituent, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexenyl group, a 5-hexenyl group, and these groups having a substituent.
“Arylene group” denotes an atomic group remaining after removing from an aromatic hydrocarbon two hydrogen atoms linked directly to carbon atoms constituting the ring. The number of carbon atoms of the arylene group is, not including the number of carbon atoms of a substituent, usually 6 to 60, preferably 6 to 30, more preferably 6 to 18.
The arylene group optionally has a substituent, and examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a naphthacenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group, a chrysenediyl group, and these groups having a substituent, preferably, groups represented by the formulae (A-1) to (A-20). The arylene group includes groups obtained by linking a plurality of these groups.
[wherein, R and Ra each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. The plurality of R and Ra each may be the same or different, and groups Ra may be combined together to form a ring together with the atoms to which they are attached.]
The number of carbon atoms of the divalent heterocyclic group is, not including the number of carbon atoms of a substituent, usually 2 to 60, preferably 3 to 20, more preferably 4 to 15.
The divalent heterocyclic group optionally has a substituent, and examples thereof include divalent groups obtained by removing from pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, azole, diazole and triazole two hydrogen atoms among hydrogen atoms linking directly to a carbon atom or a hetero atom constituting the ring, preferably groups represented by the formulae (AA-1) to (AA-34). The divalent heterocyclic group includes groups obtained by linking a plurality of these groups.
[wherein, R and Ra represent the same meaning as described above.]
“Crosslinkable group” is a group capable of forming a new bond by being subjected to a heating treatment, an ultraviolet irradiation treatment, a radical reaction and the like, and crosslinkable groups are preferably groups represented by the formulae (XL-1) to (XL-17) of Group A of crosslinkable group.
[wherein, RXL represents a methylene group, an oxygen atom or a sulfur atom, and nXL represents an integer of 0 to 5. When a plurality of RXL are present, they may be the same or different, and when a plurality of nXL are present, they may b e the same or different. *l represents a binding position. These crosslinkable groups each optionally have a substituent.]
“Substituent” represents a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a cycloalkynyl group. The substutuent may be a crosslinkable group or a dendron.
“Dendron” denotes a group having a regular dendritic branched structure having a branching point at an atom or ring (that is, a dendrimer structure). A compound having a dendron (hereinafter, referred to as “dendrimer”) includes, for example, structures described in literatures such as International Publication WO02/067343, JP-A No. 2003-231692, International Publication WO2003/079736, International Publication WO2006/097717 and the like.
The dendron is preferably a group represented by the formula (D-A) or (D-B).
[wherein,
mDA1, mDA2 and mDA3 each independently represent an integer of 0 or more.
GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups each optionally have a substituent.
ArDA1, ArDA2 and ArDA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of ArDA1, ArDA2 and ArDA3 are present, they may be the same or different at each occurrence.
TDA represents an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. The plurality of TDA may be the same or different.]
[wherein,
mDA1, mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 each independently represent an integer of 0 or more.
GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups each optionally have a substituent. The plurality of GDA may be the same or different.
ArDA1, ArDA2, ArDA3, ArDA4, ArDA5, ArDA6 and ArDA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of ArDA1, ArDA2, ArDA3, ArDA4, ArDA5, ArDA6 and ArDA7 are present, they may be the same or different at each occurrence.
TDA represents an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. The plurality of TDA may be the same or different.]
mDA1, mDA2, mDA3, mDA4, mDA5, mDA6, and mDA7 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1. It is preferable that mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 are the same integer, and it is more preferable that mDA1, mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 are the same integer.
GDA is preferably a group represented by the formula (GDA-11) to (GDA-15), and these groups each optionally have a substituent.
[wherein,
* represents a linkage to ArDA1 in the formula (D-A), ArDA1 in the formula (D-B), ArDA2 in the formula (D-B) or ArDA3 in the formula (D-B).
** represents a linkage to ArDA2 in the formula (D-A), ArDA2 in the formula (D-B), ArDA4 in the formula (D-B) or ArDA6 in the formula (D-B).
*** represents a linkage to ArDA3 in the formula (D-A), ArDA3 in the formula (D-B), ArDA5 in the formula (D-B) or ArDA7 in the formula (D-B).
RDA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of RDA are present, they may be the same or different.]
RDA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or cycloalkyl group, and these groups each optionally have a substituent.
It is preferable that ArDA1 ArDA2, ArDA3, ArDA4, ArDA5, ArDA6 and ArDA7 are groups represented by the formulae (ArDA-1) to (ArDA-3).
[wherein,
RDA represents the same meaning as described above.
RDB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of RDB are present, they may be the same or different.]
RDB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, further preferably an aryl group, and these groups each optionally have a substituent.
TDA is preferably groups represented by the formulae (TDA-1) to (TDA-3).
[wherein, RDA and RDB represent the same meaning described above.]
The group represented by the formula (D-A) is preferably a group represented by the formula (D-A1) to (D-A4), more preferably a group represented by the formula (D-A1) to (D-A3).
[wherein,
RDA represents the same meaning as described above.
Rp1, Rp2 and Rp3 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When a plurality of Rp1 and Rp2 are present, they may be the same or different at each occurrence.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. The plurality of np1 may be the same or different.]
The group represented by the formula (D-B) is preferably a group represented by the formula (D-B1) to (D-B3).
[wherein,
Rp1, Rp2 and Rp3 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When a plurality of Rp1 and Rp2 are present, they may be the same or different at each occurrence.
np1 represents an integer of 0 to 5, np2 represents an integer of 0 to 3, and np3 represents 0 or 1. When a plurality of np1 and np2 are present, they may be the same or different at each occurrence.]
np1 is preferably 0 or 1, more preferably 1. np2 is preferably 0 or 1, more preferably 0. np3 is preferably 0.
Rp1, Rp2 and Rp3 are preferably an alkyl group or a cycloalkyl group.
Next, the light emitting device of the present invention will be illustrated.
The light emitting device of the present invention is a light emitting device comprising an anode, a cathode, a first organic layer disposed between the anode and the cathode, and a second organic layer disposed between the anode and the cathode, wherein the first organic layer is a layer obtained by using a composition comprising a compound represented by the formula (H-A) and a metal complex represented by the formula (1), and the second organic layer is a layer obtained by using a polymer compound comprising a constitutional unit having a crosslinkable group.
“Obtained by using” regarding a relation between the first organic layer and a composition for forming the organic layer means that the first organic layer is formed by using the composition. The composition itself may be contained in the first organic layer, or materials contained in the composition may be crosslinked intramolecularly or intermolecularly or in both modes and contained in the first organic layer.
“Obtained by using” regarding a relation between the second organic layer and a polymer compound for forming the organic layer means that the second organic layer is formed by using the polymer compound. The polymer compound itself may be contained in the second organic layer, or the polymer compound may be crosslinked intramolecularly or intermolecularly or in both modes and contained in the second organic layer.
The method of forming the first organic layer and the second organic layer includes, for example, a vacuum vapor deposition method, and application methods typified by a spin coat method and an inkjet printing method.
When the first organic layer is formed by an application method, it is preferable to use an ink of the first organic layer described later. After formation of the first organic layer, materials contained in the composition can be crosslinked by heating or irradiation with light. When materials contained in the composition is crosslinked and contained in the first organic layer, the first organic layer is substantially insolubilized in a solvent. For this reason, the first organic layer can be suitably used for lamination of a light emitting device.
When the second organic layer is formed by an application method, it is preferable to use an ink of the second organic layer described later. After formation of the second organic layer, the polymer compound can be crosslinked by heating or irradiation with light. When the polymer compound is crosslinked and contained in the second organic layer, the second organic layer is substantially insolubilized in a solvent. For this reason, the second organic layer can be suitably used for lamination of light emitting device.
It is preferable for the light emitting device of the present invention that the polymer compound is crosslinked and contained in the second organic layer.
The temperature of heating for crosslinking is usually 25 to 300° C., preferably 50 to 250° C., more preferably 150 to 200° C.
The kind of light used for irradiation with light for crosslinking is, for example, ultraviolet light, near ultraviolet light and visible light.
The first organic layer is a layer obtained by using a composition comprising a compound represented by the formula (H-A) and a metal complex represented by the formula (1) (hereinafter, referred to also as “composition of first organic layer”.).
ZA is preferably a group represented by —C(RZA)2—, a group represented by —N(RZA)—, an oxygen atom or a sulfur atom, more preferably a group represented by —N(RZA)—, an oxygen atom or a sulfur atom, further preferably a group represented by —N(RZA)— or a sulfur atom, particularly preferably a sulfur atom, because the light emitting device of the present invention is more excellent in external quantum efficiency. That is, the compound represented by the formula (H-A) is preferably a compound represented by the formula (H-B).
RZA is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, an aryl group or a monovalent heterocyclic group, further preferably an alkyl group or an aryl group, particularly preferably an alkyl group, and these groups each optionally have a substituent.
The aryl group represented by RZA is preferably a phenyl group, a fluorenyl group or a spirobifluorenyl group, more preferably a phenyl group, and these groups each optionally have a substituent.
The monovalent heterocyclic group represented by RZA is preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group or an azacarbazolyl group, more preferably a pyridyl group, a dibenzothienyl group, a dibenzofuryl group or a carbazolyl group, and these groups each optionally have a substituent.
The substituent which RZA optionally has is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, further preferably an alkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally further have a substituent.
It is preferable that at least three of Z1, Z2, Z3 and Z4 are a carbon atom, and it is more preferable that all of them are a carbon atom, because the light emitting device of the present invention is excellent in external quantum efficiency.
RZ1, RZ2, RZ3 and RZ4 are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, further preferably a hydrogen atom, an aryl group or a monovalent heterocyclic group, particularly preferably a hydrogen atom or a monovalent heterocyclic group, because the light emitting device of the present invention is more excellent in external quantum efficiency, and these groups each optionally have a substituent. At least one of RZ1, RZ2, RZ3 and RZ4 is a monovalent heterocyclic group represented by the formula (H-1).
The examples and preferable range of the aryl group represented by RZ1, RZ2, RZ3 and RZ4 are the same as the examples and preferable range of the aryl group represented by RZA.
The examples and preferable range of the monovalent heterocyclic group represented by RZ1, RZ2, RZ3 and RZ4 are the same as the examples and preferable range of the monovalent heterocyclic group represented by RZA. At least one of RZ1, RZ2, RZ3 and RZ4 is a monovalent heterocyclic group represented by the formula (H-1).
It is preferable that RZ1 or RZ3 is a monovalent heterocyclic group represented by the formula (H-1), and it is more preferable that RZ3 is a monovalent heterocyclic group represented by the formula (H-1), because the light emitting device of the present invention is more excellent in external quantum efficiency.
The examples and preferable range of the substituent which RZ1, RZ2, RZ3 and RZ4 each optionally have are the same as the examples and preferable range of the substituent which RZA optionally has.
The ring RHA is preferably a benzene ring, a fluorene ring, a pyridine ring, a diazabenzene ring or a carbazole ring, more preferably a benzene ring, a pyridine ring or a pyrimidine ring, further preferably a benzene ring or a pyridine ring, particularly preferably a benzene ring, because the light emitting device of the present invention is more excellent in external quantum efficiency, and these rings each optionally have a substituent.
The examples and preferable range of the substituent which the ring RHA optionally has are the same as the examples and preferable range of the substituent which RZA optionally has.
The examples and preferable range of the ring RH1 and the ring RH2 are the same as the examples and preferable range of the ring RHA.
The monovalent heterocyclic group represented by the formula (H-1) is preferably a monovalent heterocyclic group represented by the formula (H-2), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein,
ZH1, ZH2, ZH3, ZH4, ZH5, ZH6, ZH7 and ZH8 each independently represent a carbon atom or a nitrogen atom.
RH1, RH2, RH3, RH4, RH5, RH6, RH7 and RH8 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups each optionally have a substituent.
RH1 is not present when ZH1 is a nitrogen atom. RH2 is not present when ZH2 is a nitrogen atom. RH3 is not present when ZH3 is a nitrogen atom. RH4 is not present when ZH4 is a nitrogen atom. RH5 is not present when ZH5 is a nitrogen atom. RH6 is not present when ZH6 is a nitrogen atom. RH7 is not present when ZH7 is a nitrogen atom. RH8 is not present when ZH8 is a nitrogen atom.
RH1 and RH2, RH2 and RH3, RH3 and RH4, RH4 and RH5, RH5 and RH6, RH6 and RH7, and RH7 and RH8 each may be combined together to form a ring together with the carbon atoms to which they are attached.]
It is preferable that at least six of ZH1, ZH2, ZH3, ZH4, ZH5, ZH6, ZH7 and ZH8 are a carbon atom, it is more preferable that at least seven of them are a carbon atom, it is further preferable that all of them are a carbon atom, because the light emitting device of the present invention is excellent in external quantum efficiency.
When two of ZH1, ZH2, ZH3, ZH4, ZH5, ZH6, ZH7 and ZH8 are a nitrogen atom, it is preferable that one of ZH1, ZH2, ZH3 and ZH4 is a nitrogen atom and one of ZH5, ZH6, ZH7 and ZH8 is a nitrogen atom.
When one of ZH1, ZH2, ZH3, ZH4, ZH5, ZH6, ZH7 and ZH8 is a nitrogen atom, it is preferable that ZH3 or ZH4 is a nitrogen atom.
RH1, RH2, RH3, RH4, RH5, RH6, RH7 and RH8 are preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, further preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom, because the light emitting device of the present invention is more excellent in external quantum efficiency, and these groups each optionally have a substituent.
The examples and preferable range of the substituent which RH1, RH2, RH3, RH4, RH5, RH6, RH7 and RH8 each optionally have are the same as the examples and preferable range of the substituent which RZA optionally has.
The monovalent heterocyclic group represented by the formula (H-2) is preferably a monovalent heterocyclic group represented by the formula (H-2-1) to the formula (H-2-6), more preferably a monovalent heterocyclic group represented by the formula (H-2-1) to the formula (H-2-3), further preferably a group represented by the formula (H-2-1).
[wherein, RH3 and RH6 represent the same meaning as described above.]
Specific examples of the monovalent heterocyclic group represented by the formula (H-2) include monovalent heterocyclic groups represented by the formula (H-2-1′) to the formula (H-2-11′).
The compound represented by the formula (H-A) is preferably a compound represented by the formula (H-A1), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein,
ZA, Z1, Z2, Z3, Z4, RZ1, RZ2, RZ3 and RZ4 represent the same meaning as described above.
Z5, Z6, Z7 and Z8 each independently represent a carbon atom or a nitrogen atom.
RZ5, RZ6, RZ7 and RZ8 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group or a halogen atom, and these groups each optionally have a substituent. RZ5 is not present when Z5 is a nitrogen atom. RZ6 is not present when Z6 is a nitrogen atom. RZ7 is not present when Z7 is a nitrogen atom. RZ8 is not present when Z8 is a nitrogen atom.
RZ4 and RZ5, RZ5 and RZ6, RZ6 and RZ7, RZ7 and RZ8, and RZ8 and RZA each may be combined together to form a ring together with the atoms to which they are attached.]
The compound represented by the formula (H-A1) is preferably a compound represented by the formula (H-B1), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein, Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, RZ1, RZ2, RZ3, RZ4, RZ5, RZ6, RZ7 and RZ8 represent the same meaning as described above.]
It is preferable that at least three of Z5, Z6, Z7 and Z8 are a carbon atom, and it is more preferable that all of them are a carbon atom, because the light emitting device of the present invention is excellent in external quantum efficiency.
RZ5, RZ6, RZ7 and RZ8 represent preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, further preferably a hydrogen atom, an aryl group or a monovalent heterocyclic group, particularly preferably a hydrogen atom or a monovalent heterocyclic group, and these groups each optionally have a substituent.
The examples and preferable range of the aryl group represented by RZ5, RZ6, RZ7 and RZ8 are the same as the examples and preferable range of the aryl group represented by RZA.
The examples and preferable range of the monovalent heterocyclic group represented by RZ5, RZ6, RZ7 and RZ8 are the same as the examples and preferable range of the monovalent heterocyclic group represented by RZA.
It is preferable that at least one of RZ5, RZ6, RZ7 and RZ8 is a monovalent heterocyclic group represented by the formula (H-1), it is more preferable that RZ6 or RZ8 is a monovalent heterocyclic group represented by the formula (H-1), it is further preferable that RZ6 is a monovalent heterocyclic group represented by the formula (H-1), because the light emitting device of the present invention is more excellent in external quantum efficiency.
The examples and preferable range of the substituent which RZ5, RZ6, RZ7 and RZ8 each optionally have are the same as the examples and preferable range of the substituent which RZA optionally has.
The compound represented by the formula (H-A1) is preferably a compound represented by the formula (H-A2), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein, ZA, RZ1, RZ3, RZ6 and RZ8 represent the same meaning as described above. At least one of RZ1 and RZ3 is a monovalent heterocyclic group represented by the formula (H-1).]
The compound represented by the formula (H-A2) is preferably a compound represented by the formula (H-B2), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein, RZ1, RZ3, RZ6 and RZ8 represent the same meaning as described above. At least one of RZ1 and RZ3 is a monovalent heterocyclic group represented by the formula (H-1).]
The compound represented by the formula (H-A) includes, for example, compounds represented by the formulae (H-A-1) to (H-A-5) and compounds represented by the formulae (H-A2-1) to (H-A2-25), preferably compounds represented by the formulae (H-A2-1) to (H-A2-15), more preferably compounds represented by the formulae (H-A2-1) to (H-A2-10). The compound represented by the formula (H-A2-1) to (H-A2-25) is a compound represented by the formula (H-A2).
[wherein, ZA and RZA represent the same meaning as described above. RHX represents a group represented by the formula (H-1).]
The compound represented by the formula (H-A2) includes, for example, compounds represented by the formulae (H-A2-1) to (H-A2-25).
In Table 1 to Table 3, specific examples of the monovalent heterocyclic group represented by the formula (H-1) include monovalent heterocyclic groups represented by the formula (H-2-1′) to the formula (H-2-11′) described above.
The compound represented by the formula (H-A) can be synthesized, for example, according to methods described in International Publication WO2009/086028, International Publication WO2009/096202, JP-A No. 2009-46408 and JP-A No. 2009-267255.
Specifically, the compound represented by the formula (H-A) can be synthesized by subjecting a compound represented by the formula (H-A′) and a compound represented by the formula (H-1′) to a known coupling reaction such as the Buchwald-Hartwig reaction and the Ullmann reaction. In detail, a chlorine atom, a bromine atom, an iodine atom or, a carbon atom linking to a group represented by O—S(═O)2RC1 in a compound represented by the formula (H-A′), and a nitrogen atom in a compound represented by the formula (H-1′) are bound.
[wherein,
ZA, Z1, Z2, Z3, Z4 and the ring RHA represent the same meaning as described above.
RZ1′, RZ2′, RZ3′ and RZ4′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom or a group represented by O—S(═O)2RC1 (wherein, RC1 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent.), and these groups each optionally have a substituent. RZ1′ is not present when Z1 is a nitrogen atom. RZ2′ is not present when Z2 is a nitrogen atom. RZ3′ is not present when Z3 is a nitrogen atom. RZ4′ is not present when Z4 is a nitrogen atom. At least one of RZ1′, RZ2′, RZ3′ and RZ4′ is a chlorine atom, a bromine atom, an iodine atom or a group represented by O—S(═O)2RC1.
RZ1′ and RZ2′, RZ2′ and RZ3′, RZ3′ and RZ4′, RZ1′ and RZA, a substituent which the ring RHA optionally has and RZA, and a substituent which the ring RHA optionally has and RZ4′ each may be combined together to form a ring together with the atoms to which they are attached.]
[wherein, the ring RH1 and the ring RH2 represent the same meaning as described above.]
The coupling reaction is conducted usually in the presence of a catalyst, a base and a reaction solvent. The catalyst, the base and the reaction solvent each may be used singly, or two or more of them may be used in combination.
The catalyst includes, for example, a palladium catalyst and a copper catalyst. The catalyst may be used in combination with an amine compound, a phosphorus compound and the like.
The base includes, for example, sodium carbonate, potassium carbonate, potassium tert-butoxide and sodium tert-butoxide.
The reaction solvent includes, for example, organic solvents such as tert-butanol, tetrahydrofuran, 1,4-dioxane, methylene chloride, chloroform, acetonitrile, toluene, xylene, tetrahydrofuran, 1,4-dioxane and N,N-dimethylformamide, and water.
The reaction temperature of the coupling reaction is usually −100 to 200° C. The reaction time of the coupling reaction is usually 30 minutes or more.
M is preferably an iridium atom or a platinum atom, more preferably an iridium atom, because the light emitting device of the present invention is excellent in luminance life.
When M is a ruthenium atom, a rhodium atom or an iridium atom, n1 is preferably 2 or 3, more preferably 3.
When M is a palladium atom or a platinum atom, n1 is preferably 2.
Two of E1A, E2A, E3A and E4A are a nitrogen atom and the remaining two are a carbon atom. The ring R2A is a triazole ring constituted of a nitrogen atom, E1A, E2A, E3A and E4A. It is preferable that E2A and E3A are a nitrogen atom or E2A and E4A are a nitrogen atom, and it is more preferable that E2A and E3A are a nitrogen atom, because the light emitting device of the present invention is more excellent in external quantum efficiency.
When E2A is a nitrogen atom and R2A is present, R2A is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably an alkyl group, an aryl group or a dendron, and these groups each optionally have a substituent.
When E2A is a carbon atom, R2A represents preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group or a dendron, further preferably a hydrogen atom or an alkyl group, and these groups each optionally have a substituent.
When E3A is a nitrogen atom and R3A is present, R3A is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably an alkyl group, an aryl group or a dendron, and these groups each optionally have a substituent.
When E3A is a carbon atom, R3A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group or a dendron, further preferably a hydrogen atom or an alkyl group, and these groups each optionally have a substituent.
When E4A is a nitrogen atom and R4A is present, R4A is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably an alkyl group, an aryl group or a dendron, and these groups each optionally have a substituent.
When E4A is a carbon atom, R4A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group or a dendron, further preferably a hydrogen atom or an alkyl group, and these groups each optionally have a substituent.
The dendron represented by R2A, R3A and R4A is preferably a group represented by the formula (D-A1) or (D-B1), more preferably a group represented by the formula (D-A1), because the light emitting device of the present invention is excellent in external quantum efficiency.
When E2A is a nitrogen atom and R2A is present, the dendron represented by R2A is preferably a group represented by the formula (D-A1), (D-A4) or (D-B1), more preferably a group represented by the formula (D-A4), because the light emitting device of the present invention is excellent in external quantum efficiency.
When E3A is a nitrogen atom and R3A is present, the dendron represented by R3A is preferably a group represented by the formula (D-A1), (D-A4) or (D-B1), more preferably a group represented by the formula (D-A4), because the light emitting device of the present invention is excellent in external quantum efficiency.
When E4A is a nitrogen atom and R4A is present, the dendron represented by R4A is preferably a group represented by the formula (D-A1), (D-A4) or (D-B1), more preferably a group represented by the formula (D-A4), because the light emitting device of the present invention is excellent in external quantum efficiency.
E2 is preferably a carbon atom, because synthesis of a metal complex represented by the formula (1) is easy.
The ring RB is preferably a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a pyridine ring, a diazabenzene ring or a triazine ring, more preferably a benzene ring, a pyridine ring or a pyrimidine ring, further preferably a benzene ring, and these rings each optionally have a substituent.
The substituent which the ring RB optionally has is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group or a dendron, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a dendron, further preferably an alkyl group, an aryl group or a dendron, particularly preferably an aryl group or a dendron, and these groups each optionally further have a substituent.
The examples and preferable range of the dendron as the substituent which the ring RB optionally has are the same as the examples and preferable range of the dendron represented by R2A, R3A and R4A.
The anionic bidentate ligand represented by A1-G1-A2 includes, for example, ligands represented by the following
[wherein, *2 represents a site binding to M or M1 described later.]
The anionic bidentate ligand represented by A1-G1-A2 may be a ligand represented by the following formula.
[wherein,
*2 represents the same meaning as described above.
RL1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups each optionally have a substituent. The plurality of RL1 may be the same or different.
RL2 represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups each optionally have a substituent.]
RL1 represents preferably a hydrogen atom, an alkyl group, an aryl group, a fluorine atom or a dendron, and these groups each optionally have a substituent.
RL2 is preferably an alkyl group, an aryl group or a dendron, and these groups each optionally have a substituent.
The metal complex represented by the formula (1) is preferably a metal complex represented by the formula (1-A), because the light emitting device of the present invention is more excellent in external quantum efficiency.
[wherein,
E1A, E2A, E3A, E4A, R2A, R3A, R4A, the ring R1A and A1-G1-A1 represent the same meaning as described above.
M1 represents an iridium atom or a platinum atom.
n3 represents an integer of 1 or more, n4 represents an integer of 0 or more, and n3+n4 is 2 or 3. n3+n4 is 3 when M1 is an iridium atom, while n3+n4 is 2 when M is a platinum atom.
E2B, E3B, E4B and E5B each independently represent a nitrogen atom or a carbon atom. When a plurality of E2B, E3B, E4B and E5B are present, they may be the same or different at each occurrence. R2B is not present when E2B is a nitrogen atom. R3B is not present when E3B is a nitrogen atom. R4B is not present when E4B is a nitrogen atom. R5B is not present when E5B is a nitrogen atom.
R2B, R3B, R4B and R5B each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom or a dendron, and these groups each optionally have a substituent. When a plurality of R2B, R3B, R4B and R5B are present, they may be the same or different at each occurrence. R2A and R3A, R3A and R4A, R2A and R2B, RB and R3B, R3B and R4B, and R4B and R5B each may be combined together to form a ring together with the atoms to which they are attached.
The ring R1B represents a benzene ring, a pyridine ring or a pyrimidine ring constituted of two carbon atoms, E2B, E3B, E4B and E5B.]
M1 is preferably an iridium atom.
When M1 is an iridium atom, n3 is preferably 2 or 3, more preferably 3.
When M1 is a platinum atom, n3 is preferably 2.
When the ring R1B is a pyridine ring, it is preferable that E3B, E4B or E5B is a nitrogen atom, and it is more preferable that E3B is a nitrogen atom.
When the ring R1B is a pyrimidine ring, it is preferable that E2B and E4B or E3B and E5B are a nitrogen atom, and it is more preferable that E3B and E5B are a nitrogen atom.
The ring R1B is preferably a benzene ring.
R2B is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a fluorine atom or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a fluorine atom, further preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom, and these groups each optionally have a substituent.
R3B is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, further preferably a hydrogen atom, an alkyl group, an aryl group or a dendron, particularly preferably a hydrogen atom, an aryl group or a dendron, and these groups each optionally have a substituent.
R4B is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a fluorine atom or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, further preferably a hydrogen atom, an alkyl group, an aryl group or a dendron, particularly preferably a hydrogen atom, an aryl group or a dendron, and these groups each optionally have a substituent.
R5B is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, a fluorine atom or a dendron, more preferably a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a dendron, further preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom, and these groups each optionally have a substituent.
The examples and preferable range of the dendron represented by R2B, R3B, R4B and R5B are the same as the examples and preferable range of the dendron represented by R2A, R3A and R4A.
The metal complex represented by the formula (1-A) is preferably a metal complex represented by the formula (1-A1) or (1-A2), more preferably a metal complex represented by the formula (1-A1).
[wherein,
M1, R2A, R3A, R4A, R2B, R3B, R4B and R5B represent the same meaning as described above.
n1A represents an integer of 2 or 3, and n1A is 3 when M1 is iridium, while n1A is 2 when M1 is platinum.]
The metal complex represented by the formula (1) includes, for example, metal complexes represented by the formulae (1-1) to (1-7), the formulae (1-A1-1) to (1-A1-18) and the formulae (1-A2-1) to (1-A2-12), preferably metal complexes represented by the formulae (1-A1-1) to (I-A1-18) or the formulae (1-A2-1) to (1-A2-12), more preferably metal complexes represented by the formulae (1-A1-1) to (1-A1-18). The metal complex represented by the formula (1-A1-1) to (1-A1-18) is a metal complex represented by the formula (1-A1), and the metal complex represented by the formula (1-A2-1) to (1-A2-12) is a metal complex represented by the formula (1-A2).
In Tables 4 to 6, the groups represented by the formulae (D-A-1) to (D-A-4) are as described below.
[wherein, RP represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, and these groups each optionally have a substituent. The plurality of RP may be the same or different.]
RP is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, further preferably a methyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group or a group represented by the formula (Rp-1), particularly preferably a tert-butyl group or a group represented by the formula (Rp-1).
The metal complex represented by the formula (1) can be produced, for example, by methods described in “Journal of the American Chemical Society, Vol. 107, 1431-1432 (1985)”, “Journal of the American Chemical Society, Vol. 106, 6647-6653 (1984)”, International Publication WO2004/101707, JP-A No. 2013-147449, JP-A No. 2013-147450 and JP-A No. 2013-147451.
The composition of the first organic layer comprises a compound represented by the formula (H-A) and a metal complex represented by the formula (1).
In the composition of the first organic layer, the compound represented by the formula (H-A) may be contained singly, or two or more of the compounds represented by the formula (H-A) may be contained. In the composition of the first organic layer, the metal complex represented by the formula (1) may be contained singly, or two or more of the metal complexes represented by the formula (1) may be contained.
In the composition of the first organic layer, the content of the metal complex represented by the formula (1) is usually 0.01 to 90 parts by weight when the sum of the compound represented by the formula (H-A) and the compound represented by the formula (1) is 100 parts by weight, and preferably 1 to 60 parts by weight, more preferably 10 to 40 parts by weight, further preferably 20 to 30 parts by weight, because the light emitting device of the present invention is more excellent in external quantum efficiency.
It is preferable that the composition of the first organic layer comprises a compound represented by the formula (H-B) as the compound represented by the formula (H-A) and at least one metal complex selected from the group consisting of a metal complex represented by the formula (1-A1) and a metal complex represented by the formula (1-A2) as the metal complex represented by the formula (1), because the light emitting device of the present invention is more excellent in external quantum efficiency.
In the composition of the first organic layer, at least one material selected from the group consisting of a hole transporting material, a hole injection material, an electron transporting material, an electron injection material, a light emitting material (different from the metal complex represented by the formula (1)), an antioxidant and a solvent may be further contained.
The hole transporting material is classified into low molecular weight compounds and polymer compounds, and polymer compounds are preferable, and polymer compounds having a crosslinkable group are more preferable.
The polymer compound includes, for example, polyvinylcarbazole and derivatives thereof; polyarylene having an aromatic amine structure in the side chain or main chain and derivatives thereof. The polymer compound may also be a compound in which an electron accepting portion is linked. The electron accepting portion includes, for example, fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene and trinitrofluorenone, preferably fullerene.
In the composition of the first organic layer, the compounding amount of the hole transporting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The hole transporting material may be used singly, or two or more hole transporting materials may be used in combination.
The electron transporting material is classified into low molecular weight compounds and polymer compounds. The electron transporting material optionally has a crosslinkable group.
The low molecular weight compound includes, for example, a metal complexe having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene, diphenoquinone and derivatives thereof.
The polymer compound includes, for example, polyphenylene, polyfluorene and derivatives thereof. These polymer compounds may be doped with a metal.
In the composition of the first organic layer, the compounding amount of the electron transporting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The electron transporting material may be used singly, or two or more electron transporting materials may be used in combination.
The hole injection material and the electron injection material are each classified into low molecular weight compounds and polymer compounds. The hole injection material and the electron injection material each optionally have a crosslinkable group.
The low molecular weight compound includes, for example, metal phthalocyanines such as copper phthalocyanine; carbon; oxides of metals such as molybdenum and tungsten; metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride and potassium fluoride.
The polymer compound includes, for example, polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, polythienylenevinylene, polyquinoline and polyquinoxaline, and derivatives thereof; electrically conductive polymers such as a polymer comprising an aromatic amine structure in the main chain or side chain.
In the composition of the first organic layer, the compounding amounts of the hole injection material and the electron injection material are each usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The hole injection material and the electron injection material may each be used singly, or two or more of them may be used in combination.
When the hole injection material or the electron injection material comprises an electrically conductive polymer, the electric conductivity of the electrically conductive polymer is preferably 1×10−5 S/cm to 1×103 S/cm. For adjusting the electric conductivity of the electrically conductive polymer within such a range, the electrically conductive polymer can be doped with a suitable amount of ions.
The kind of the ion to be doped is an anion for a hole injection material and a cation for an electron injection material. The anion includes, for example, a polystyrenesulfonate ion, an alkylbenzenesulfonate ion and a camphorsulfonate ion. The cation includes, for example, a lithium ion, a sodium ion, a potassium ion and a tetrabutylammonium ion.
The ion to be doped may be used singly, or two or more ions to be doped may be used.
The light emitting material (different from a metal complex represented by the formula (1)) is classified into low molecular weight compounds and polymer compounds. The light emitting material optionally has a crosslinkable group.
The low molecular weight compound includes, for example, naphthalene and derivatives thereof, anthracene and derivatives thereof, perylene and derivatives thereof, and, triplet light emitting complexes having iridium, platinum or europium as the central metal.
The polymer compound includes, for example, polymer compounds comprising a phenylene group, a naphthalenediyl group, an anthracenediyl group, a fluorenediyl group, a phenanthrenediyl group, dihydrophenanthrenediyl group, a group represented by the formula (X), a carbazolediyl group, a phenoxazinediyl group, a phenothiazinediyl group, a pyrenediyl group and the like.
The light emitting material preferably comprises a triplet light emitting complex and a polymer compound.
The triplet light emitting complex includes, for example, metal complexes listed below.
In the composition of the first organic layer, the compounding amount of the light emitting material is usually 0.1 to 400 parts by weight, preferably 5 to 150 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The light emitting material may be used singly, or two or more light emitting materials may be used in combination.
The antioxidant may advantageously be one which is soluble in the same solvent as for a compound represented by the formula (H-A) and a metal complex represented by the formula (1) and does not disturb light emission and charge transportation, and the examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.
In the composition of the first organic layer, the compounding amount of the antioxidant is usually 0.001 to 10 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The antioxidant may be used singly, or two or more antioxidants may be used in combination.
The composition of the first organic layer comprising a solvent (hereinafter, referred to also as “ink of first organic layer”.) can be suitably used in application methods such as a spin coat method, a casting method, a micro gravure coat method, a gravure coat method, a bar coat method, a roll coat method, a wire bar coat method, a dip coat method, a spray coat method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method, a capillary coat method and a nozzle coat method.
The viscosity of the ink of the first organic layer may be adjusted depending on the kind of the application method, and when a solution goes through a discharge apparatus such as in an inkjet printing method, the viscosity is preferably in the range of 1 to 20 mPa·s at 25° C. because curved aviation and clogging in discharging are unlikely.
As the solvent contained in the ink of the first organic layer, those capable of dissolving or uniformly dispersing solid components in the ink are preferable. The solvent includes, for example, chlorine-based solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as THF, dioxane, anisole and 4-methylanisole; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, ethylbenzene, n-hexylbenzene and cyclohexylbenzene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane and bicyclohexyl; ketone solvents such as acetone, methylethylketone, cyclohexanone and acetophenone; ester solvents such as ethyl acetate, butyl acetate, ethylcellosolve acetate, methyl benzoate and phenyl acetate; poly-hydric alcohol solvents such as ethylene glycol, glycerin and 1,2-hexanediol and derivatives thereof; alcohol solvents such as isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide. These solvents may be used singly, or two or more of them may be used in combination.
In the ink of the first organic layer, the compounding amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20000 parts by weight when the sum of the compound represented by the formula (H-A) and the metal complex represented by the formula (1) is 100 parts by weight.
The second organic layer is a layer obtained by using a polymer compound comprising a constitutional unit having a crosslinkable group (hereinafter, referred to also as “polymer compound of second organic layer”.).
The second organic layer may also be a layer obtained by using a composition comprising the polymer compound of the second organic layer and the metal complex represented by the formula (1). In the composition comprising the polymer compound of the second organic layer and the metal complex represented by the formula (1), the content of the metal complex represented by the formula (1) is usually 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight when the sum of the metal complex represented by the formula (1) and the polymer compound of the second organic layer is 100 parts by weight.
The crosslinkable group which the constitutional unit contained in the polymer compound of the second organic layer has is preferably a crosslinkable group selected from Group A of crosslinkable group, more preferably a crosslinkable group represented by the formula (XL-1), (XL-3), (XL-5), (XL-7), (XL-9), (XL-10), (XL-16) or (XL-17), further preferably a crosslinkable group represented by the formula (XL-1), (XL-3), (XL-7), (XL-9), (XL-10), (XL-16) or (XL-17), particularly preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-17), especially preferably a crosslinkable group represented by the formula (XL-17), because the polymer compound of the second organic layer is excellent in crosslinkability.
The crosslinkable group which the constitutional unit contained in the polymer compound of the second organic layer has may be present singly, or two or more of the crosslinkable groups may be present.
The constitutional unit having a crosslinkable group contained in the polymer compound of the second organic layer is preferably a constitutional unit represented by the formula (2) or a constitutional unit represented by the formula (2′) described later, and may also be a constitutional unit represented by the following formula.
The constitutional unit having a crosslinkable group contained in the polymer compound of the second organic layer is preferably a constitutional unit represented by the formula (2) or a constitutional unit represented by the formula (2′).
[wherein,
nA represents an integer of 0 to 5, and n represents, 1 or 2.
Ar3 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups each optionally have a substituent.
LA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups each optionally have a substituent. R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of LA are present, they may be the same or different.
X represents a crosslinkable group selected from Group A of crosslinkable group. When a plurality of X are present, they may be the same or different.]
nA is preferably 0 to 2, more preferably 0 or 1, further preferably 0, because the light emitting device of the present invention is more excellent in external quantum efficiency.
n is preferably 2, because the light emitting device of the present invention is more excellent in external quantum efficiency.
Ar3 is preferably an aromatic hydrocarbon group which optionally has a substituent, because the light emitting device of the present invention is more excellent in external quantum efficiency.
The number of carbon atoms of the aromatic hydrocarbon group represented by Ar3, not including the number of carbon atoms of a substituent, is usually 6 to 60, preferably 6 to 30, more preferably 6 to 18.
The arylene group portion obtained by removing n substituents of the aromatic hydrocarbon group represented by Ar3 is preferably a group represented by the formula (A-1) to the formula (A-20), more preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-6) to the formula (A-10), the formula (A-19) or the formula (A-20), further preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-7), the formula (A-9) or the formula (A-19), and these groups each optionally have a substituent.
The number of carbon atoms of the heterocyclic group represented by Ar3, not including the number of carbon atoms of a substituent, is usually 6 to 60, preferably 6 to 30, more preferably 6 to 18.
The divalent heterocyclic group portion obtained by removing n substituents of the heterocyclic group represented by Ar3 is preferably a group represented by the formula (AA-1) to the formula (AA-34).
The aromatic hydrocarbon group and the heterocyclic group represented by Ar3 each optionally have a substituent, and the substituent includes an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group and a cyano group.
The number of carbon atoms of the alkylene group represented by LA, not including the number of carbon atoms of a substituent, is usually 1 to 10, preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms of the cycloalkylene group represented by LA, not including the number of carbon atoms of a substituent, is usually 3 to 10.
The alkylene group and the cycloalkylene group each optionally have a substituent, and the substituent includes, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group and an octylene group.
The substituent which the alkylene group and the cycloalkylene group represented by LA each optionally have includes, for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom and a cyano group.
The arylene group represented by LA optionally has a substituent. The arylene group includes, for example, an o-phenylene group, a m-phenylene group and a p-phenylene group. The arylene group is preferably a phenylene group or a fluorenediyl group, more preferably a m-phenylene group, a p-phenylene group, a fluorene-2,7-diyl group or a fluorene-9,9-diyl group. The substituent which the arylene group optionally has includes, for example, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom, a cyano group and a crosslinkable group selected from Group A of crosslinkable group.
LA is preferably an arylene group or an alkylene group, more preferably a phenylene group, a fluorenediyl group or an alkylene group, further preferably a phenylene group or an alkylene group, because production of the polymer compound of the second organic layer is easy, and these groups each optionally have a substituent.
The crosslinkable group represented by X is preferably a crosslinkable group represented by the formula (XL-1), (XL-3), (XL-7), (XL-9), (XL-10), (XL-16) or (XL-17), more preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-17), further preferably a crosslinkable group represented by the formula (XL-17), because the polymer compound of the second organic layer is excellent in crosslinkability.
The amount of the constitutional unit represented by the formula (2) is preferably 0.5 to 50 mol %, more preferably 3 to 30 mol %, further preferably 3 to 20 mol %, with respect to the total amount of constitutional units contained in the polymer compound of the second organic layer, because the polymer compound of the second organic layer is excellent in stability and crosslinkability.
The constitutional unit represented by the formula (2) may be contained singly or two or more of the constitutional units may be contained in the polymer compound of the second organic layer.
[wherein,
mA represents an integer of 0 to 5, m represents an integer of 1 to 4, and c represents an integer of 0 or 1. When a plurality of mA are present, they may be the same or different.
Ar5 represents an aromatic hydrocarbon group, a heterocyclic group or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are bonded directly to each other, and these groups each optionally have a substituent.
Ar4 and Ar6 each independently represent an arylene group or a divalent heterocyclic group, and these groups each optionally have a substituent.
Each of Ar4, Ar5 and Ar6 may be bonded directly or via an oxygen atom or a sulfur atom to a group that is different from that group and that is attached to the nitrogen atom to which that group is attached, thereby forming a ring.
KA represents an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, a group represented by —NR′—, an oxygen atom or a sulfur atom, and these groups each optionally have a substituent. R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. When a plurality of KA are present, they may be the same or different.
X′ represents a crosslinkable group selected from Group A of crosslinkable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. At least one X′ is a crosslinkable group selected from Group A of crosslinkable group.]
mA is preferably 0 or 1, more preferably 0, because the light emitting device of the present invention is more excellent in external quantum efficiency.
m is preferably 2, because the light emitting device of the present invention is more excellent in external quantum efficiency.
c is preferably 0, because production of the polymer compound of the second organic layer is easy and because the light emitting device of the present invention is more excellent in external quantum efficiency.
Ar5 is preferably an aromatic hydrocarbon group which optionally has a substituent, because the light emitting device of the present invention is more excellent in external quantum efficiency.
The examples and preferable range of the arylene group portion obtained by removing m substituents of the aromatic hydrocarbon group represented by Ar5 are the same as the examples and preferable range of the arylene group represented by ArX2 in the formula (X).
The examples and preferable range of the divalent heterocyclic group portion obtained by removing m substituents of the heterocyclic group represented by Ar5 are the same as the examples and preferable range of the divalent heterocyclic group portion represented by ArX2 in the formula (X) described later.
The definition and examples of the divalent group obtained by removing m substituents of the group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are bonded directly to each other represented by Ar5 are the same as the examples and preferable range of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArX2 in the formula (X) described later.
Ar4 and A6 are preferably an arylene group optionally having a substituent, because the light emitting device of the present invention is more excellent in external quantum efficiency.
The examples and preferable range of the arylene group represented by Ar4 and Ar6 are the same as the examples and preferable range of the arylene group represented by ArX1 and ArX3 in the formula (X) described later.
The examples and preferable range of the divalent heterocyclic group represented by Ar4 and Ar6 are the same as the examples and preferable range of the divalent heterocyclic group represented by ArX1 and ArX3 in the formula (X) described later.
The group represented by Ar4, A5 and Ar6 optionally has a substituent, and the substituent includes an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group and a cyano group.
The examples and preferable range of the alkylene group, the cycloalkylene group, the arylene group and the divalent heterocyclic group represented by KA are the same as the examples and preferable range of the alkylene group, the cycloalkylene group, the arylene group and the divalent heterocyclic group represented by LA, respectively.
KA is preferably a phenylene group or a methylene group, because production of the polymer compound of the second organic layer is easy.
The crosslinkable group represented by X′ is preferably a crosslinkable group represented by the formula (XL-1), (XL-3), (XL-7), (XL-9), (XL-10), (XL-16) or (XL-17), more preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-17), further preferably a crosslinkable group represented by the formula (XL-17), because the polymer compound of the second organic layer is excellent in crosslinkability.
The amount of the constitutional unit represented by the formula (2′) is preferably 0.5 to 50 mol %, more preferably 3 to 30 mol %, further preferably 3 to 20 mol %, with respect to the total amount of constitutional units contained in the polymer compound of the second organic layer, because the polymer compound of the second organic layer is excellent in stability and because the polymer compound of the second organic layer is excellent in crosslinkability.
The constitutional unit represented by the formula (2′) may be contained singly or two or more of the constitutional units may be contained in the polymer compound of the second organic layer.
The constitutional unit represented by the formula (2) includes, for example, constitutional units represented by the formula (2-1) to the formula (2-30), and the constitutional unit represented by the formula (2′) includes, for example, constitutional units represented by the formula (2′-1) to the formula (2′-13). Of them, preferable are constitutional units represented by the formula (2-1) to the formula (2-30), more preferable are constitutional units represented by the formula (2-1) to the formula (2-15), the formula (2-19), the formula (2-20), the formula (2-23), the formula (2-25) or the formula (2-30), further preferable are constitutional units represented by the formula (2-1) to the formula (2-9) or the formula (2-30), because the polymer compound of the second organic layer is excellent in crosslinkability.
It is preferable that the polymer compound of the second organic layer further comprises a constitutional unit represented by the formula (X), because hole transportability is excellent.
[wherein, aX1 and aX2 each independently represent an integer of 0 or more. ArX1 and ArX3 each independently represent a n arylene group or a divalent heterocyclic ring group, and these groups each optionally have a substituent. ArX2 and ArX4 each independently represent an arylene group, a divalent heterocyclic ring group or a divalent group in which at least one arylene group and at least one divalent heterocyclic ring group are bonded directly to each other, and these groups each optionally have a substituent. RX1, RX2 and RX3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent.]
aX1 is preferably 2 or less, more preferably 1, because the external quantum efficiency of the light emitting device of the present invention is excellent.
aX2 is preferably 2 or less, more preferably 0, because the external quantum efficiency of the light emitting device of the present invention is excellent.
RX1, RX2 and RX3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups each optionally have a substituent.
The arylene group represented by ArX1 and ArX3 is more preferably a group represented by the formula (A-1) or the formula (A-9), further preferably a group represented by the formula (A-1), and these groups each optionally have a substituent.
The divalent heterocyclic group represented by ArX1 and ArX3 is more preferably a group represented by the formula (AA-1), the formula (AA-2) or the formula (AA-7) to (AA-26), and these groups each optionally have a substituent.
ArX1 and ArX3 are preferably an arylene group optionally having a substituent.
The arylene group represented by ArX2 and ArX4 is more preferably a group represented by the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to (A-11) or the formula (A-19), and these groups each optionally have a substituent.
The more preferable range of the divalent heterocyclic group represented by ArX2 and ArX4 is the same as the more preferable range of the divalent heterocyclic group represented by ArX1 and ArX3.
The more preferable range and the further preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArX2 and ArX4 are the same as the more preferable range and the further preferable range of the arylene group and the divalent heterocyclic group represented by ArX1 and ArX3, respectively.
The divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArX2 and ArX4 includes, for example, groups represented by the following formulae, and they each optionally have a substituent.
[wherein, RXX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent.]
RXX is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent.
ArX2 and ArX4 are preferably an arylene group optionally having a substituent.
The substituent which the group represented by ArX1 to ArX4 and RX1 to RX3 optionally has is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally further have a substituent.
The constitutional unit represented by the formula (X) is preferably a constitutional unit represented by the formula (X-1) to (X-7), more preferably a constitutional unit represented by the formula (X-3) to (X-7), further preferably a constitutional unit represented by the formula (X-3) to (X-6).
[wherein, RX4 and RX5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or a cyano group, and these groups each optionally have a substituent. The plurality of RX4 may be the same or different. The plurality of RX5 may be the same or different, and adjacent groups RX5 may be combined together to form a ring together with the carbon atoms to which they are attached.]
The content of the constitutional unit represented by the formula (X) is preferably 0.1 to 90 mol %, more preferably 5 to 70 mol %, further preferably 10 to 50 mol % with respect to the total content of constitutional units contained in the polymer compound of the second organic layer, because hole transportability is excellent.
The constitutional unit represented by the formula (X) includes, for example, constitutional units represented by the formulae (X1-1) to (X1-19), preferably constitutional units represented by the formulae (X1-6) to (X1-14).
The constitutional unit represented by the formula (X) may be contained only singly or two or more units thereof may be contained in the polymer compound of the second organic layer.
It is preferable that the polymer compound of the second organic layer further comprises a constitutional unit represented by the formula (Y), because the external quantum efficiency of the light emitting device of the present invention is excellent.
It is preferable that the polymer compound of the second organic layer further comprises a constitutional unit represented by the formula (X) and a constitutional unit represented by the formula (Y), because the external quantum efficiency of the light emitting device of the present invention is excellent.
[wherein, ArY1 represents an arylene group, a divalent heterocyclic ring group or a divalent group in which at least one arylene group and at least one divalent heterocyclic ring group are bonded directly to each other, and these groups each optionally have a substituent.]
The arylene group represented by ArY1 is more preferably a group represented by the formula (A-1), the formula (A-6), the formula (A-7), the formula (A-9) to (A-11), the formula (A-13) or the formula (A-19), further preferably a group represented by the formula (A-1), the formula (A-7), the formula (A-9) or the formula (A-19), and these groups each optionally have a substituent.
The divalent heterocyclic group represented by ArY1 is more preferably a group represented by the formula (AA-4), the formula (AA-10), the formula (AA-13), the formula (AA-15), the formula (AA-18) or the formula (AA-20), further preferably a group represented by the formula (AA-4), the formula (AA-10), the formula (AA-18) or the formula (AA-20), and these groups each optionally have a substituent.
The more preferable range and the further preferable range of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArY1 are the same as the more preferable range and the further preferable range of the arylene group and the divalent heterocyclic group represented by ArY1 described above, respectively.
The divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArY1 includes the same groups as the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other represented by ArX2 and ArX4 in the formula (X).
The substituent which the group represented by ArY1 optionally has is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally further have a substituent.
The constitutional unit represented by the formula (Y) includes, for example, constitutional units represented by the formulae (Y-1) to (Y-7), and from the standpoint of the external quantum efficiency of the light emitting device of the present invention preferable is a constitutional unit represented by the formula (Y-1) or (Y-2), from the standpoint of electron transportability of the polymer compound of the second organic layer preferable is a constitutional unit represented by the formula (Y-3) or (Y-4), and from the standpoint of hole transportability of the polymer compound of the second organic layer preferable are constitutional units represented by the formulae (Y-5) to (Y-7).
[wherein, RY1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. The plurality of RY1 may be the same or different, and adjacent groups RY1 may be combined together to form a ring together with the carbon atoms to which they are attached.]
RY1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent.
The constitutional unit represented by the formula (Y-1) is preferably a constitutional unit represented by the formula (Y-1′).
[wherein, RY11 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. The plurality of RY1 may be the same or different.]
RY11 is preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group, and these groups each optionally have a substituent.
[wherein, RY1 represents the same meaning as described above. XY1 represents a group represented by —C(RY2)2—, —C(RY2)═C(RY2)— or —C(RY2)2—C(RY2)2—. RY2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent. The plurality of RY2 may be the same or different, and groups RY2 may be combined together to form a ring together with the carbon atoms to which they are attached.]
RY2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group a cycloalkyl group or an aryl group, and these groups each optionally have a substituent.
Regarding the combination of two RY2s in the group represented by —C(RY2)2— in XY1, it is preferable that the both are an alkyl group or a cycloalkyl group, the both are an aryl group, the both are a monovalent heterocyclic group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, it is more preferable that one is an alkyl group or cycloalkyl group and the other is an aryl group, and these groups each optionally have a substituent. The two groups RY2 may be combined together to form a ring together with the atoms to which they are attached, and when the groups RY2 form a ring, the group represented by —C(RY2)2— is preferably a group represented by the formula (Y-A1) to (Y-A5), more preferably a group represented by the formula (Y-A4), and these groups each optionally have a substituent.
Regarding the combination of two RY2s in the group represented by —C(RY2)═C(RX2)— in XY1, it is preferable that the both are an alkyl group or cycloalkyl group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group, and these groups each optionally have a substituent.
Four RY2s in the group represented by —C(RY2)2—C(RY2)2— in XY1 are preferably an alkyl group or a cycloalkyl group optionally having a substituent. The plurality of RY2 may be combined together to form a ring together with the atoms to which they are attached, and when the groups RY2 form a ring, the group represented by —C(RY2)2—C(RY2)2— is preferably a group represented by the formula (Y-B1) to (Y-B5), more preferably a group represented by the formula (Y-B3), and these groups each optionally have a substituent.
[wherein, RY2 represents the same meaning as described above.]
It is preferable that the constitutional unit represented by the formula (Y-2) is a constitutional unit represented by the formula (Y-2′).
[wherein, RY11 and XY1; represent the same meaning as described above.]
[wherein, RY1 represents the same meaning as described above. RY3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent.]
RY3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups each optionally have a substituent.
[wherein, RY1 represents the same meaning as described above. RY4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, and these groups each optionally have a substituent.]
RY4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups each optionally have a substituent.
The constitutional unit represented by the formula (Y) includes, for example, constitutional units represented by the formulae (Y-11) to (Y-55).
The content of the constitutional unit represented by the formula (Y) in which ArY1 is an arylene group is preferably 0.5 to 80 mol %, more preferably 30 to 60 mol % with respect to the total content of constitutional units contained in the polymer compound of the second organic layer, because the external quantum efficiency of the light emitting device of the present invention is excellent.
The content of the constitutional unit represented by the formula (Y) in which ArY1 is a divalent heterocyclic group or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other is preferably 0.5 to 50 mol %, more preferably 3 to 40 mol % with respect to the total content of constitutional units contained in the polymer compound of the second organic layer, because the charge transportability of the light emitting device of the present invention is excellent.
The constitutional unit represented by the formula (Y) may be contained only singly or two or more units thereof may be contained in the polymer compound of the second organic layer.
The polymer compound of the second organic layer includes, for example, polymer compounds P-1 to P-9 shown in Table 7. “Other constitutional unit” denotes a constitutional unit other than constitutional units represented by the formula (2), the formula (2′), the formula (X) and the formula (Y).
[in the table, q, r, s, t and u represent the mole fraction of each constitutional unit. q+r+s+t+u=100 and, 70 S q+r+s+t≦100.]
The examples and preferable ranges of constitutional units represented by the formula (2), the formula (2′), the formula (X) and the formula (Y) in the polymer compounds P-1 to P-9 are as described above.
The polymer compound of the second organic layer can be produced by using known polymerization methods described in Chem. Rev., vol. 109, pp. 897-1091 (2009) and the like, and the known polymerization methods include, for example, methods for causing polymerization by a coupling reaction using a transition metal catalyst such as the Suzuki reaction, the Yamamoto reaction, the Buchwald reaction, the Stille reaction, the Negishi reaction and the Kumada reaction.
In the above-described polymerization methods, the monomer charging method includes a method in which the total amount of monomers is charged in a lump into the reaction system, a method in which a part of monomers is charged and reacted, then, the remaining monomers are charged in a lump, continuously or in divided doses, a method in which monomers are charged continuously or in divided doses, and the like.
The transition metal catalyst includes a palladium catalyst and a nickel catalyst.
The post treatment of the polymerization reaction is conducted by using known methods, for example, a method in which water-soluble impurities are removed by liquid-separation, a method in which the reaction solution after the polymerization reaction is added to a lower alcohol such as methanol and the like, the deposited precipitate is filtrated, then, dried, and other methods, singly or in combination. When the purity of the polymer host is low, purification can be carried out by usual methods such as, for example, recrystallization, reprecipitation, continuous extraction using a Soxhlet extractor, column chromatography and the like.
The second organic layer may be a layer obtained by using a composition comprising the polymer compound of the second organic layer and at least one material selected from the group consisting of a hole transporting material, a hole injection material, an electron transporting material, an electron injection material, a light emitting material, an antioxidant and a solvent (hereinafter, referred to also as “composition of second organic layer”.).
The examples and preferable range of the hole transporting material, the electron transporting material, the hole injection material, the electron injection material and the light emitting material contained in the composition of the second organic layer are the same as the examples and preferable range of the hole transporting material, the electron transporting material, the hole injection material, the electron injection material and the light emitting material contained in the composition of the first organic layer. In the composition of the second organic layer, the compounding amount of each of the hole transporting material, the electron transporting material, the hole injection material, the electron injection material and the light emitting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the amount of the polymer compound of the second organic layer is 100 parts by weight.
The examples and preferable range of the antioxidant contained in the composition of the second organic layer are the same as the examples and preferable range of the antioxidant contained in the composition of the first organic layer. In the composition of the second organic layer, the compounding amount of the antioxidant is usually 0.001 to 10 parts by weight when the amount of the polymer compound of the second organic layer is 100 parts by weight.
The composition of the second organic layer comprising a solvent (hereinafter, referred to also as “ink of second organic layer”.) can be suitably used in application methods such as a spin coat method and an inkjet printing method, like the ink of the first organic layer.
The preferable range of the viscosity of the ink of the second organic layer is the same as the preferable range of the viscosity of the ink of the first organic layer.
The examples and preferable range of the solvent contained in the ink of the second organic layer are the same as the examples and preferable range of the solvent contained in the ink of the first organic layer.
In the ink of the second organic layer, the compounding amount of the solvent is usually 1000 to 100000 parts by weight, preferably 2000 to 20000 parts by weight when the amount of the polymer compound of the second organic layer is 100 parts by weight.
The light emitting device of the present invention comprises an anode, a cathode, a first organic layer disposed between the anode and the cathode and a second organic layer disposed between the anode and the cathode. The light emitting device of the present invention may have a layer other than the anode, the cathode, the first organic layer and the second organic layer.
In the light emitting device of the present invention, the first organic layer is usually a light emitting layer.
In the light emitting device of the present invention, the second organic layer is usually a second light emitting layer, a hole transporting layer or an electron transporting layer, more preferably a hole transporting layer. The second organic layer is a layer obtained by using the polymer compound of the second organic layer, and the polymer compound of the second organic layer may be used singly, or two or more of the polymer compounds may be used.
In the light emitting device of the present invention, it is preferable that the first organic layer and the second organic layer are adjacent, because the light emitting device of the present invention is more excellent in external quantum efficiency.
In the light emitting device of the present invention, the second organic layer is preferably a layer disposed between the anode and the first organic layer, more preferably a hole transporting layer disposed between the anode and the first organic layer, because the light emitting device of the present invention is more excellent in external quantum efficiency.
It is preferable that the light emitting device of the present invention has further a hole injection layer between the anode and the second organic layer disposed between the anode and the first organic layer, because the light emitting device of the present invention is further excellent in external quantum efficiency. Further, it is preferable that the light emitting device of the present invention has further at least one of an electron injection layer and an electron transporting layer between the cathode and the first organic layer disposed between the cathode and the second organic layer, because the light emitting device of the present invention is further excellent in external quantum efficiency.
The light emitting device of the present invention may further have an arbitrary layer such as a charge generating layer.
The specific layer constitution of the light emitting device of the present invention includes, for example, layer constitutions represented by the following (D1) to (D19). The light emitting device of the present invention usually has a substrate, and an anode may be laminated on the substrate, or a cathode may be laminated on the substrate.
(D1) anode/second light emitting layer (second organic layer)/light emitting layer (first organic layer)/cathode
(D2) anode/light emitting layer (first organic layer)/second light emitting layer (second organic layer)/cathode
(D3) anode/light emitting layer (first organic layer)/electron transporting layer (second organic layer)/cathode
(D4) anode/hole injection layer/light emitting layer (first organic layer)/electron transporting layer (second organic layer)/electron injection layer/cathode
(D5) anode/hole injection layer/hole transporting layer/second light emitting layer/light emitting layer (first organic layer)/electron transporting layer (second organic layer)/electron injection layer/cathode
(D6) anode/hole injection layer/second light emitting layer (second organic layer)/light emitting layer (first organic layer)/electron injection layer/cathode
(D7) anode/hole injection layer/hole transporting layer/second light emitting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D8) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/cathode
(D9) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron injection layer/cathode
(D10) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/cathode
(D11) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D12) anode/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/cathode
(D13) anode/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron injection layer/cathode
(D14) anode/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/cathode
(D15) anode/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D16) anode/second light emitting layer (second organic layer)/charge generating layer/light emitting layer (first organic layer)/cathode
(D17) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/charge generating layer/hole transporting layer/second light emitting layer/cathode
(D18) anode/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/charge generating layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/cathode
(D19) anode/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/charge generating layer/hole injection layer/hole transporting layer (second organic layer)/light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
In the above-described (D1) to (D19), “/” means that layers before and after it are adjacently laminated. Specifically, “hole transporting layer (second organic layer)/light emitting layer (first organic layer)” means that a hole transporting layer (second organic layer) and a light emitting layer (first organic layer) adjacently laminated.
Layer constitutions represented by the above-described (D6) to (D15) are preferable, and layer constitutions represented by the above-described (D12) to (D1S) are more preferable, because the light emitting device of the present invention is more excellent in external quantum efficiency.
In the light emitting device of the present invention, if necessary, two or more of each of an anode, a cathode, a hole injection layer, a hole transporting layer, a light emitting layer, a second light emitting layer, an electron transporting layer, an electron injection layer and a charge generating layer may be provided.
When a plurality of anodes, cathodes, hole injection layers, hole transporting layers, light emitting layers, second light emitting layers, electron transporting layers, electron injection layers and charge generating layers are present, they may be the same or different at each occurrence.
The thickness of an anode, a cathode, a hole injection layer, a hole transporting layer, a light emitting layer, a second light emitting layer, an electron transporting layer, an electron injection layer and a charge transporting layer is usually 1 nm to 1 m, preferably 2 nm to 500 nm, further preferably 5 nm to 150 nm.
In the light emitting device of the present invention, the order, the number and the thickness of layers to be laminated may be advantageously adjusted in view of the external quantum efficiency and the device life of the light emitting device.
The light emitting layer is usually a first organic layer. The first organic layer is a layer obtained by using the composition of the first organic layer as described above.
The second light emitting layer is usually a second organic layer or a layer formed by using a light emitting material, preferably a layer formed by using a light emitting material. The second organic layer is a layer obtained by using the polymer compound of the second organic layer, as described above. The light emitting material used for formation of the second light emitting layer includes, for example, light emitting materials which the composition of the first organic layer may comprise described above.
The hole transporting layer is usually a second organic layer or a layer formed by using a hole transporting material, preferably a second organic layer. The second organic layer is a layer obtained by using the polymer compound of the second organic layer, as described above. The hole transporting material used for formation of the hole transporting layer includes, for example, hole transporting materials which the composition of the first organic layer may comprise described above.
The electron transporting layer is usually a second organic layer or a layer formed by using an electron transporting material, preferably a layer obtained by using an electron transporting material. The second organic layer is a layer obtained by using the polymer compound of the second organic layer as described above. The electron transporting material used for formation of the electron transporting layer includes, for example, electron transporting materials which the composition of the first organic layer may comprise described above.
When the light emitting device of the present invention has an electron transporting layer and the electron transporting layer is not a second organic layer, a polymer compound comprising at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (ET-1) and a constitutional unit represented by the formula (ET-2) is preferable as the electron transporting material used for formation of an electron transporting layer.
[wherein,
nE1 represents an integer of 1 or more.
ArE1 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups each optionally have a substituent other than RE1.
RE1 represents a group represented by the formula (ES-1). When a plurality of RE1 are present, they may be the same or different.]
—RE3-{(QE1)nE3-YE1(ME1)aE1(ZE1)bE1}mE1 (ES-1)
[wherein,
nE3 represents an integer of 0 or more, aE1 represents an integer of 1 or more, bE1 represents an integer of 0 or more, and mE1 represents an integer of 1 or more. When a plurality of nE3, aE1 and bE1 are present, they may be the same or different at each occurrence. mE1 is 1 when RE3 is a single bond. aE1 and bE1 are selected so that the charge of the group represented by the formula (ES-1) is 0.
RE3 represents a single bond, a hydrocarbon group, a heterocyclic group or —O—RE3′ (RE3′ represents a hydrocarbon group or a heterocyclic group.), and these groups each optionally have a substituent.
QE1 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups each optionally have a substituent. When a plurality of QE1 are present, they may be the same or different.
YE1 represents —CO2−, —SO3−, —SO2− or PO32−. When a plurality of YE1 are present, they may be the same or different.
ME1 represents an alkali metal cation, an alkaline earth metal cation or an ammonium cation, and this ammonium cation optionally has a substituent. When a plurality of ME1 are present, they may be the same or different.
ZE1 represents F−, Cl−, Br−, I−, OH−, B(RE4)4−, RE4SO3−, RE4COO−, NO3−, SO42−, HSO4−, PO43−, HPO42−, H2PO4−, BF4− or PF6−. RE4 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent. When a plurality of ZE1 are present, they may be the same or different.]
nE1 is usually an integer of 1 to 4, preferably 1 or 2.
The aromatic hydrocarbon group or the heterocyclic group represented by ArE1 is preferably a group obtained by removing from a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2,6-naphthalenediyl group, a 1,4-naphthalenediyl group, a 2,7-fluorenediyl group, a 3,6-fluorenediyl group, a 2,7-phenanthrenediyl group or a 2,7-carbazoledilyl group nE1 hydrogen atoms bonding directly to atoms constituting the ring, and may have a substituent other than RE1.
The substituent other than RB1 which ArB1 optionally has includes a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an amino group, a substituted amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, a carboxyl group and a group represented by the formula (ES-3).
—O—(Cn,H2n,O)nx—Cm,H2m,+1 (ES-3)
[wherein, n′, m′ and nx each independently represent an integer of 1 or more.]
nE3 is usually an integer of 0 to 10, preferably an integer of 0 to 8, more preferably an integer of 0 to 2.
aE1 is usually an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 or 2.
bE1 is usually an integer of 0 to 10, preferably an integer of 0 to 4, more preferably 0 or 1.
mE1 is usually an integer of 1 to 5, preferably 1 or 2, more preferably 0 or 1.
When RE3 is —O—RE3′, the group represented by the formula (ES-1) is a group represented by the following formula.
—O—RE3′-{(QE1)nE3-YE1(ME1)aE1(ZE1)bE1}mE1
RE3 is preferably a hydrocarbon group or a heterocyclic group, more preferably an aromatic hydrocarbon group or an aromatic heterocyclic ring group, further preferably an aromatic hydrocarbon group.
The substituent which RE3 optionally has includes an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group and a group represented by the formula (ES-3), and a group represented by the formula (ES-3) is preferable.
QE1 is preferably an alkylene group, an arylene group or an oxygen atom, more preferably an alkylene group or an oxygen atom.
YB1 is preferably —CO2−, −SO2− or PO32−, more preferably —CO2−.
The alkali metal cation represented by ME1 includes, for example, Li+, Na+, K+, Rb+, Cs+, preferably K+, Rb+ or Cs+, more preferably Cs+.
The alkaline earth metal cation represented by ME1 includes, for example, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, preferably Mg2+, Ca2+, Sr2+ or Ba2+, more preferably Ba2+.
ME1 is preferably an alkali metal cation or an alkaline earth metal cation, more preferably an alkali metal cation.
ZE1 is preferably F−, Cl−, Br−, I−, OH−, B(RE4)4−, RE4SO3−, RE4COO− or NO3−, more preferably F−, Cl−, Br−, I−, OH−, RE4SO3− or RE4COO−. RE4 is preferably an alkyl group.
The group represented by the formula (ES-1) includes, for example, groups represented by the following formulae.
[wherein, M+ represents Li+, Na+, K+, Cs+ or N(CH3)4+. When a plurality of M+ are present, they may be the same or different.]
[wherein,
nE2 represents an integer of 1 or more.
ArE2 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups each optionally have a substituent other than RE2.
RE2 represents a group represented by the formula (ES-2). When a plurality of RE2 are present, they may be the same or different.]
—RE5-{(QE2)nE4-YE2(ME2)aE2(ZE2)bE2}mE2 (ES-2)
[wherein,
nE4 represents an integer of 0 or more, aE2 represents an integer of 1 or more, bE2 represents an integer of 0 or more, and mE2 represents an integer of 1 or more. When a plurality of nE4, aE2 and bE2 are present, they may be the same or different at each occurrence. mE2 is 1 when RE is a single bond. aE2 and bE2 are selected so that the charge of the group represented by the formula (ES-2) is 0.
RE5 represents a single bond, a hydrocarbon group, a heterocyclic group or —O—RE5′(RE5′ represents a hydrocarbon group or a heterocyclic group.), and these groups each optionally have a substituent.
QE2 represents an alkylene group, a cycloalkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups each optionally have a substituent. When a plurality of QE2 are present, they may be the same or different.
YE2 represents —C+RE62, —N+RE63, —P+RE63, —S+RE62 or I+RE62. RE6 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent. The plurality of RE6 may be the same or different. When a plurality of YE2 are present, they may be the same or different.
ME2 represents F−, Cl−, Br−, I−, OH−, B(RE7)4−, RE7SO3−, RE7COO−, BF4—, SbCl6− or SbF6−. RE7 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups each optionally have a substituent. When a plurality of ME2 are present, they may be the same or different.
ZE2 represents an alkali metal cation or an alkaline earth metal cation. When a plurality of ZE2 are present, they may be the same or different.]
nE2 is usually an integer of 1 to 4, preferably 1 or 2.
The aromatic hydrocarbon group or the heterocyclic group represented by ArE2 is preferably a group obtained by removing from a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2,6-naphthalenediyl group, a 1,4-naphthalenediyl group, a 2,7-fluorenediyl group, a 3,6-fluorenediyl group, a 2,7-phenanthrenediyl group or a 2,7-carbazoledilyl group nE2 hydrogen atoms bonding directly to atoms constituting the ring, and optionally has a substituent other than RE2.
The substituent other than RB2 which ArB2 optionally has is the same as the substituent other than RE1 which ArE1 optionally has.
nE4 is usually an integer of 0 to 10, preferably an integer of 0 to 8, more preferably an integer of 0 to 2.
aE2 is usually an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 or 2.
bE2 is usually an integer of 0 to 10, preferably an integer of 0 to 4, more preferably 0 or 1.
mE2 is usually an integer of 1 to 5, preferably 1 or 2, more preferably 0 or 1.
When RE5 is —O-RE5′, the group represented by the formula (ES-2) is a group represented by the following formula.
—O—RE5′{(QE1)nE3-YE1(ME1)aE1(ZE1)bE1}mE1
RE5 is preferably a hydrocarbon group or a heterocyclic group, more preferably an aromatic hydrocarbon group or an aromatic heterocyclic ring group, further preferably an aromatic hydrocarbon group.
The substituent which RE5 optionally has includes an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group and a group represented by the formula (ES-3), and a group represented by the formula (ES-3) is preferable.
QE2 is preferably an alkylene group, an arylene group or an oxygen atom, more preferably an alkylene group or an oxygen atom.
YE2 is preferably —C+RE62, —N+RE63, —P+RE63 or S+RE62, more preferably —N+RE63. RE6 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.
ME2 is preferably F−, Cl−, Br−, I−, B(RE7)4−, RE7SO3−, RE7COO−, BF4− or SbF6−, more preferably Br−, I−, B(R7)4−, RE7COO− or SbF6−. An alkyl group is preferable as RE7.
The alkali metal cation represented by ZE2 includes, for example, Li+, Na+, K+, Rb+, Cs+, preferably Li+, Na+ or K+.
The alkaline earth metal cation represented by ZE2 includes, for example, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, preferably Mg2+ or Ca2+.
ZE2 is preferably an alkali metal cation.
The group represented by the formula (ES-2) includes, for example, groups represented by the following formulae.
[wherein, X− represents F−, Cl−, Br−, I−, B(C6H5)4−, CH3COO− or CF3SO3−. When a plurality of X− are present, they may be the same or different.]
The constitutional unit represented by the formula (ET-1) and the formula (ET-2) includes, for example, constitutional units represented by the formula (ET-31) to the formula (ET-34) described below.
The hole injection layer is usually a layer formed by using a hole injection material. The hole injection material used for formation of the hole injection layer includes, for example, hole injection materials which the composition of the first organic layer may comprise described above.
The electron injection layer is usually a layer formed by using an electron injection material. The electron injection material used for formation of the electron injection layer includes, for example, electron injection materials which the composition of the first organic layer may comprise described above.
The charge generating layer is usually a layer formed by using a charge generating material. The charge generating material used for formation of the charge generating layer includes, for example, layers obtained by using a metal oxide such as vanadium oxide, molybdenum oxide and tungsten oxide; layers obtained by using a composition comprising the metal oxide and an aromatic amine compound typified by 1,1-bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane (TAPC), 4,4′-bis[N-(m-tolyl)-N-phenylamino]biphenyl (TPD), N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPB) and the like; and layers obtained by using a composition comprising an aromatic amine compound typified by TAPC, TPD, NPB and the like and an electron-accepting substance typified by fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene and the like.
The substrate in the light emitting device may advantageously be a substrate on which an electrode can be formed and which does not chemically change in forming an organic layer, and is a substrate made of a material such as, for example, glass, plastic and silicon. In the case of an opaque substrate, it is preferable that an electrode most remote from the substrate is transparent or semi-transparent.
The material of the anode includes, for example, electrically conductive metal oxides and semi-transparent metals, preferably, indium oxide, zinc oxide and tin oxide; electrically conductive compounds such as indium.tin.oxide (ITO) and indium.zinc.oxide; a composite of silver, palladium and copper (APC); NESA, gold, platinum, silver and copper.
The material of the cathode includes, for example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc and indium; alloys composed of two or more of them; alloys composed of one or more of them and at least one of silver, copper, manganese, titanium, cobalt, nickel, tungsten and tin; and graphite and graphite intercalation compounds. The alloy includes, for example, a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy and a calcium-aluminum alloy.
In the light emitting device, at least one of the anode and the cathode is usually transparent or semi-transparent, and it is preferable that the anode is transparent or semi-transparent.
Methods for forming the anode and the cathode include, for example, vacuum vapor deposition method, sputtering method, ion plating method, plating method, lamination method and the like.
The method of forming a light emitting layer, a second light emitting layer, a hole transporting layer, an electron transporting layer, a hole injection layer, an electron injection layer and a charge generating layer in the light emitting device of the present invention includes, for example, a vacuum vapor deposition method from a powder and a method of film formation from a solution or melted state when a low molecular weight compound is used, and includes, for example, a method of film formation from a solution or melted state when a polymer compound is used.
The light emitting layer, the second light emitting layer, the hole transporting layer, the electron transporting layer, the hole injection layer, the electron injection layer and the charge generating layer can be formed by application methods typified by a spin coat method and an inkjet printing method using inks containing the composition of the first organic layer, the polymer compound of the second organic layer, the light emitting material, the hole transporting material, the electron transporting material, the hole injection material, the electron injection material and the charge generating material described above, respectively.
When the material used for formation of a hole injection layer, the material used for formation of a hole transporting layer, the material used for formation of a light emitting layer, the material used for formation of a second light emitting layer, the material used for formation of an electron transporting layer, the material used for formation of an electron injection layer and the material used for formation of a charge generating layer are dissolvable in a solvent used in forming a layer adjacent to a hole injection layer, a hole transporting layer, a light emitting layer, a second light emitting layer, an electron transporting layer, an electron injection layer and a charge generating layer, respectively, in fabrication of a light emitting device, it is preferable that the materials have a crosslinkable group to avoid dissolution of the materials in the solvent. Each layer is formed using a material having a crosslinkable group, then, the crosslinkable group can be crosslinked to insolubilize the layer.
For obtaining planar light emission by using a light emitting device of the present invention, a planar anode and a planar cathode are disposed so as to overlap with each other. Patterned light emission can be produced by a method of placing a mask with a patterned window on the surface of a planer light emitting device, a method of forming an extremely thick layer intended to be a non-light emitting, thereby having the layer essentially no-light emitting or a method of forming an anode, a cathode or both electrodes in a patterned shape. By forming a pattern with any of these methods and disposing certain electrodes so as to switch ON/OFF independently, a segment type display capable of displaying numbers and letters and the like is provided. For producing a dot matrix display, both an anode and a cathode are formed in a stripe shape and disposed so as to cross with each other. Partial color display and multi-color display are made possible by a method of printing separately certain polymer compounds showing different emission or a method of using a color filter or a fluorescence conversion filter. The dot matrix display can be passively driven, or actively driven combined with TFT and the like. These displays can be used in computers, television sets, portable terminals and the like. The planar light emitting device can be suitably used as a planer light source for backlight of a liquid crystal display or as a planar light source for illumination. If a flexible substrate is used, it can be used also as a curved light source and a curved display.
The present invention will be illustrated further in detail by examples below, but the present invention is not limited to these examples.
In the present examples, the polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of a polymer compound were measured by size exclusion chromatography (SEC) (manufactured by Shimadzu Corp., trade name: LC-10Avp). SEC measurement conditions are as described below.
The polymer compound to be measured was dissolved in THF at a concentration of about 0.05 wt %, and 10 μL of the solution was injected into SEC. As the mobile phase of SEC, tetrahydrofuran was used and allowed to flow at a flow rate of 2.0 mL/min. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. As the detector, UV-VIS detector (manufactured by Shimadzu Corp., trade name: SPD-10Avp) was used.
Measurement of liquid chromatograph mass spectrometry (LC-MS) was carried out according to the following method.
A measurement sample was dissolved in chloroform or THF so as to give a concentration of about 2 mg/mL, and about 1 μL of the solution was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). As the mobile phase of LC-MS, acetonitrile and THF were used while changing the ratio thereof and allowed to flow at a flow rate of 0.2 mL/min. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, internal diameter: 2.1 mm, length: 100 mm, particle size: 3 m) was used.
Measurement of NMR was carried out according to the following method.
5 to 10 mg of a measurement sample was dissolved in about 0.5 mL of deuterated chloroform (CDCl3), deuterated tetrahydrofuran (THF-de), deuterated acetone (CD3-(C═O)—CD3), deuterated N,N-dimethylformamide (DMF-di), deuterated toluene (C6D5-CD3), deuterated methanol (CD3OD), deuterated ethanol (CD3CD2OD), deuterated 2-pronanol (CD3-CDOD-CD3) or deuterated methylene chloride (CD2Cl2), and measurement was performed using an NMP apparatus (manufactured by Agilent, trade name: INOVA 300 or MERCURY 400VX).
As the index of the purity of a compound, a value of the high performance liquid chromatography (HPLC) area percentage was used. This value is a value in high performance liquid chromatography (HPLC, manufactured by Shimadzu Corp., trade name: LC-20A) at 254 nm, unless otherwise stated. In this operation, the compound to be measured was dissolved in THF or chloroform so as to give a concentration of 0.01 to 0.2 wt %, and depending on the concentration, 1 to 10 μL of the solution was injected into HPLC. As the mobile phase of HPLC, acetonitrile and THF were used and allowed to flow at a flow rate of 1 mL/min as gradient analysis of acetonitrile/THF-100/0 to 0/100 (volume ratio). As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having an equivalent performance was used. As the detector, a photo diode array detector (manufactured by Shimadzu Corp., trade name: SPD-M20A) was used.
Metal complexes 1 and, 2 were synthesized according to a method described in JP-A No. 2013-147551.
A metal complex 3 was synthesized according to a method described in International Publication WO2006/121811.
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, 4-tert-octylphenol (250.00 g, manufactured by Aldrich), N,N-dimethyl-4-aminopyridine (177.64 g) and dichloromethane (3100 mL) were added, and this mixture was cooled down to 5° C. with ice. Thereafter, trifluoromethanesulfonic anhydride (376.06 g) was dropped into this over a period of 45 minutes. After completion of dropping, the mixture was stirred for 30 minutes under ice cool, then, returned to room temperature and further stirred for 1.5 hours. To the resultant reaction mixture was added hexane (3100 mL), and this reaction mixture was filtrated using 410 g of silica gel, and further, the silica gel was washed with a mixed solvent (2.5 L) of hexane/dichloromethane (1/1 (by volume)). The resultant filtrate and the wash solution were concentrated, to obtain a compound S1-a (410.94 g, HPLC purity: 99.7%) as a colorless oil.
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, the compound S1-a (410.94 g), bis(pinacolato)diboron (338.47 g), potassium acetate (237.83 g), 1,4-dioxane (2600 mL), palladium acetate (4.08 g) and tricyclohexylphosphine (10.19 g) were added, and the mixture was refluxed for 2 hours. After cooling down to room temperature, the resultant reaction mixture was filtrated and the filtrate was collected, and further, the filtrated substance was washed with 1, 4-dioxane (2.5 L), and the resultant filtrate and the wash solution were concentrated. The resultant residue was dissolved into a mixed solvent of hexane/dichloromethane (1/1 (by volume)), and the solution was filtrated using 770 g silica gel, and further, the silica gel was washed with a mixed solvent (2.5 L) of hexane/dichloromethane (1/1 (by volume)). The resultant filtrate and the wash solution were concentrated, and to the resultant residue was added methanol (1500 mL), and the mixture was ultrasonically cleaned for 30 minutes. Thereafter, this was filtrated to obtain a compound S1-b (274.27 g). The filtrate and the wash solution were concentrated, and methanol was added, and the mixture was ultrasonically cleaned and filtrated, and such an operation was repeated, to obtain a compound S1-b (14.29 g). The total yielded amount of the resultant compound S1-b was 288.56 g.
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, 1,3-dibromobenzene (102.48 g), the compound S1-b (288.56 g), toluene (2100 mL), a 20 wt % tetraethyl ammonium hydroxide aqueous solution (962.33 g) and bis(triphenylphosphine)palladium(II) dichloride (3.04 g) were added, and the mixture was refluxed for 7 hours. After cooling down to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was collected. To this aqueous layer was added toluene (1 L), and the organic layer was further extracted. The resultant organic layers were combined, and this mixture was washed with a mixed aqueous solution of distilled water/saturated saline (1.5 L/1.5 L). The resultant organic layer was filtrated through 400 g silica gel, and further, the silica gel was washed with toluene (2 L). The resultant solution was concentrated, and the resultant residue was dissolved in hexane. This solution was purified by silica gel column chromatography. Impurities were eluted with a developing solvent hexane, then, developed with a mixed solvent of hexane/dichloromethane (10/1 (by volume)). The each resultant fraction was concentrated under reduced pressure to remove the solvent, obtaining a colorless crystalline compound S1-c (154.08 g, HPLC purity: 99.1%) and a coarse compound S1-c (38.64 g, HPLC purity: 83%). This coarse compound S1-c was column-purified again under the same developing conditions, and the solvent was distilled off under reduced pressure, to obtain a compound S1-c (28.4 g, HPLC purity: 99.6%). The total yielded amount the resultant compound S1-c was 182.48 g.
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, the compound S1-c (182, 48 g), bis(pinacolato)diboron (112.09 g), 4,4′-di-tert-butyl-2,2′-dipyridyl (3.23 g), cyclohexane (2000 mL) and bis(1,5-cyclooctadiene)di-μ-methoxydiiridium(I) (3.99 g) were added, and the mixture was refluxed for 2 hours. After cooling with air down to room temperature, silica gel (220 g) was added over a period of 20 minutes while stirring the resultant reaction mixture. The resultant suspension was filtrated through 440 g of silica gel, and further, the silica gel was washed with dichloromethane (2 L), and the solution was concentrated. To the resultant residue were added methanol (1100 mL) and dichloromethane (110 mL), and the mixture was refluxed for 1 hour. After cooling down to room temperature, this was filtrated. The resultant filtrated substance was washed with methanol (500 mL), and the resultant solid was dried, to obtain a compound S1 (220.85 g).
1H-NMR (CDCl3, 300 MHz): δ (ppm)=8.00 (s, 2H), 7.92 (s, 1H), 7.60 (d, J=8.5 Hz, 4H), 7.44 (d, J=8.5 Hz, 4H), 1.78 (s, 4H), 1.41 (s, 12H), 1.37 (s, 12H), 0.75 (s, 18H).
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, the compound S1 (91.49 g), m-dibromobenzene (17.70 g) and toluene (478 mL) were added, and the mixture was bubbled with a nitrogen gas for 20 minutes. Thereafter, to this were added a 20 wt % tetraethyl ammonium hydroxide aqueous solution (166 mL) and bis(triphenylphosphine)palladium(II) dichloride (0.26 g), and the mixture was refluxed for 6.5 hours. After cooling down to room temperature, the organic layer was separated from the resultant reaction solution, and this organic layer was washed with water (300 mL) and saturated saline (300 mL) in this order. The resultant organic layer was dried over sodium sulfate, then, the solvent was distilled off under reduced pressure. The resultant residue was dissolved into a mixed solvent of hexane/chloroform (20/l (by volume)), and the solution was purified by silica gel column chromatography, and concentrated under reduced pressure, to remove the solvent. To the resultant residue were added methanol (845 mL) and chloroform (56 mL), and the mixture was refluxed for 30 minutes. The resultant solution was cooled to obtain a precipitate which was then filtrated and dried, to obtain a compound S2-a (74.40 g).
The atmosphere in a reaction vessel was turned into a nitrogen gas stream, then, the compound S2-a (74.40 g), bis(pinacolato)diboron (21.13 g), 4,4′-di-tert-butyl-2,2′-dipyridyl (609 mg), cyclohexane (734 mL) and bis(1, 5-cyclooctadiene)di-μ-methoxydiiridium(I) (752 mg) were added, and the mixture was refluxed for 8 hours. After cooling with air down to room temperature, then, to the resultant reaction solution was added silica gel (83.93 g), and it was purified by silica gel column chromatography (developing solvent: a mixed solvent of dichloromethane/acetonitrile (100/1 (by volume))). Thereafter, the solvent was distilled off under reduced pressure, and the resultant residue was dissolved in toluene (420 mL), and this solution was heated at 50° C. Thereafter, acetonitrile (839 mL) was dropped into this, and the deposited solid was filtrated. The resultant solid was refluxed in a mixed solvent of hexane/acetonitrile (1/1 (by volume)) for 30 minutes, then, cooled down to room temperature and the precipitate was collected by filtration, and dried, to obtain a compound S2 (68.53 g).
1H-NMR (CDCl3, 300 MHz): δ (ppm)=8.14 (d, J=1.8 Hz, 2H), 8.09 (m, 1H), 7.85 (d, J=1.6 Hz, 4H), 7.82 (m, 2H), 7.64 (d, J=8.5 Hz, 8H), 7.48 (d, J=8.5 Hz, 8H), 1.79 (s, 8H), 1.42 (s, 24H), 1.39 (s, 12H), 0.77 (s, 36H).
An inert gas atmosphere was prepared in a reaction vessel, then, 3-bromobenzoyl chloride (117 g), ethyl butylimidate hydrochloride (81 g) and chloroform (3732 ml) were added, and they were mixed by stirring at room temperature, and triethylamine (113 g) was dropped at room temperature over a period of 2 hours, and further, the mixture was stirred at room temperature for 2 hours, to obtain a reaction liquid. The resultant reaction liquid was concentrated under reduced pressure, then, the reaction product was extracted into an organic layer using water (700 ml) and chloroform (1000 ml), and the resultant organic layer was washed with water (700 ml) and saturated saline (700 ml) in series, then, dried over anhydrous magnesium sulfate. Thereafter, the inorganic salt was removed by filtration, and the resultant filtrate was concentrated, to obtain a mixture (197.57 g) containing a compound IL1-a as a yellow oil. The purity by HPLC was 98.24%.
An inert gas atmosphere was prepared in a reaction vessel, then, a mixture (197.57 g) containing a compound IL1-a, and chloroform (2666 ml) were added, and they were mixed by stirring at room temperature, and a solution prepared by adding methylhydrazine (21.61 g) to water (21.61 g) was dropped slowly while keeping the temperature of the reaction liquid around room temperature, then, the mixture was stirred for 2 hours at room temperature, to obtain a reaction liquid. The resultant reaction liquid was washed with water (1000 ml) twice, then, the resultant organic layer was dried over anhydrous magnesium sulfate. The inorganic salt was removed by filtration, and further, the solvent was removed by concentration under reduced pressure, to obtain a mixture (1.71 g) containing a compound IL1. An operation of purifying the resultant mixture by silica gel column chromatography (developing solvent; a mixed solvent of dichloromethane/ethyl acetate) was repeated twice, to obtain 92.9 g of a compound IL1 (HPLC area percentage value: 98.91%, yield based on bromobenzoyl chloride: 62.2%) as a yellow oil.
1H-NMR (300 MHz, CDCl3) δ (ppm)=1.01 (t, 9 Hz, 3H), 1.65-1.85 (m, 2H), 2.71 (t, 6 Hz, 2H), 3.93 (s, 3H), 7.30-7.45 (m, 1H), 7.55-7.65 (m, 2H), 7.84 (s, 1H).
A nitrogen gas atmosphere was prepared in a reaction vessel, then, iridium chloride trihydrate (20 g) and a compound IL1 (39.73 g) were added, and further, ethoxyethanol (794 ml) previously bubbled with an argon gas and water (265 ml) previously bubbled with an argon gas were added, and further, the mixture was bubbled with an argon gas for 20 minutes while stirring, to remove dissolved oxygen. Thereafter, the mixture was stirred under reflux for 22 hours while heating by using an oil bath of 125° C., to obtain a reaction liquid. The resultant reaction liquid was cooled down to room temperature, then, water (794 g) was added, and the mixture was stirred vigorously, and the deposited precipitate was isolated as a solid by filtration, and the resultant solid was washed with water (300 ml) and hexane (300 ml) in this order, and dried under reduced pressure at 50° C., to obtain an intended coarse compound IM1-a (40.61 g) as a yellow powder. The purity by HPLC was 98.24%.
A nitrogen gas atmosphere was prepared in a reaction vessel, then, a coarse compound IM1-a (40.61 g), a compound IL1 (95.34 g) synthesized by the same method as described above, diethylene glycol dimethyl ether (567 ml) and silver trifluoroacetate (29.15 g) were added, and further, the mixture was bubbled with a nitrogen gas for 20 minutes while stirring, to remove dissolved oxygen. Thereafter, this was stirred for 22 hours while heating by using an oil bath of 170° C., to obtain a reaction liquid. The resultant reaction liquid was cooled, then, a solid was removed by filtration, to the resultant filtrate was added water (567 g) and the mixture was stirred, and the deposited precipitate was isolated as a solid by filtration. The resultant solid was washed with water (200 ml) once, and further washed with methanol (200 ml) twice, and dried under reduced pressure, to obtain a yellow solid (64.59 g, purity: 96.23%). The resultant yellow solid was dissolved in dichloromethane, and the solution was allowed to pass through a silica gel column (silica gel amount: 292 g), and the resultant solution was concentrated, to obtain a mixture containing an intended substance (58.72 g, purity: 96.25%) as a yellow solid. The resultant mixture was purified by recrystallization (a mixed solvent of dichloromethane/methanol), and further purified by recrystallization (a mixed solvent of dichloromethane/ethyl acetate), to obtain a metal complex IM1 (48.66 g). To the resultant coarse metal complex IM1 was added ethyl acetate (487 ml), and the mixture was stirred under reflux with heating, then, methanol (487 ml) was dropped, the mixture was cooled down to room temperature to cause generation of a crystal which was then isolated by filtration, and this was washed with methanol and dried under reduced pressure, to obtain an intended metal complex IM1 (48.03 g, purity: 99.36%).
LC-MS (APPI: pos): calcd. [C36H39Br8IrN9]=1027.05, measured=1028.1 (m+H)
A nitrogen gas flow was prepared in a reaction vessel, then, a metal complex IM1 (2.50 g) and a compound S2 (8.89 g) were added, and this was dissolved in tetrahydrofuran (200 ml) at room temperature. Thereafter, to this were added a 20 wt % tetraethylammonium hydroxide aqueous solution (12.51 g) and tetrakis(triphenylphosphine)palladium(0) (56.1 mg), and the mixture was refluxed for 23 hours while shading. After cooling to room temperature, the resultant reaction mixture was poured into distilled water (200 ml), and extracted with toluene (150 ml). The resultant organic layer was washed with distilled water (200 ml) and saturated saline (350 ml) in this order. The resultant organic layer was dried over sodium sulfate, then, filtrated, and the filtrate was concentrated. The resultant residue was purified by silica gel column chromatography (a mixed solvent of hexane/ethyl acetate=10/1 (by volume)), and concentrated under reduced pressure, to remove the solvent. To the resultant residue were added toluene (115 ml) and acetonitrile (655 ml), and the mixture was heated at 50° C. for 1 hour while shading. Thereafter, this was filtrated, and dried under reduced pressure, to obtain a metal complex 4 (7.07 g) represented by the above-described formula.
1H-NMR (CD2Cl2, 300 MHz) δ (ppm)=8.00 (m, 9H), 7.95-7.93 (m, 15H), 7.87 (s, 6H), 7.67 (d, 24H), 7.47 (d, 24H), 7.31 (d, 3H), 6.97 (d, 3H), 4.29 (s, 9H), 2.31-2.21 (m, 3H), 2.02-1.92 (m, 3H), 1.77 (s, 24H), 1.51-1.19 (m, 78H), 0.78-0.71 (m, 117H).
In a reaction vessel, sodium nitrite (1.38 g) was weighed and dissolved in 11 mL of water of 0° C. under a nitrogen gas atmosphere. Thereafter, 4-bromo-2,6-dimethylaniline (4.0 g) was suspended in 33 mL of concentrated hydrochloric acid, and the suspension was dropped into a nitrous acid aqueous solution so as not to exceed 5° C. Thereafter, the mixture was stirred at 0° C. for 15 minutes, and 15 mL of a concentrated hydrochloric acid solution of tin(II) chloride (5.31 g) was added to the resultant reaction liquid, and the mixture was returned to room temperature and stirred for 6 hours. The resultant suspension was filtrated with suction, and washed with concentrated hydrochloric acid and cold water, and dried in a vacuum, to obtain 4.98 g of a compound S3-1 as a milky white solid.
In a reaction vessel, a compound $3-1 (1.26 g), a compound IL1-a (1.19 g) and sodium acetate (410 mg) were weighed, and each 8 mL of acetic acid and dioxane were added, then, the mixture was placed under a nitrogen gas atmosphere. The resultant reaction mixture was heated at 90° C. for 15 hours, then, left to cool. Thereafter, toluene was added to this before filtration with suction, and the filtrate was concentrated. The resultant coarse product was allowed to pass through a silica gel column, and separated and purified using a mixed solvent of hexane and ethyl acetate, to obtain 1.0 g of a compound S3-2 as a pale yellow liquid (yield: 56%). The results of 1H-NMR analysis are shown below.
1H-NMR (400 MHz/(CD3)2CO) δ (ppm)=7.60 (dt, 1H), 7.49 (s, 2H), 7.34-7.27 (m, 3H), 2.74 (t, 2H), 1.95 (s, 6H), 1.83 (q, 2H), 0.99 (t, 3H).
In a reaction vessel, a compound $3-2 (990 mg), 3,5-di(4-tert-butylphenyl)phenylboronic acid pinacol ester (2.2 g) and sodium carbonate 1.4 g (13 mmol) were weighed, and 5 mL of water and 15 mL of dioxane were added, then, the mixture was refluxed with heating for 6 hours under a nitrogen gas atmosphere. After left to cool, toluene was added to this and the solution was filtrated with suction, and the filtrate was concentrated. Thereafter, water and toluene were added and water-washing was performed, and the resultant oil layer was recovered, then, concentrated. The resultant coarse product was allowed to pass through a silica gel column and separated and purified using a mixed solvent of chloroform and ethyl acetate. The resultant eluent was concentrated, and recrystallized from hexane, to obtain 2.0 g of a compound S3 as a white solid (yield: 94%). The results of 1H-NMR analysis are shown below.
1H-NMR (400 MHz, CDCl3) δ (ppm)=7.97 (s, 1H), 7.82 (s, 1H), 7.75-7.70 (m, 4H), 7.62-7.54 (m, 11H), 7.49-7.46 (m, 6H), 7.42 (d, 1H), 7.37 (d, 4H), 2.88 (t, 2H), 2.10 (s, 6H), 1.92 (td, 2H), 1.37 (s, 18H), 1.31 (s, 18H), 1.06 (t, 3H).
In a reaction vessel, iridium chloride (91 mg) and a compound S3 (500 mg) were weighed, and 10 mL of water and 10 mL of 2-butoxyethanol were added, then, the mixture was refluxed with heating for 18 hours under an argon gas atmosphere. After left to cool, water and methanol were poured into this, and the deposited precipitate was filtrated with suction. The resultant filtrated material was dried, to obtain 500 mg of a yellowish brown solid.
In another reaction vessel, 500 mg of this brown solid, a compound S3 (1.23 g) and 67 mg of silver trifluoromethanesulfonate were weighed, and 10 mL of diethylene glycol dimethyl ester was added, then, the mixture was refluxed with heating for 11 hours under an argon gas atmosphere. After left to cool, toluene was poured into this, and the solution was filtrated with suction. The resultant filtrate was concentrated before passing through a silica gel column, and separated and purified using a mixed solvent of toluene and hexane. The resultant eluent was concentrated, and recrystallized from a mixed solvent of toluene and hexane, to obtain 420 mg of a metal complex 5 (yield: 52%) as a powdery yellow solid. The results of 1H-NMR analysis are shown below.
1H-NMR (400 MHz, CDCl3) δ (ppm)=7.85-7.82 (m, 9H), 7.64 (s, 3H), 7.70 (s, 3H), 7.58-7.52 (m, 15H), 7.39-7.46 (m, 30H), 7.23-7.13 (m, 18H), 6.82 (d, 3H), 2.55 (m, 6H), 2.41 (s, 9H), 2.05 (s, 9H), 1.86-1.73 (m, 6H), 1.36 (s, 54H), 1.19 (s, 54H), 0.88 (t, 9H).
A metal complex 6 was synthesized according to a method described in Synthesis Example 3 described above.
A metal complex 7 was synthesized according to a method described in JP-A No. 2012-6914.
(Step 1) An inert gas atmosphere was prepared in a reaction vessel, then, a compound CM1 (0.995 g) synthesized according to a method described in JP-A No. 2010-189630, a compound CM2 (0.106 g) synthesized according to a method described in JP-A No. 2008-106241, a compound CM3 (0.0924 g) synthesized according to a method described in JP-A No. 2010-215886, a compound CM4 (0.736 g) synthesized according to a method described in International Publication WO2002/045184, dichlorobis[tris(2-methoxyphenyl)phosphine]palladium (1.8 mg) and toluene (50 ml) were added, and the mixture was heated at 105° C.
(Step 2) Into the resultant reaction liquid, a 20 wt % tetraethylammonium hydroxide aqueous solution (6.6 ml) was dropped, and the mixture was refluxed for 5.5 hours.
(Step 3) Thereafter, to this were added phenylboronic acid (24.4 mg), a 20 wt % tetraethylammonium hydroxide aqueous solution (6.6 ml) and dichlorobis[tris(2-methoxyphenyl)phosphine]palladium (1.8 mg), and the mixture was refluxed for 14 hours.
(Step 4) Thereafter, to this was added a sodium diethyldithiacarbamate aqueous solution, and the mixture was stirred at 80° C. for 2 hours. The resultant reaction liquid was cooled, then, washed with water twice, with a 3 wt % acetic acid aqueous solution twice and with water twice, and the resultant solution was dropped into methanol, to cause precipitation. The resultant precipitate was dissolved in toluene, and the solution was allowed to pass through an alumina column and a silica gel column in this order to accomplish purification. The resultant solution was dropped into methanol, and the mixture was stirred, to cause precipitation. The resultant precipitate was isolated by filtration, and dried, to obtain 0.91 g of a polymer compound HTL-1. The polymer compound HTL-1 had a Mn of 5.2×104 and a Mw of 2.5×105.
The polymer compound HTL-1 is a copolymer constituted of a constitutional unit derived from a compound CM1, a constitutional unit derived from a compound CM2, a constitutional unit derived from a compound CM3 and a constitutional unit derived from a compound CM4 at a molar ratio of 50:5:5:40, according to theoretical values calculated from the amounts of charged raw materials.
A nitrogen gas atmosphere was prepared in a reaction vessel, then, a compound CM1 (1.73 g), a compound CM5 (2.68 g) synthesized according to a method described in International Publication WO2005/049546, a compound CM6 (0.223 g) synthesized according to a method described in International Publication WO2011/049241 and toluene (73 ml) were added, and the mixture was heated at about 80° C. Thereafter, to this were added palladium acetate (0.77 mg), tris(2-methoxyphenyl)phosphine (4.90 mg) and a 20 wt % tetraethylammonium hydroxide aqueous solution (12.3 g), and the mixture was stirred for about 4 hours under reflux. Thereafter, to this were added phenylboronic acid (85.6 mg), palladium acetate (0.72 mg), tris(2-methoxyphenyl)phosphine (4.89 mg) and a 20 wt % tetraethylammonium hydroxide aqueous solution (12.3 g), and the mixture was further stirred for about 19.5 hours under reflux. Thereafter, to this was added a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.98 g) in ion exchanged water (20 ml), and the mixture was stirred for 2 hours while heating at 85° C. Thereafter, the organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water five times, in series. The resultant organic layer was dropped into methanol to cause precipitation, and the precipitate was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause precipitation, and the filtrate was isolated by filtration, and dried, to obtain a polymer compound HTL-2 (2.907 g). The polystyrene-equivalent number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymer compound HTL-2 were Mn=1.9×104 and Mw=9.9×104.
The polymer compound HTL-2 is a copolymer constituted of a constitutional unit derived from a compound CM1, a constitutional unit derived from a compound CM5 and a constitutional unit derived from a compound CM6 at a molar ratio of 50:42.5:7.5, according to theoretical values calculated from the charging amounts of monomers.
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, a compound Ma2 (64.6 g) and tetrahydro furan (615 mL) were added, and the mixture was cooled down to −70° C. Into this, a n-butyllithium hexane solution (1.6 M, 218 mL) was dropped over a period of 1 hour, then, the mixture was stirred at −70° C. for 2 hours. To this, a compound Ma 1 (42.1 g) was added in several batches, then, the mixture was stirred at −70° C. for 2 hours. Into this, methanol (40 mL) was dropped over a period of 1 hour, then, the mixture was heated up to room temperature. Thereafter, the solvent was distilled off by concentrating under reduced pressure, and toluene and water were added. Thereafter, an aqueous layer was separated and the resultant organic layer was further washed with water. The resultant organic layer was concentrated under reduced pressure, and the resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and ethyl acetate), thereby obtaining 71 g of a compound Ma3 as a colorless oil. The compound Ma3 had an HPLC area percentage value (UV: 254 nm) of 97.5%. This operation was repeated, thereby obtaining a necessary amount of the compound Ma3.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 2.43 (1H, s), 3.07-3.13 (4H, m), 6.95 (1H, d), 7.07 (1H. s), 7.18-7.28 (3H, m), 7.28-7.40 (4H, m), 7.66 (2H, s).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Ma3 (72.3 g), toluene (723 mL) and triethylsilane (118.0 g) were added, and the mixture was heated up to 70° C. Into this, methanesulfonic acid (97.7 g) was dropped over a period of 1.5 hours, then, the mixture was stirred at 70° C. for 0.5 hours. Thereafter, the mixture was cooled down to room temperature, and toluene (1 L) and water (1 L) were added, then, an aqueous layer was separated. The resultant organic layer was washed with water, a 5 wt % sodium hydrogen carbonate aqueous solution and water in this order. The resultant organic layer was concentrated under reduced pressure, and the resultant coarse product was recrystallized from a mixed solvent of toluene and ethanol, thereby obtaining 51.8 g of a compound Ma4 as a white solid.
The compound Ma4 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more. This operation was repeated, thereby obtaining a necessary amount of the compound Ma4.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 3.03-3.14 (4H, m), 4.99 (1H, s), 6.68 (1H, s), 6.92-7.01 (2H, m), 7.20-7.28 (2H, m), 7.29-7.38 (4H, m), 7.78 (2H, d).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, a compound Mb1 (185.0 g), a compound Mb2 (121.1 g), CuI (3.2 g), dichloromethane (185 mL) and triethylamine (2.59 L) were added, and the mixture was heated up to the reflux temperature. Thereafter, the mixture was stirred at the reflux temperature for 0.5 hours, and cooled down to room temperature. To this was added dichloromethane (1.85 L), then, the mixture was filtrated through a filter paved with celite. To the resultant filtrate was added a 10 wt % sodium hydrogen carbonate aqueous solution, then, an aqueous layer was separated. The resultant organic layer was washed with water twice, washed with a saturated NaCl aqueous solution, then, magnesium sulfate was added. The resultant mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of chloroform and ethyl acetate), thereby obtaining a coarse product. The resultant coarse product was dissolved in ethanol (1.4 L), then, activated carbon (5 g) was added, and the mixture was filtrated. The resultant filtrate was concentrated under reduced pressure, and the resultant residue was recrystallized from hexane, thereby obtaining 99.0 g of a compound Mb3 as a white solid. The compound Mb3 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more.
This operation was repeated, thereby obtaining a necessary amount of the compound Mb3.
1H-NMR (DMSO-d6, 300 MHz): δ (ppm): 1.52-1.55 (8H, m), 2.42 (4H, t), 3.38-3.44 (4H, m), 4.39-4.43 (2H, m), 7.31 (4H, s).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb3 (110.0 g), ethanol (1.65 L) and palladium/carbon (Pd weight: 10%) (11.0 g) were added, and the mixture was heated up to 30° C. Thereafter, a gas in the flask was purged with a hydrogen gas. Thereafter, the mixture was stirred at 30° C. for 3 hours while feeding a hydrogen gas into the flask. Thereafter, a gas in the flask was purged with a nitrogen gas. The resultant mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of chloroform and ethyl acetate), thereby obtaining a coarse product. The resultant coarse product was recrystallized from hexane, thereby obtaining 93.4 g of a compound Mb4 as a white solid. The compound Mb4 had an HPLC area percentage value (UV: 254 nm) of 98.3%.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 1.30-1.40 (8H, m), 1.55-1.65 (8H, m), 2.58 (4H, t), 3.64 (4H, t), 7.09 (4H, s).
13C-NMR (CDCl3, 75 MHz): δ (ppm): 25.53, 28.99, 31.39, 32.62, 35.37, 62.90, 128.18, 139.85.
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb4 (61.0 g), pyridine (0.9 g) and toluene (732 mL) were added, and the mixture was heated up to 60° C. Into this, thionyl chloride (91.4 g) was dropped over a period of 1.5 hours, then, the mixture was stirred at 60° C. for 5 hours. The resultant mixture was cooled down to room temperature, then, concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and ethyl acetate), thereby obtaining 64.3 g of a compound Mb5 as a colorless oil. The resultant compound Mb5 had an HPLC area percentage value (UV: 254 nm) of 97.2%.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 1.35-1.40 (4H, m), 1.41-1.50 (4H, m), 1.60-1.68 (4H, m), 1.75-1.82 (4H, m), 2.60 (4H, t), 3.55 (4H, t), 7.11 (4H, s).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb5 (42.0 g), an iron powder (1.7 g), iodine (0.3 g) and dichloromethane (800 mL) were added. Thereafter, the whole flask was light-shielded, and cooled at 0 to 5° C. Into this, a mixed liquid of bromine (44.7 g) and dichloromethane (200 mL) was dropped over a period of 1 hour, then, the mixture was stirred at 0 to 5° C. overnight. The resultant mixed liquid was added to water (1.2 L) cooled at 0 to 5° C., then, an organic layer was separated. The resultant organic layer was washed with a 10 wt % sodium thiosulfate aqueous solution, and further, washed with a saturated sodium chloride aqueous solution and water in this order. To the resultant organic layer was added sodium sulfate, then, the mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent; hexane), thereby obtaining a coarse product. The resultant coarse product was recrystallized from hexane, there by obtaining 47.0 g of a compound Mb6 as a white solid. The compound Mb6 had an HPLC area percentage value (UV: 254 nm) of 98.3%.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 1.38-1.45 (4H, m), 1.47-1.55 (4H, n), 1.57-1.67 (4H, m), 1.77-1.84 (4H, m), 2.66 (4H, t), 3.55 (4H, t), 7.36 (2H, s).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium iodide (152.1 g) and acetone (600 mL) were added, and the mixture was stirred at room temperature for 0.5 hours. To this was added the compound Mb6 (40.0 g), then, the mixture was heated up to the reflux temperature, and stirred at the reflux temperature for 24 hours. Thereafter, the mixture was cooled down to room temperature, and the resultant mixed liquid was added to water (1.2 L). The deposited solid was separated by filtration, then, washed with water, thereby obtaining a coarse product. The resultant coarse product was recrystallized from a mixed liquid of toluene and methanol, thereby obtaining 46.0 g of a compound Mb7 as a white solid. The resultant compound Mb7 had an HPLC area percentage value (UV: 254 nm) of 99.4%. This operation was repeated, thereby obtaining a necessary amount of the compound Mb7.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 1.35-1.50 (8H, m), 1.57-1.65 (4H, m), 1.80-1.89 (4H, m), 2.65 (4H, t), 3.20 (4H, t), 7.36 (2H, s).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium hydride (60 wt %, dispersed in liquid paraffin) (9.4 g), tetrahydrofuran (110 mL) and the compound Mb7 (63.2 g) were added. To this, a compound Ma4 (55.0 g) was added in several batches, then, the mixture was stirred for 12 hours. To this were added toluene (440 mL) and water (220 mL), then, an aqueous layer was separated. The resultant organic layer was washed with water, then, magnesium sulfate was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and toluene). Thereafter, the product was recrystallized from heptane, thereby obtaining 84.1 g of a compound Mb8 as a white solid. The resultant compound Mb8 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 0.70-0.76 (4H, m), 1.10-1.21 (8H, m), 1.32-1.44 (4H, m), 2.39-2.58 (8H, m), 3.00-3.12 (8H, m), 6.82-6.94 (4H, m), 7.00-7.05 (2H, m), 7.17-7.28 (10H, m), 7.30-7.38 (4H, m), 7.71-7.77 (4H, m).
A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb8 (84.0 g), [1,1′-bis(diphenylphosphino) ferrocene]palladium(II) dichloride dichloromethane adduct (PdCl2(dppf).CH2Cl2, 2.2 g), bispinacolatodiboron (68.3 g), potassium acetate (52.8 g) and cyclopentyl methyl ether (840 mL) were added, and the mixture was heated up to the reflux temperature, then, stirred at the reflux temperature for 5 hours. Thereafter, the mixture was cooled d own to room temperature, and toluene (500 mL) and water (300 mL) were added, then, an aqueous layer was separated. The resultant organic layer was washed with water, then, activated carbon (18.5 g) was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and toluene). Thereafter, an operation of recrystallizing from a mixed liquid of toluene and acetonitrile was repeated, there by obtaining 45.8 g of a compound CM7 as a white solid. The resultant compound CM7 had an HPLC area percentage value (UV: 254 nm) of 99.4%.
1H-NMR (CDCl3, 300 MHz): δ (ppm): 0.70-0.76 (4H, m), 1.24-1.40 (36H, m), 2.39-2.48 (4H, m), 2.66-2.75 (4H, m), 3.00-3.10 (8H, m), 6.76-6.90 (4H, m), 7.00-7.05 (2H, m), 7.19-7.30 (8H, m), 7.30-7.36 (4H, m), 7.43 (2H, s), 7.72 (4H, d).
A polymer compound HTL-3 (1.05 g) was obtained by a method according to Synthesis of polymer compound HTL-1, excepting that (Step 1) in Synthesis of polymer compound HTL-1 was changed to “An inert gas atmosphere was prepared in a reaction vessel, then, a compound CM7 (0.12976 g), a compound CM8 (0.0620 g) synthesized according to a method described in International Publication WO2013/146806, a compound CM1 (0.493 g), a compound CM5 (1.15 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.20 mg) and toluene (30 ml) were added, and the mixture was heated at 105CC.”.
The polymer compound HTL-3 had a polystyrene-equivalent number-average molecular weight of 2.4×104 and a polystyrene-equivalent weight-average molecular weight of 1.8×105.
The polymer compound HTL-3 is a copolymer constituted of a constitutional unit derived from a compound CM7, a constitutional unit derived from a compound CM8, a constitutional unit derived from a compound CM1 and a constitutional unit derived from a compound CM5 at a molar ratio of 5:5:40:50, according to theoretical values calculated from the amounts of charged raw materials.
A polymer compound HTL-4 was synthesized according to a method described in International Publication WO2011/049241, using a compound CM9 synthesized according to a method described in International Publication WO2002/045184, and a compound CM4 and a compound CM6.
The polystyrene-equivalent number-average molecular weight and weight-average molecular weight of the polymer compound HTL-4 were Mn=8.9×104 and Mw=4.2×105, respectively.
The polymer compound HTL-4 is a copolymer constituted of a constitutional unit derived from a compound CM9, a constitutional unit derived from a compound CM4 and a constitutional unit derived from a compound CM6 at a molar ratio of 50:42.5:7.5, according to theoretical values calculated from the amounts of charged raw materials.
A polymer compound HTL-5 was synthesized according to a method described in JP-A No. 2012-36381, using a compound CM9 and a compound CM4.
The polystyrene-equivalent number-average molecular weight and weight-average molecular weight of the polymer compound HTL-5 were Mn=8.1×104 and Mw=3.4×105, respectively.
The polymer compound HTL-5 is a copolymer constituted of a constitutional unit derived from a compound CM9 and a constitutional unit derived from a compound CM4 at a molar ratio of 50:50, according to theoretical values calculated from the amounts of charged raw materials.
A polymer compound ETL-1a was synthesized according to a method described in JP-A No. 2012-33845, using a compound CM10 synthesized according to a method described in JP-A No. 2012-33845 and a compound CM11 synthesized according to a method described in JP-A No. 2012-33845.
The polymer compound ETL-1a had a Mn of 5.2×104.
The polymer compound ETL-1a is a copolymer constituted of a constitutional unit derived from a compound CM10 and a constitutional unit derived from a compound CM11 at a molar ratio of 50:50, according to theoretical values calculated from the amounts of charged raw materials.
An inert gas atmosphere was prepared in a reaction vessel, then, a polymer compound ETL-1a (200 mg), tetrahydrofuran (20 ml) and ethanol (20 ml) were added, and the mixture was heated at 55° C. To this was added cesium hydroxide (200 mg) dissolved in water (2 ml), and the mixture was stirred at 55° C. for 6 hours. Thereafter, the mixture was cooled down to room temperature, then, concentrated under reduced pressure, to obtain a solid. The resultant solid was washed with water, then, dried under reduced pressure, to obtain a polymer compound ETL-1 (150 mg, pale yellow solid). It was confirmed that a signal derived from an ethyl group of an ethyl ester portion of a polymer compound ETL-1a disappeared completely, by the NMR spectrum of the resultant polymer compound ETL-1.
An ITO film with a thickness of 45 nm was attached to a glass substrate by a sputtering method, to form an anode. On the anode, a polythiophene.sulfonic acid type hole injection material AQ-1200 (manufactured by Plextronics) was spin-coated to form a film with a thickness of 35 nm, and the film was heated on a hot plate at 170° C. for 15 minutes under an air atmosphere, to form a hole injection layer.
A polymer compound HTL-1 was dissolved at a concentration of 0.7 wt % in xylene. The resultant xylene solution was spin-coated on the hole injection layer to form a film with a thickness of 20 nm, and the film was heated on a hot plate at 180° C. for 60 minutes under a nitrogen gas atmosphere, to form a hole transporting layer.
A low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) were dissolved at a concentration of 2.0 wt % in toluene. The resultant toluene solution was spin-coated on the hole transporting layer to form a film with a thickness of 75 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.
The substrate carrying the light emitting layer formed thereon was placed in a vapor deposition machine, and the pressure was reduced to 1.0×10−4 Pa or less, then, as a cathode, sodium fluoride was vapor-deposited with a thickness of about 7 nm on the light emitting layer, then, aluminum was vapor-deposited with a thickness of about 120 nm on the sodium fluoride layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D1.
Voltage was applied to the light emitting device D1, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 3.23%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.22).
A light emitting device D2 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 2 (low molecular weight compound SM1/metal complex 2=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device D2, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 12.89%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.32).
A light emitting device D3 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM2 (manufactured by Luminescense Technology) and a metal complex 1 (low molecular weight compound SM2/metal complex 1=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device D3, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 1.75%, and the CIE chromaticity coordinate (x, y) was (0.18, 0.27).
A light emitting device D4 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 4 (low molecular weight compound SM1/metal complex 4=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device D4, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 13.82%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.32).
A light emitting device D5 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 5 (low molecular weight compound SM1/metal complex 5=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device D5, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 18.68%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.34).
A light emitting device D6 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 6 (low molecular weight compound SM1/metal complex 6=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1-75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device D6, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 11.52%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.35).
A light emitting device D7 was fabricated in the same manner as in Example D2, excepting that a polymer compound HTL-2 was used instead of the polymer compound HTL-1 in Example D2.
Voltage was applied to the light emitting device D7, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 5.23%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.30).
A light emitting device D8 was fabricated in the same manner as in Example D2, excepting that a polymer compound HTL-3 was used instead of the polymer compound HTL-1 in Example D2.
Voltage was applied to the light emitting device D8, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 5.95%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.31).
A light emitting device D9 was fabricated in the same manner as in Example D1, excepting that a polymer compound HTL-4 was used instead of the polymer compound HTL-1 in Example D1.
Voltage was applied to the light emitting device D9, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 2.99%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.23).
A light emitting device CD1 was fabricated in the same manner as in Example D1, excepting that (Formation of light emitting layer) in Example D1 was changed to “A low molecular weight compound SM3 (manufactured by DOJINDO Molecular Technologies, Inc.) and a metal complex 1 (low molecular weight compound SM3/metal complex 1=75 wt %/25 wt %) were dissolved at a concentration of 0.7 wt % in chloroform. The resultant chloroform solution was spin-coated on the hole transporting layer to form a film with a thickness of 75 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.”.
Voltage was applied to the light emitting device CD1, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 0.49%, and the CIE chromaticity coordinate (x, y) was (0.17, 0.25).
A light emitting device CD2 was fabricated in the same manner as in Example D1, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 3 (low molecular weight compound SM1/metal complex 3=7 5 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D1.
Voltage was applied to the light emitting device CD2, to observe EL emission. The external quantum efficiency at 250 cd/m2 was 1.03%, and the CIE chromaticity coordinate (x, y) was (0.24, 0.50).
An ITO film with a thickness of 45 nm was attached to a glass substrate by a sputtering method, to form an anode. On the anode, a polythiophene.sulfonic acid type hole injection material AQ-1200 (manufactured by Plextronics) was spin-coated to form a film with a thickness of 35 nm, and the film was heated on a hot plate at 170° C. for 15 minutes under an air atmosphere, to form a hole injection layer.
A polymer compound HTL-1 was dissolved at a concentration of 0.7 wt % in xylene. The resultant xylene solution was spin-coated on the hole injection layer to form a film with a thickness of 20 nm, and the film was heated on a hot plate at 180° C. for 60 minutes under a nitrogen gas atmosphere, to form a hole transporting layer.
A low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) were dissolved at a concentration of 2.0 wt % in toluene. The resultant toluene solution was spin-coated on the hole transporting layer to form a film with a thickness of 75 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.
A polymer compound ETL-1 was dissolved at a concentration of 0.25 wt % in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol. The resultant 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution was spin-coated on the light emitting layer to form a film with a thickness of 10 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form an electron transporting layer.
The substrate carrying the electron transporting layer formed thereon was placed in a vapor deposition machine, and the pressure was reduced to 1.0×10−4 Pa or less, then, as a cathode, sodium fluoride was vapor-deposited with a thickness of about 7 nm on the electron transporting layer, then, aluminum was vapor-deposited with a thickness of about 120 nm on the sodium fluoride layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D10.
Voltage was applied to the light emitting device D10, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 4.60%, and the CIE chromaticity coordinate (x, y) was (0.16, 0.25).
A light emitting device D11 was fabricated in the same manner as in Example D10, excepting that a low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 2 (low molecular weight compound SM1/metal complex 2=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D10.
Voltage was applied to the light emitting device D11, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 10.98%, and the CIE chromaticity coordinate (x, y) was (0.17, 0.38).
A light emitting device 012 was fabricated in the same manner as in Example D10, excepting that a low molecular weight compound SM2 (manufactured by Luminescense Technology) and a metal complex 1 (low molecular weight compound SM2/metal complex 1=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1-75 wt %/25 wt %) in Example D10.
Voltage was applied to the light emitting device D12, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 4.35%, and the CIE chromaticity coordinate (x, y) was (0.18, 0.27).
A light emitting device D13 was fabricated in the same manner as in Example D10, excepting that a low molecular weight compound SM4 and a metal complex 1 (low molecular weight compound SM4/metal complex 1=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D10.
Voltage was applied to the light emitting device D13, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 3.23%, and the CIE chromaticity coordinate (x, y) was (0.16, 0.25).
A light emitting device D14 was fabricated in the same manner as in Example D10, excepting that a low molecular weight compound SM1 and a metal complex 7 (low molecular weight compound SM1/metal complex 7=75 wt %/25 wt %) were used instead of the low molecular weight compound SM1 (manufactured by Luminescense Technology) and the metal complex 1 (low molecular weight compound SM1/metal complex 1=75 wt %/25 wt %) in Example D10.
Voltage was applied to the light emitting device D14, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 1.93%, and the CIE chromaticity coordinate (x, y) was (0.30, 0.55).
A light emitting device CD3 was fabricated in the same manner as in Example D10, excepting that (Formation of light emitting layer) in Example D10 was changed to “A low molecular weight compound SM3 (manufactured by DOJINDO Molecular Technologies, Inc.) and a metal complex 1 (low molecular weight compound SM3/metal complex 1=75 wt %/25 wt %) were dissolved at a concentration of 0.7 wt % in chloroform. The resultant chloroform solution was spin-coated on the hole transporting layer to form a film with a thickness of 75 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.”.
Voltage was applied to the light emitting device CD3, to observe EL emission. The external quantum efficiency at 2000 cd/m2 was 1.28%, and the CIE chromaticity coordinate (x, y) was (0.17, 0.28).
An ITO film with a thickness of 45 nm was attached to a glass substrate by a sputtering method, to form an anode. On the anode, a polythiophene.sulfonic acid type hole injection material AQ-1200 (manufactured by Plextronics) was spin-coated to form a film with a thickness of 35 nm, and the film was heated on a hot plate at 170° C. for 15 minutes under an air atmosphere, to form a hole injection layer.
A polymer compound HTL-1 was dissolved at a concentration of 0.7 wt % in xylene. The resultant xylene solution was spin-coated on the hole injection layer to form a film with a thickness of 20 nm, and the film was heated on a hot plate at 180° C. for 60 minutes under a nitrogen gas atmosphere, to form a hole transporting layer.
A low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 2 (low molecular weight compound SM1/metal complex 2=70 wt %/30 wt %) were dissolved at a concentration of 2.0 wt % in toluene. The resultant toluene solution was spin-coated on the hole transporting layer to form a film with a thickness of 60 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.
A polymer compound ETL-1 was dissolved at a concentration of 0.25 wt % in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol. The resultant 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution was spin-coated on the light emitting layer to form a film with a thickness of 10 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form an electron transporting layer.
The substrate carrying the electron transporting layer formed thereon was placed in a vapor deposition machine, and the pressure was reduced to 1.0×10−4 Pa or less, then, as a cathode, sodium fluoride was vapor-deposited with a thickness of about 7 nm on the electron transporting layer, then, aluminum was vapor-deposited with a thickness of about 120 nm on the sodium fluoride layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D15.
Voltage was applied to the light emitting device D15, to observe EL emission. The external quantum efficiency at 1000 cd/m2 was 13.32%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.30).
A light emitting device D16 was fabricated in the same manner as in Example D15, excepting that a polymer compound HTL-1 and a metal complex 2 (polymer compound HTL-1/metal complex 2=95 wt %/5 wt %) were used instead of the polymer compound HTL-1 in Example D15.
Voltage was applied to the light emitting device D16, to observe EL emission. The external quantum efficiency at 1000 cd/m2 was 8.77%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.30).
A light emitting device D17 was fabricated in the same manner as in Example D15, excepting that a polymer compound HTL-1 and a metal complex 2 (polymer compound HTL-1/metal complex 2=85 wt %/15 wt %) were used instead of the polymer compound HTL-1 in Example D15.
Voltage was applied to the light emitting device D17, to observe EL emission. The external quantum efficiency at 1000 cd/m2 was 7.88%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.30).
A light emitting device D18 was fabricated in the same manner as in Example D15, excepting that a polymer compound HTL-1 and a metal complex 2 (polymer compound HTL-1/metal complex 2=70 wt %/30 wt %) were used instead of the polymer compound HTL-1 in Example D15.
Voltage was applied to the light emitting device D01, to observe EL emission. The external quantum efficiency at 1000 cd/m2 was 7.18%, and the CIE chromaticity coordinate (x, y) was (0.15, 0.29).
An ITO film with a thickness of 45 nm was attached to a glass substrate by a sputtering method, to form an anode. On the anode, a polythiophene.sulfonic acid type hole injection material AQ-1200 (manufactured by Plextronics) was spin-coated to form a film with a thickness of 35 nm, and the film was heated on a hot plate at 170° C. for 15 minutes under an air atmosphere, to form a hole injection layer.
A polymer compound HTL-4 was dissolved at a concentration of 0.7 wt % in xylene. The resultant xylene solution was spin-coated on the hole injection layer to form a film with a thickness of 20 nm, and the film was heated on a hot plate at 180° C. for 60 minutes under a nitrogen gas atmosphere, to form a hole transporting layer.
A low molecular weight compound SM1 (manufactured by Luminescense Technology) and a metal complex 7 (low molecular weight compound SM1/metal complex 7=75 wt %/25 wt %) were dissolved at a concentration of 2.0 wt % in chlorobenzene. The resultant chlorobenzene solution was spin-coated on the hole transporting layer to form a film with a thickness of 75 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form a light emitting layer.
A polymer compound ETL-1 was dissolved at a concentration of 0.25 wt % in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol. The resultant 2,2,3,3,4,4,5,5-octafluoro-1-pentanol solution was spin-coated on the light emitting layer to form a film with a thickness of 10 nm, and the film was heated at 130° C. for 10 minutes under a nitrogen gas atmosphere, to form an electron transporting layer.
The substrate carrying the electron transporting layer formed thereon was placed in a vapor deposition machine, and the pressure was reduced to 1.0×10−4 Pa or less, then, as a cathode, sodium fluoride was vapor-deposited with a thickness of about 7 nm on the electron transporting layer, then, aluminum was vapor-deposited with a thickness of about 120 nm on the sodium fluoride layer. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D19.
Voltage was applied to the light emitting device D19, to observe EL emission. The external quantum efficiency at 50 cd/m2 was 3.04%, and the CIE chromaticity coordinate (x, y) was (0.29, 0.55).
A light emitting device CD4 was fabricated in the same manner as in Example D19, excepting that a polymer compound HTL-5 was used instead of the polymer compound HTL-4 in Example D19.
Voltage was applied to the light emitting device CD4, to observe EL emission. The external quantum efficiency at 50 cd/m2 was 1.84%, and the CIE chromaticity coordinate (x, y) was (0.28, 0.53).
According to the present invention, a light emitting device excellent in external quantum efficiency is obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-080028 | Apr 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/060679 | 3/30/2015 | WO | 00 |
