Patent Application
20210074922
The present invention relates to a light emitting device.
Light emitting devices such as organic electroluminescent devices and the like can be suitably used for display and lighting applications, and research and development thereof have been conducted. For example, JP-A No. 2012-131995 (Patent Document 1) discloses a light emitting device having a hole transporting layer containing only a polymer compound containing no block (for example, polymer compound CP2) and a light emitting layer containing a phosphorescent compound. Further, JP-A No. 2016-111355 (Patent Document 2) discloses a light emitting device having a hole transporting layer containing a cured product of a polymer compound containing a block (for example, polymer compound P4) and a light emitting layer containing a phosphorescent compound.
However, the above-described light emitting devices were not necessarily sufficient in luminance life.
Then, the present invention has an object of providing a light emitting device excellent in luminance life.
The present invention provides the following [1] to [14].
[1] A light emitting device comprising an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode, wherein
the first organic layer is a layer comprising a phosphorescent compound,
the second organic layer is a layer comprising at least one of a block copolymer comprising an end group, a block that binds to the end group and a block that does not bind to the end group, and a crosslinked product of the block copolymer,
the above-described block that does not bind to the end group comprises at least one constitutional unit selected from the group consisting of a non-crosslinkable constitutional unit represented by the following formula (X) and a non-crosslinkable constitutional unit represented by the following formula (Z), and
at least one of the following formulae (i) to (iii) is satisfied when the total number of the above-described non-crosslinkable constitutional unit represented by the formula (X) and the total number of the above-described non-crosslinkable constitutional unit represented by the formula (Z) in the above-described block that does not bind to the end group are represented by XI and ZI, respectively, and the total number of the above-described non-crosslinkable constitutional unit represented by the formula (X) and the total number of the above-described non-crosslinkable constitutional unit represented by the formula (Z) in the above-described block that binds to the end group are represented by XII and ZII, respectively:
XI>XII (i)
ZI>ZII (ii)
XI+ZI>XII+ZII (iii)
[wherein,
aX1 and aX2 each independently represent an integer of 0 or more and 10 or less.
ArX1 and ArX3 each independently represent an arylene group or a divalent heterocyclic group, and the foregoing groups optionally have a substituent.
ArX2 and ArX4 each independently represent an arylene group, 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, and the foregoing groups optionally have a substituent. When a plurality of ArX2 are present, they may be the same or different. When a plurality of ArX4 are present, they may be the same or different.
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 the foregoing groups optionally have a substituent. When a plurality of RX2 are present, they may be the same or different. When a plurality of RX3 are present, they may be the same or different.]
[Chemical Formula 2]
ArZ (Z)
[wherein, Arz represents 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, and the foregoing groups optionally have a substituent.].
[2] The light emitting device according to [1], wherein the above-described phosphorescent compound is a phosphorescent compound represented by the following formula (1):
[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, and n2 represents an integer of 0 or more. However, 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.
E1 and E2 each independently represent a carbon atom or a nitrogen atom. However, at least one of E1 and E2 is a carbon atom. When a plurality of E1 are present, they may be the same or different. When a plurality of E2 are present, they may be the same or different.
Ring L1 represents an aromatic hetero ring which optionally has a substituent. When a plurality of the substituents are present, they may be combined together to form a ring together with atoms to which they are attached. When a plurality of Rings L1 are present, they may be the same or different.
Ring L2 represents an aromatic hydrocarbon ring or an aromatic hetero ring, and the foregoing rings optionally have a substituent. When a plurality of the substituents are present, they may be combined together to form a ring together with atoms to which they are attached. When a plurality of Rings L2 are present, they may be the same or different.
The substituent which Ring L1 optionally has and the substituent which Ring L2 optionally has may be combined together to form a ring together with atoms to which they are attached.
A1-G1-A2 represents an anionic bidentate ligand. A1 and A2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be ring constituent atoms. G1 represents a single bond or an atomic group constituting a bidentate ligand together with A1 and A2. When a plurality of A1-G1-A2 are present, they may be the same or different.].
[3] The light emitting device according to [2], wherein the above-described phosphorescent compound represented by the formula (1) is a phosphorescent compound represented by the following formula (1-A):
[wherein,
M, n1, n2, E1 and A1-G1-A2 represent the same meaning as described above.
Ring L1A represents a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, a triazole ring or a diazole ring, and the foregoing rings optionally have a substituent. When a plurality of the substituents are present, they may be combined together to form a ring together with carbon atoms to which they are attached. When a plurality of Rings L1A are present, they may be the same or different.
E21A, E22A, E23A and E24A each independently represent a nitrogen atom or a carbon atom. When a plurality of E21A, E22A, E23A and E24A are present, they may be the same or different at each occurrence. When E21A is a nitrogen atom, R21A is absent. When E22A is a nitrogen atom, R22A is absent. When E23A is a nitrogen atom, R23A is absent. When E24A is a nitrogen atom, R24A is absent.
R21A, R22A, R23A and R24A 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 substituted amino group or a halogen atom, and the foregoing groups optionally have a substituent. When a plurality of R21A, R22A, R23A and R24A are present, they may be the same or different at each occurrence. R21A and R22A, R22A and R23A, R23A and R24A, and the substituent which Ring L1A optionally has and R21A may each be combined together to form a ring together with atoms to which they are attached.
Ring L2A represents a benzene ring, a pyridine ring or a diazabenzene ring.].
[4] The light emitting device according to [3], wherein the above-described phosphorescent compound represented by the formula (1-A) is a phosphorescent compound represented by the following formula (1-B1), formula (1-B2), formula (1-B3), formula (1-B4) or formula (1-B5):
[wherein,
M, n1, n2, R21A, R22A, R23A, R24A and A1-G1-A2 represent the same meaning as described above.
n11 and n21 each independently represent 1 or 2. However, n11+n21 is 3 when M is a ruthenium atom, a rhodium atom or an iridium atom, while n11+n21 is 2 when M is a palladium atom or a platinum atom.
R11B, R12B, R13B, R14B, R15B, R16B, R17B and R13B 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 substituted amino group or a halogen atom, and the foregoing groups optionally have a substituent. When a plurality of R11B, R12B, R13B, R14B, R15B, R16B, R17B and R18B are present, they may be the same or different at each occurrence.
In the formula (1-B1), R11B and R12B, R12B and R13B, R13B and R14B, and R11B and R21A may each be combined together to form a ring together with atoms to which they are attached. In the formula (1-B2), R13B and R14B, R13B and R13B, R15B and R16B, R16B and R17B, R17B and R18B, and R18B and R23A may each be combined together to form a ring together with atoms to which they are attached. In the formula (1-B3), R11B and R12B, R12B and R13B, R13B, and R14B, R11B and R21A, R13B and R15B, R15B and R16B, R16B and R17B, R17B and R18B, and R18B and R21A may each be combined together to form a ring together with atoms to which they are attached. In the formula (1-B4), R11B and R18B, R14B and R15B, R15B and R16B, R16B and R17B, R17B and R18B, and R11B and R21A may each be combined together to form a ring together with atoms to which they are attached. In the formula (1-B5), R11B and R12B, R12B and R18B, R15B and R16B, R16B and R17B, R17B and R18B, and R11B and R21A may each be combined together to form a ring together with atoms to which they are attached.].
[5] The light emitting device according to [3], wherein the above-described phosphorescent compound represented by the formula (1-A) is a phosphorescent compound represented by the following formula (1-A1), formula (1-A2), formula (1-A3) or formula (1-A4):
[wherein, M, n1, n2, R21A, R22A, R23A, R24A and A1-G1-A2 represent the same meaning as described above.
R11A, R12A and R13A 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 substituted amino group or a halogen atom, and the foregoing groups optionally have a substituent. When a plurality of R11A, R12A and R13A are present, they may be the same or different at each occurrence.
In the formula (1-A1), R11A and R21A may be combined together to form a ring together with atoms to which they are attached. In the formula (1-A2), R12A and R13A may be combined together to form a ring together with atoms to which they are attached. In the formula (1-A3) and the formula (1-A4), R11A and R12A, R12A and R13A, and R11A and R21A may each be combined together to form a ring together with atoms to which they are attached.].
[6] The light emitting device according to any one of [1] to [5], wherein the above-described block that binds to the end group comprises at least one constitutional unit selected from the group consisting of a non-crosslinkable constitutional unit represented by the following formula (Y), a non-crosslinkable constitutional unit represented by the above-described formula (X), a non-crosslinkable constitutional unit represented by the above-described formula (Z) and a constitutional unit having a crosslinkable group:
[Chemical Formula 8]
ArY1 (Y)
[wherein, ArY1 represents an arylene group which optionally has a substituent.].
[7] The light emitting device according to any one of [1] to [6], wherein the above-described block that binds to the end group does not comprise the above-described non-crosslinkable constitutional unit represented by the formula (X) and the above-described non-crosslinkable constitutional unit represented by the formula (Z).
[8] The light emitting device according to any one of [1] to [7], wherein the above-described block that does not bind to the end group further comprises at least one constitutional unit selected from the group consisting of a non-crosslinkable constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group:
[Chemical Formula 9]
ArY1 (Y)
[wherein, ArY1 represents an arylene group which optionally has a substituent.].
[9] The light emitting device according to any one of [1] to [8], wherein the above-described block copolymer comprises a constitutional unit having a crosslinkable group.
[10] The light emitting device according to any one of [6] to [9], wherein the above-described constitutional unit having a crosslinkable group is at least one selected from the group consisting of a constitutional unit represented by the following formula (2) and a constitutional unit represented by the following formula (2′):
[wherein,
nA represents an integer of 0 or more and 5 or less, and n represents an integer of 1 or more and 5 or less. When a plurality of nA are present, they may be the same or different.
Ar3 represents an aromatic hydrocarbon group or a heterocyclic group, and the foregoing groups 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 the foregoing groups optionally have a substituent. R′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent. When a plurality of LA are present, they may be the same or different.
X represents the above-described crosslinkable group. When a plurality of X are present, they may be the same or different.]
[wherein,
mA represents an integer of 0 or more and 5 or less, m represents an integer of 1 or more and 5 or less, and c represents 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 group and at least one heterocyclic group are bonded directly, and the foregoing groups optionally have a substituent.
Ar4 and Ar6 each independently represent an arylene group or a divalent heterocyclic group, and the foregoing groups optionally have a substituent.
Ar4, Ar5 and Ar6 each may be bonded directly or via an oxygen atom or a sulfur atom, to a group other than that group bonding to a nitrogen atom to which that group is bonded, to form 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 the foregoing groups optionally have a substituent. R″ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent. When a plurality of KA are present, they may be the same or different.
X′ represents the above-described crosslinkable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent. When a plurality of X′ are present, they may be the same or different. However, at least one X′ is the above-described crosslinkable group.].
[11] The light emitting device according to any one of [6] to [10], wherein the above-described crosslinkable group comprises at least one structure selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, oxirane, oxetane, aziridine, azetidine, azide, benzocyclobutene and naphthocyclobutene.
[12] The light emitting device according to any one of [6] to [11], wherein the above-described crosslinkable group includes at least one group selected from the group consisting of crosslinkable groups represented by the formula (XL-1) to the formula (XL-19) in Group A:
(Group A)
[wherein,
nXL represents an integer of 0 or more and 5 or less. A plurality of nXL may be the same or different.
RXL represents a methylene group, an oxygen atom or a sulfur atom. When a plurality of RXL are present, they may be the same or different.
The wavy line indicates that the group having the wavy line is any one of a plurality of geometric isomers or comprises a plurality of geometric isomers.
* 1 represents a binding position.
The crosslinkable group in Group A optionally has a substituent, and when a plurality of the substituents are present, they may be combined together to form a ring together with carbon atoms to which they are attached.].
[13] The light emitting device according to any one of [6] to [12], wherein the above-described crosslinkable group includes at least one group selected from the group consisting of a crosslinkable group represented by the following formula (XL-1), a crosslinkable group represented by the following formula (XL-16), a crosslinkable group represented by the following formula (XL-17), a crosslinkable group represented by the following formula (XL-18) and a crosslinkable group represented by the following formula (XL-19):
[wherein,
*1 represents a binding position.
The crosslinkable group represented by the formula (XL-1), the formula (XL-16), the formula (XL-17), the formula (XL-18) or the formula (XL-19) optionally has a substituent, and when a plurality of the substituents are present, they may be combined together to form a ring together with carbon atoms to which they are attached.].
[14] The light emitting device according to any one of [1] to [13], which satisfies the above-described formula (i).
[15] The light emitting device according to any one of [1] to [14], wherein the above-described first organic layer is a layer further comprising a compound represented by the following formula (H-1), a polymer compound comprising at least one selected from the group consisting of a non-crosslinkable constitutional unit represented by the following formula (Y) and a non-crosslinkable constitutional unit represented by the following formula (Z), or both the compounds:
[wherein,
ArH1 and ArH2 each independently represent an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent.
nH1 and nH2 each independently represent 0 or 1. When a plurality of nH1 are present, they may be the same or different. The plurality of nK2 may be the same or different.
nH3 represents an integer of 0 or more and 10 or less.
LH1 represents an arylene group, a divalent heterocyclic group, or a group represented by —[C(RH11)2]nH11-, and the foregoing groups optionally have a substituent. When a plurality of LH1 are present, they may be the same or different. nH11 represents an integer of 1 or more and 10 or less.
RH11 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 the foregoing groups optionally have a substituent.
A plurality of RHU may be the same or different and may be combined together to form a ring together with carbon atoms to which they are attached.
LH2 represents a group represented by —N(-LH21-RH21)—. When a plurality of LK2 are present, they may be the same or different. LH21 represents a single bond, an arylene group or a divalent heterocyclic group, and the foregoing groups optionally have a substituent. RH21 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent.]
[Chemical Formula 15]
ArY1 (Y)
[wherein, ArY1 represents an arylene group which optionally has a substituent.]
[Chemical Formula 16]
ArZ (Z)
[wherein, ArZ represents a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and the foregoing groups optionally have a substituent.].
[16] The light emitting device according to any one of [1] to [15], wherein the above-described first organic layer further comprises 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 and a light emitting material.
[17] The light emitting device according to any one of [1] to [16], wherein the above-described first organic layer and the above-described second organic layer are adjacent to each other.
[18] The light emitting device according to any one of [1] to [17], wherein the above-described second organic layer is a layer provided between the above-described anode and the above-described first organic layer.
According to the present invention, it is possible to provide a light emitting device excellent in luminance life.
Unless otherwise specified, the terms commonly used in the present specification will be described as follows with specific examples given as needed.
“Me” represents a methyl group, “Et” represents an ethyl group, “i-Pr” represents an isopropyl group, and “t-Bu” represents a tert-butyl group.
The hydrogen atom may be a heavy hydrogen atom or a light hydrogen atom.
In the formula representing a metal complex and a phosphorescent compound, the solid line representing a bond with a metal means a covalent bond or a coordination bond.
The “polymer compound” means a polymer having molecular weight distribution and having a polystyrene-equivalent number-average molecular weight of 1×103 or more and 1×108 or less.
The “low molecular weight compound” means a compound having no molecular weight distribution and having a molecular weight of 1×104 or less.
The “constitutional unit” means a unit occurring once or more times in the molecular chain of the polymer compound. In addition, the constitutional unit occurring twice or more times in the molecular chain of the polymer compound is particularly referred to as a “repeating unit”.
The “block” refers to a block that constitutes a molecular chain of a polymer compound that is a block copolymer, and is a molecular chain portion (block) composed of one or two or more kinds of constitutional units.
The “block copolymer” means a polymer compound containing two or more types of blocks. In the block copolymer, it is preferable that adjacent blocks have different constitutions.
The “adjacent blocks have different constitutions” means, for example, that the constitutional units contained in the blocks adjacent to each other are the same, but their compositions and/or chain distributions are different, and that at least one constitutional unit contained in one of adjacent blocks and at least one constitutional unit contained in the other are different. The adjacent block can be produced by, for example, a method in which one block (hereinafter, also referred to as “first block”) is formed by polymerization, and then, the other block is formed, in the presence of the first block, by polymerization and bonded to the first block, and a method in which adjacent blocks are each independently formed, then, these blocks are combined.
The “crosslinkable group” is a group capable of forming a new bond by being subjected to heating, ultraviolet irradiation, near-ultraviolet irradiation, visible light irradiation, infrared irradiation, radical reaction and the like. The crosslinkable group preferably contains at least one structure selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, oxirane, oxetane, aziridine, azetidine, azide, benzocyclobutene and naphthocyclobutene, as the crosslinkable site, because the polymer compound is excellent in crosslinkability.
The crosslinkable group having the above structure includes the above Group A, namely, crosslinkable groups represented by the formula (XL-1) to the formula (XL-19).
The “non-crosslinkable” constitutional unit denotes that the constitutional unit has no crosslinkable group.
The “alkyl group” may be any one linear or branched. The number of carbon atoms of the linear alkyl group, not including the number of carbon atoms of the substituent, is usually 1 or more and 50 or less, and preferably 1 or more and 20 or less. The number of carbon atoms of the branched alkyl group, not including the number of carbon atoms of the substituent, is usually 3 or more and 50 or less, and preferably 3 or more and 20 or less. 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, a 2-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-propyl-heptyl 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 replacing 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 (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-hexylphenyl)propyl group, and a 6-ethyloxyhexyl group).
The number of carbon atoms of the “cycloalkyl group”, not including the number of carbon atoms of the substituent, is usually 3 or more and 50 or less, and preferably 4 or more and 20 or less. The cycloalkyl group optionally has a substituent, and examples thereof include a cyclohexyl group, a cyclohexylethyl group, and a cyclohexylethyl group.
The “aryl group” means an atomic group remaining after removing from an aromatic hydrocarbon one hydrogen atom bonding directly to a carbon atom constituting the ring. The number of carbon atoms of the aryl group, not including the number of carbon atoms of the substituent, is usually 6 or more and 60 or less, preferably 6 or more and 20 or less, and more preferably 6 or more and 10 or less. 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, and a 4-phenylphenyl group, and groups obtained by replacing 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.
The “alkoxy group” may be any of linear or branched. The number of carbon atoms of the linear alkoxy group, not including the number of carbon atoms of the substituent, is usually 1 or more and 40 or less, and preferably 1 or more and 10 or less. The number of carbon atoms of the branched alkoxy group, not including the number of carbon atoms of the substituent, is usually 3 or more and 40 or less, and preferably 3 or more and 10 or less. 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 replacing 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 the “cycloalkoxy group”, not including the number of carbon atoms of the substituent, is usually 3 or more and 40 or less, and preferably 4 or more and 10 or less. The cycloalkoxy group optionally has a substituent, and examples thereof include a cyclohexyloxy group.
The number of carbon atoms of the “aryloxy group”, not including the number of carbon atoms of the substituent, is usually 6 or more and 60 or less, and preferably 6 or more and 20 or less. 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 and 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.
The “p-valent heterocyclic group” (p represents an integer of 1 or more) means an atomic group remaining after removing from a heterocyclic compound p hydrogen atoms among hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring. Of the p-valent heterocyclic groups, “p-valent aromatic heterocyclic group” as an atomic group remaining after removing from an aromatic heterocyclic compound p hydrogen atoms among hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring is preferable.
The “aromatic heterocyclic compound” includes compounds in which the hetero ring itself shows aromaticity such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole and the like, and compounds in which an aromatic ring is condensed to a hetero ring even if the hetero ring itself shows no aromaticity such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, benzopyran and the like.
The number of carbon atoms of the monovalent heterocyclic group, not including the number of carbon atoms of the substituent, is usually 2 to 60, and 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 piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group and a triazinyl group, and groups obtained by replacing a hydrogen atom in these groups with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or the like.
The “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The “amino group” optionally has a substituent, and a substituted amino group is preferable. The substituent which the 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 substituted amino group includes, more specifically, 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.
The “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 or more and 30 or less, and preferably 3 or more and 20 or less. The number of carbon atoms of the branched alkenyl group, not including the number of carbon atoms of the substituent, is usually 3 or more and 30 or less, and preferably 4 or more and 20 or less.
The number of carbon atoms of the “cycloalkenyl group”, not including the number of carbon atoms of the substituent, is usually 3 or more and 30 or less, and preferably 4 or more and 20 or less.
The alkenyl group and the cycloalkenyl group 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 and a 7-octenyl group, and these groups having a substituent.
The “alkynyl group” may be any of linear or branched. The number of carbon atoms of the linear alkynyl group, not including the carbon atoms of the substituent, is usually 2 or more and 20 or less, and preferably 3 or more and 20 or less. The number of carbon atoms of the branched alkynyl group, not including the carbon atoms of the substituent, is usually 4 or more and 30 or less, and preferably 4 or more and 20 or less.
The number of carbon atoms of the “cycloalkynyl group”, not including the carbon atoms of the substituent, is usually 4 or more and 30 or less, and preferably 4 or more and 20 or less.
The alkynyl group and the cycloalkynyl group 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-hexynyl group and a 5-hexynyl group, and these groups having a substituent.
The “arylene group” means an atomic group remaining after removing from an aromatic hydrocarbon two hydrogen atoms bonding directly to carbon atoms constituting the ring. The number of carbon atoms of the arylene group, not including the number of carbon atoms of the substituent, is usually 6 or more and 60 or less, preferably 6 or more and 30 or less, and more preferably 6 or more and 18 or less. The arylene group optionally has a substituent and examples thereof include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenedilyl group, a dihydrophenanthrenedilyl group, a naphthacenediyl group, a fluorenediyl group, a pyrenediyl group, a perylenediyl group, a chrysenediyl group and a dibenzocycloheptanediyl group, and these groups having a substituent, and groups represented the formula (A-1) to the formula (A-23) described below are preferable. The arylene group may be a group in which a plurality of these groups are bonded.
[wherein, R and Ra each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group. A plurality of R and Ra each may be the same or different, and the plurality of Ra may be combined together to form a ring together with atoms to which they are attached.]
The number of carbon atoms of the divalent heterocyclic group, not including the number of carbon atoms of the substituent, is usually 2 or more and 60 or less, preferably 3 or more and 20 or less, and more preferably 4 or more and 15 or less. 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 bonding directly to carbon atoms or hetero atoms constituting the ring, and groups represented by the formula (AA-1) to the formula (AA-34) described below are preferable. The divalent heterocyclic group may be a group in which a plurality of these groups are bonded.
[wherein, R and Ra represent the same meaning as described above.]
The “substituent” means 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 substituent may be a crosslinkable group.
The constitutional unit represented by the formula (X) is a non-crosslinkable constitutional unit.
The constitutional unit represented by the formula (X) is a constitutional unit which is useful for improving charge transportability (especially, improving hole transportability).
In the above-described formula (X), aX1 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, further preferably 0 or 1, and particularly preferably 1, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
aX2 is preferably an integer of 0 or more and 5 or less, more preferably an integer of 0 or more and 2 or less, and further preferably 0, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
RX1, RX2 and RX3 are each preferably an aryl group or a monovalent heterocyclic group, and more preferably an aryl group, and the foregoing groups optionally have a substituent.
The aryl group represented by RX1, RX2 and RX3 is preferably a group obtained by removing from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a dihydrophenanthrene ring, a naphthacene ring, a fluorene ring, a pyrene ring, a perylene ring or a chrysene ring one hydrogen atom bonding directly to a carbon atom constituting the ring, more preferably a group obtained by removing from a benzene ring, a naphthalene ring, a phenanthrene ring, a dihydrophenanthrene ring or a fluorene ring one hydrogen atom bonding directly to a carbon atom constituting the ring, further preferably a phenyl group or a fluorenyl group, and particularly preferably a phenyl group, and the foregoing groups optionally have a substituent.
The monovalent heterocyclic group represented by RX1, RX2 and RX3 is preferably a group obtained by removing from a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring or a dihydroacridine ring one hydrogen atom bonding directly to a carbon atom or a hetero atom constituting the ring, and more preferably a group obtained by removing from a pyridine ring, a diazabenzene ring, a triazine ring, a carbazole ring, a dibenzofuran ring or dibenzothiophene ring one hydrogen atom bonding directly to a carbon atom or a hetero atom constituting the ring, and the foregoing groups optionally have a substituent.
The arylene group represented by ArX1, ArX2, ArX3 and ArX4 is preferably a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group, a pyrenediyl group, a fluorenediyl group or a dibenzocycloheptanediyl group, more preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group or a fluorenediyl group, and further preferably a phenylene group or a fluorenediyl group, and the foregoing groups optionally have a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The divalent heterocyclic group represented by ArX1, ArX2, ArX3 and ArX4 is preferably a group obtained by removing from a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a phenoxazine ring, a phenothiazine ring or a dihydroacridine ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and more preferably a group obtained by removing from a pyridine ring, a diazabenzene ring, a triazine ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and further preferably, the foregoing groups optionally have a substituent.
The arylene group represented by ArX1 and ArX3 is preferably a group represented by the formula (A-1) to the formula (A-9) or the formula (A-19) to the formula (A-21), more preferably a group represented by the formula (A-1) to the formula (A-3), the formula (A-8) or the formula (A-9), further preferably a group represented by the formula (A-1) to the formula (A-3), and particularly preferably a group represented by the formula (A-1), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The divalent heterocyclic group represented by ArX1 and ArX3 is preferably a group represented by the formula (AA-1) to the formula (AA-15) or the formula (AA-18) to the formula (AA-22), and more preferably a group represented by the formula (AA-1) to the formula (AA-6) or the formula (AA-10) to the formula (AA-15), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
ArXI and ArX3 are each preferably an arylene group optionally having a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The arylene group represented by ArX2 and ArX4 is preferably a group represented by the formula (A-1) to the formula (A-14) or the formula (A-19) to the formula (A-23), more preferably a group represented by the formula (A-1) to the formula (A-10) or the formula (A-19) to the formula (A-21), further preferably a group represented by the formula (A-1) to the formula (A-3), the formula (A-6) to the formula (A-9) or the formula (A-19) to the formula (A-21), particularly preferably a group represented by the formula (A-1) to the formula (A-3), the formula (A-8) or the formula (A-9), and especially preferably a group represented by the formula (A-1) or the formula (A-9), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
Preferable examples of the divalent heterocyclic group represented by ArX2 and ArX4 are the same as the preferable examples of the divalent heterocyclic group represented by ArX1 and ArX3.
Preferable examples 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 represented by ArX2 and ArX4 are the same as the preferable examples of the arylene group and the divalent heterocyclic group represented by ArX2 and ArX4.
The divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by ArX2 and ArX4 includes, for example, groups represented by the following formulae, and the foregoing groups 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 the foregoing groups optionally have a substituent.]
RXX is preferably an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally have a substituent.
ArX2 and ArX4 are each preferably an arylene group optionally having a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have is preferably a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, further preferably an alkyl group, a cycloalkyl group or an aryl group, and particularly preferably an alkyl group, and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by RX1 to RX3, respectively.
In the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, the substituent which the amino group has is preferably an aryl group or a monovalent heterocyclic group, and more preferably an aryl group, and the foregoing groups optionally further have a substituent. Examples and preferable examples of the aryl group as the substituent which the amino group has are the same as the examples and preferable examples of the aryl group represented by RX1, RX2 and RX3. Examples and preferable examples of the monovalent heterocyclic group as the substituent which the amino group has are the same as the examples and preferable examples of the monovalent heterocyclic group represented by RX1 to RX3.
The substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has is preferably a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and further preferably an alkyl group or a cycloalkyl group, and the foregoing groups optionally further have a substituent, but preferably have no substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
The constitutional unit represented by the formula (X) is preferably a constitutional unit represented by the following formula (X-1) to the formula (X-7), and more preferably a constitutional unit represented by the formula (X-1) to the formula (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, a cyano group or a substituted amino group, and the foregoing groups optionally have a substituent. A plurality of RX4 may be the same or different. A plurality of RX5 may be the same or different, and groups RX3 (preferably adjacent groups RX5) may be combined together to form a ring together with carbon atoms to which they are attached.]
RX4 and RX5 are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and further preferably a hydrogen atom or an alkyl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group represented by RX4 and R5 are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the groups represented by RX4 and RX5 optionally have are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
The constitutional unit represented by the formula (X) includes, for example, constitutional units represented by the formula (X1-1) to the formula (X1-19) described below.
The constitutional unit represented by the formula (Z) is a non-crosslinkable constitutional unit.
The number of carbon atoms of the divalent heterocyclic group represented by ArZ, not including the number of carbon atoms of the substituent, is usually 2 or more and 60 or less, preferably 2 or more and 30 or less, and more preferably 3 or more and 15 or less.
The number of hetero atoms of the divalent heterocyclic group represented by ArZ, not including the number of hetero atoms of the substituent, is usually 1 or more and 30 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and further preferably 1 or more and 3 or less.
The divalent heterocyclic group represented by ArZ is preferably a group obtained by removing from a hetero ring containing as the ring constituent atom at least one hetero atom selected from the group consisting of a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom and a selenium atom two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, more preferably a group obtained by removing from a hetero ring containing as the ring constituent atom at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and further preferably a group obtained by removing from a hetero ring containing as the ring constituent atom a nitrogen atom two hydrogen atoms bonded directly to carbon atoms or hetero atoms constituting the ring (hereinafter, also referred to as “divalent nitrogen-containing heterocyclic group”), and the foregoing groups optionally have a substituent.
Regarding the divalent heterocyclic group represented by Arz, the divalent heterocyclic group other than the divalent nitrogen-containing heterocyclic group includes, for example, groups obtained by removing from a borole ring, a furan ring, a silole ring, a phosphole ring, a thiophene ring, a selenophene ring, a benzofuran ring, a benzothiophene ring, dibenzoborole ring, a dibenzofuran ring, a dibenzosilole ring, a dibenzophosphole ring, a dibenzothiophene ring or a dibenzoselenophene ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and is, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention, preferably a group obtained by removing from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring or a dibenzothiophene ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and more preferably a group represented by the formula (AA-12) to the formula (AA-15), and the foregoing groups optionally have a substituent.
Regarding the divalent heterocyclic group represented by ArZ, the divalent nitrogen-containing heterocyclic group is preferably a divalent nitrogen-containing heterocyclic group containing a nitrogen atom having no double bond as the ring constituent atom and not containing a nitrogen atom having a double bond as the ring constituent atom (hereinafter, also referred to as “divalent nitrogen-containing heterocyclic group containing nitrogen atom having no double bond”), and this group optionally has a substituent, from the standpoint of improving charge transportability (especially, improving hole transportability). Further, regarding the divalent nitrogen-containing heterocyclic group represented by ArZ, the divalent nitrogen-containing heterocyclic group is preferably a divalent nitrogen-containing heterocyclic group containing a nitrogen atom having a double bond as the ring constituent atom (hereinafter, also referred to as “divalent nitrogen-containing heterocyclic group containing nitrogen atom having double bond”), and this group optionally has a substituent, from the standpoint of improving charge transportability (especially, improving electron transportability).
The “nitrogen atom having no double bond” means a nitrogen atom having only a single bond between the nitrogen atom and all the atoms bonded to the nitrogen atom.
The phrase “containing a nitrogen atom having no double bond as the ring constituent atom” means that —N(—RN)— (wherein, RN represents a hydrogen atom or a substituent) or a group represented by the following formula is contained in the ring.
The divalent nitrogen-containing heterocyclic group containing a nitrogen atom having no double bond includes, for example, groups obtained by removing from a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, a dihydroacridine ring, a 5,10-dihydrophenazine ring, an acridone ring, a quinacridone ring, a phenoxazine ring, a phenothiazine ring, an indolocarbazole ring or an indenocarbazole ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and is, from the standpoint of improving the luminance life and improving the charge transportability (especially, improving hole transportability) of the light emitting device according to the present invention, preferably a group obtained by removing from a carbazole ring, a dihydroacridine ring, a 5,10-dihydrophenazine ring, a phenoxazine ring, a phenothiazine ring, an indolocarbazole ring or an indenocarbazole ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, more preferably a group obtained by removing from a carbazole ring, a dihydroacridine ring, a 5,10-dihydrophenazine ring, a phenoxazine ring or a phenothiazine ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, further preferably a group obtained by removing from a carbazole ring, a phenoxazine ring or a phenothiazine ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, particularly preferably a group represented by the formula (AA-10), the formula (AA-11) or the formula (AA-18) to the formula (AA-21), and especially preferably a group represented by the formula (AA-18) or the formula (AA-19).
The “nitrogen atom having a double bond” means a nitrogen atom having a double bond between the nitrogen atom and the atom bonded to the nitrogen atom.
The phrase “containing a nitrogen atom having a double bond as the ring constituent atom” means that a group represented by —N═ is contained in the ring.
The divalent nitrogen-containing heterocyclic group containing a nitrogen atom having a double bond includes, for example, groups obtained by removing from a diazole ring, a triazole ring, an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a benzodiazole ring, a benzotriazole ring, a benzooxadiazole ring, a benzothiadiazole ring, an azacarbazole ring, a diazacarbazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, a triazanaphthalene ring, an azaanthracene ring, a diazaanthracene ring, a triazaanthracene ring, an azaphenanthrene ring, a diazaphenanthrene ring or a triazaphenanthrene ring two hydrogen atoms bonding directly to carbon atoms or hetero atoms constituting the ring, and is, from the standpoint of improving the luminance life and improving the charge transportability (especially, improving electron transportability) of the light emitting device according to the present invention, preferably a group obtained by removing from a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring, a diazanaphthalene ring, an azaanthracene ring, a diazaanthracene ring, an azaphenanthrene ring or a diazaphenanthrene ring two hydrogen atoms bonding directly to carbon atoms constituting the ring, more preferably a group obtained by removing from a pyridine ring, a diazabenzene ring or triazine ring two hydrogen atoms bonding directly to carbon atoms constituting the ring, further preferably a group represented by the formula (AA-1) to the formula (AA-4), and particularly preferably a group represented by the formula (AA-4), and the foregoing groups optionally have a substituent.
Examples and preferable examples of the arylene group in the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by ArZ are the same as the examples and preferable examples of the arylene group represented by ArX1 and ArX3.
Examples and preferable examples of 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 represented by ArZ are the same as the examples and preferable examples of the divalent heterocyclic group represented by ArZ.
Examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by ArZ include, for example, examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by ArX2 and ArX4.
The substituent which the group represented by ArZ optionally has is preferably a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and further preferably an alkyl group or an aryl group, and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the group represented by ArZ optionally has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the substituent which the group represented by ArZ optionally has optionally further has are the same as the examples and preferable examples of the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has.
The constitutional unit represented by the formula (Z) is preferably a constitutional unit represented by the formula (Z-1) to the formula (Z-4), more preferably a constitutional unit represented by the formula (Z-1) or the formula (Z-3), and further preferably a constitutional unit represented by the formula (Z-1), from the standpoint of improving the luminance life and improving the charge transportability (especially, improving electron transportability) of the light emitting device according to the present invention.
Further, the constitutional unit represented by the formula (Z) is preferably a constitutional unit represented
by the formula (Z-5) to the formula (Z-1), and more preferably a constitutional unit represented by the formula (Z-5), from the standpoint of improving the luminance life and improving the charge transportability (especially, improving hole transportability) of the light emitting device according to the present invention.
[wherein, RY1 and RY3 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, and the foregoing groups optionally have a substituent. A plurality of RV1 may be the same or different and may be combined together to form a ring together with carbon atoms to which they are attached.]
RY1 is 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, a cycloalkyl group or an aryl group, and further preferably a hydrogen atom or an alkyl group, and the foregoing groups optionally have a substituent.
RY3 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, and further preferably an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the group represented by RY1 and RY3 are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which RY1 and RY3 optionally have are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
The constitutional unit represented by the formula (Z-1) is preferably a constitutional unit represented by the formula (Z-1′). Further, the constitutional unit represented by the formula (Z-3) is preferably a constitutional unit represented by the formula (Z-3′).
[wherein, RY1 and RY3 represent the same meaning as described above.]
[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 the foregoing groups optionally have a substituent.]
RY4 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, and further preferably an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group as the group represented by RY4 are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which RY4 optionally has are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
The constitutional unit represented by the formula (Z) includes, for example, constitutional units composed of a divalent heterocyclic group represented by the formula (Z-201) to the formula (Z-215), and constitutional units composed of a divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by the formula (Z-301) to the formula (Z-310).
ZA represents a group represented by —O— or a group represented by —S—. When a plurality of ZA are present, they may be the same or different.
ZB represents a group represented by —CH═ or a group represented by —N═. When a plurality of Z3 are present, they may be the same or different.]
ZA is preferably a group represented by —O—. ZB is preferably a group represented by —N═.
The block copolymer contained in the second organic layer according to the present invention (hereinafter, also referred to as “block copolymer according to the present invention”) can contain a crosslinkable group.
When the block copolymer according to the present invention contains a crosslinkable group, the crosslinkable group is preferably a crosslinkable group represented by the formula (XL-1) to the formula (XL-4), the formula (XL-7) to the formula (XL-10) or the formula (XL-14) to the formula (XL-19), more preferably a crosslinkable group represented by the formula (XL-1), the formula (XL-3), the formula (XL-9), the formula (XL-10) or the formula (XL-16) to the formula (XL-19), further preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-16) to the formula (XL-19), particularly preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-17), and especially preferably a crosslinkable group represented by the formula (XL-17), because the block copolymer according to the present invention is excellent in crosslinkability.
In the block copolymer according to the present invention, the crosslinkable group may be contained only singly or in combination of two or more.
Examples and preferable examples of the substituent which crosslinkable groups in the above Group A optionally have are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
When the block copolymer according to the present invention contains a crosslinkable group, the block copolymer according to the present invention preferably contains a crosslinkable group as a constitutional unit having a crosslinkable group, and more preferably contains a constitutional unit having at least one crosslinkable group selected from the group consisting of a constitutional unit represented by the above-described formula (2) and a constitutional unit represented by the above-described formula (2′).
That is, the constitutional unit having a crosslinkable group is preferably a constitutional unit represented by the formula (2) or a constitutional unit represented by the above-described formula (2′). As a result, the block copolymer according to the present invention tends to have excellent crosslinkability.
From the standpoint of improving the luminance life of the light emitting device according to the present invention, nA is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and further preferably 0 or 1.
From the standpoint of improving the luminance life of the light emitting device according to the present invention, n is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and further preferably 2.
In the above-described formula (2), Ar3 represents an aromatic hydrocarbon group or a heterocyclic group, and the foregoing groups optionally have a substituent. Ar3 is preferably an aromatic hydrocarbon group which optionally has a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The number of carbon atoms of the aromatic hydrocarbon group represented by Ar3, not including the number of carbon atoms of the substituent, is usually 6 or more and 60 or less, preferably 6 or more and 30 or less, and more preferably 6 or more and 18 or less.
Examples and preferable range of the arylene group portion obtained by removing n substituents from the aromatic hydrocarbon group represented by Ar3 are the same as the examples and preferable examples of the group represented by ArY1.
The arylene group portion obtained by removing n substituents from 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 the foregoing groups optionally have a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The number of carbon atoms of the heterocyclic group represented by Ar3, not including the number of carbon atoms of the substituent, is usually 2 or more and 60 or less, preferably 3 or more and 30 or less, and more preferably 4 or more and 18 or less.
Examples and preferable range of the divalent heterocyclic group portion obtained by removing n substituents from the heterocyclic group represented by Ar3 are the same as the examples and preferable examples of the group represented by Ar2.
The divalent heterocyclic group portion obtained by removing n substituents from the heterocyclic group represented by Ar3 is preferably a group represented by the formula (AA-1) to the formula (AA-34), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The substituent which the aromatic hydrocarbon group and the heterocyclic group represented by Ar3 optionally have is preferably 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, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and further preferably an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the group represented by Ar3 optionally has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the substituent which the group represented by Ar3 optionally has optionally further has are the same as the examples and preferable examples of the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has.
The number of carbon atoms of the alkylene group represented by LA, not including the number of carbon atoms of the substituent, is usually 1 or more and 20 or less, preferably 1 or more and 15 or less, and more preferably 1 or more and 10 or less. The number of carbon atoms of the cycloalkylene group represented by LA, not including the number of carbon atoms of the substituent, is usually 3 or more and 20 or less.
The alkylene group and the cycloalkylene group optionally have a substituent. The alkylene group and the cycloalkylene group include, 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 optionally have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom or a cyano group, and the foregoing groups optionally further have a substituent.
The arylene group represented by LA optionally has a substituent. Examples and preferable examples of the arylene group represented by LA are the same as the examples and preferable examples of the group represented by ArY1, and it is preferably a phenylene group or a fluorenediyl group, more preferably a m-phenylene group, a p-phenylene, a fluorene-2,7-diyl group or a fluorene-9,9-diyl group, and the foregoing groups optionally have a substituent.
The substituent which the arylene group represented by LA optionally has is preferably 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 or a crosslinkable group (preferably a crosslinkable group selected from the above Group A), and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the divalent heterocyclic group represented by LA are the same as the examples and preferable examples of the group represented by ArZ.
The divalent heterocyclic group represented by LA is preferably a group represented by the formula (AA-1) to the formula (AA-34).
LA is preferably an arylene group or an alkylene group, more preferably a phenylene group, a fluorenediyl group or an alkylene group, and further preferably an alkylene group, and the foregoing groups optionally have a substituent, from the standpoint of easy production of the block copolymer according to the present invention.
Examples and preferable examples of the substituent which the group represented by LA optionally has are the same as the examples and preferable examples of the substituent which the group represented by Ar3 optionally has.
R′ is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the substituent which the group represented by R′ optionally has are the same as the examples and preferable examples of the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has.
In the above-described formula (2), X is preferably a crosslinkable group selected from the above Group A. When a plurality of X are present, they may be the same or different.
The crosslinkable group represented by X is preferably a crosslinkable group represented by the formula (XL-1) to the formula (XL-4), the formula (XL-7) to the formula (XL-10), or the formulae (XL-14) to (XL-19), more preferably a crosslinkable group represented by the formula (XL-1), the formula (XL-3), the formula (XL-9), the formula (XL-10), or the formula (XL-16) to the formula (XL-19), further preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-16) to the formula (XL-19), particularly preferably a crosslinkable group represented by the formula (XL-1) or the formula (XL-17), and especially preferably a crosslinkable group represented by the formula (XL-17), because the block copolymer is excellent in crosslinkability.
mA is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, further preferably 0 or 1, and particularly preferably 0, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
m is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and further preferably 2, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
c is preferably 0, from the standpoint of easy production of the block copolymer according to the present invention and from the standpoint of improving the luminance life of the light emitting device according to the present invention.
Ar5 is preferably an aromatic hydrocarbon group optionally having a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The definition and examples of the arylene group portion obtained by removing m substituents from the aromatic hydrocarbon group represented by Ar5 are the same as the definition and examples of the arylene group represented by ArX2 in the above-described formula (X).
The definition and examples of the divalent heterocyclic group portion obtained by removing m substituents from the heterocyclic group represented by Ar5 are the same as the definition and examples of the divalent heterocyclic group portion represented by ArX2 in the above-described formula (X).
The definition and examples of the divalent group obtained by removing m substituents from the group in which at least one aromatic hydrocarbon ring and at least one hetero ring are directly bonded represented by Ar5 are the same as the definition and examples of the divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly represented by ArX2.
Ar4 and Ar6 are preferably arylene groups optionally having a substituent, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The definition and examples of the arylene group represented by Ar4 and Ar6 are the same as the definition and examples of the arylene group represented by ArX1 and ArX3 in the above-described formula (X).
The definition and examples of the divalent heterocyclic group represented by Ar4 and Ar6 are the same as the definition and examples of the divalent heterocyclic group represented by ArX1 and ArX3 in the above-described formula (X).
The substituent which Ar4, Ar5 and Ar6 optionally have is preferably 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, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, further preferably an alkyl group, a cycloalkyl group or an aryl group, and particularly preferably an alkyl group, and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by Ar4 to Ar6 optionally have are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
Examples and preferable examples of the substituent which the substituent which the groups represented by Ar4 to Ar6 optionally have optionally further has are the same as the examples and preferable examples of the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has.
Definition and examples of the alkylene group, the cycloalkylene group, the arylene group and the divalent heterocyclic group represented by KA are the same as the definition and examples of the alkylene group, the cycloalkylene group, the arylene group and the divalent heterocyclic group represented by LA in the above-described formula (2).
Examples and preferable examples of KA are the same as the examples and preferable examples of LA, and KA is preferably a phenylene group or a methylene group, and the foregoing groups optionally have a substituent, from the standpoint of easy production of the block copolymer according to the present invention.
Examples and preferable examples of the substituent which the group represented by KA optionally has are the same as the examples and preferable examples of the substituent which the group represented by LA optionally has.
Examples and preferable examples of R″ are the same as the examples and preferable examples of R′.
X′ is preferably a crosslinkable group, an aryl group or a monovalent heterocyclic group, more preferably a crosslinkable group or an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by X′ are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the group represented by X′ optionally has are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
In the above-described formula (2′), at least one X′ is a crosslinkable group, preferably a crosslinkable group selected from the above Group A.
The definition and examples of the crosslinkable group represented by X′ are the same as the definition and examples of the crosslinkable group represented by X in the above-described formula (2).
The constitutional unit represented by the formula (2) includes, for example, constitutional units represented by the following 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 following formula (2′-1) to the formula (2′-9). Of them, the constitutional unit having a crosslinkable group is preferably a constitutional unit represented by the formula (2-1) to the formula (2-30), more preferably a constitutional unit 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), and further preferably a constitutional unit represented by the formula (2-1) to the formula (2-9) or the formula (2-30), from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
When the block copolymer according to the present invention contains a crosslinkable group, the block copolymer according to the present invention may contain a crosslinkable group by containing a constitutional unit other than the above-described constitutional unit represented by the formula (2) and the above-described constitutional unit represented by the formula (2′).
That is, the constitutional unit having a crosslinkable group may be a constitutional unit having a crosslinkable group other than the constitutional unit represented by the formula (2) and the constitutional unit represented by the formula (2′). The constitutional unit having a crosslinkable group other than the constitutional unit represented by the formula (2) and the constitutional unit represented by the formula (2′) includes, for example, constitutional units represented by the following formulae.
The constitutional unit represented by the formula (Y) is a non-crosslinkable constitutional unit.
The group represented by ArY1 is preferably a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrendiyl group, a dihydrophenanthrenediyl group, a pyrenediyl group, a fluorenediyl group or a dibenzocycloheptanediyl group, more preferably a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a dihydrophenanthrenediyl group or a fluorenediyl group, and further preferably a phenylene group, an anthracenediyl group or a fluorenediyl group, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device.
The substituent which the group represented by ArY1 optionally has is preferably a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, further preferably an alkyl group, a cycloalkyl group or an aryl group, and particularly preferably an alkyl group or an aryl group, and the foregoing group optionally further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the group represented by ArY1 optionally has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the substituent which the group represented by ArY1 optionally has optionally further has are the same as the examples and preferable examples of the substituent which the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have optionally further has.
From the standpoint of improving the luminance life of the light emitting device according to the present invention, the constitutional unit represented by the formula (Y) includes preferably, for example, constitutional units represented by the following formulae (Y-1) to (Y-4), and is more preferably a constitutional unit represented by the formula (Y-1), the formula (Y-2) or the formula (Y-4), and further preferably a constitutional unit represented by the formula (Y-2).
[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, a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, and the foregoing groups optionally have a substituent. A plurality of RY2 may be the same or different, and groups RY2 may be combined together to form a ring together with carbon atoms to which they are attached.]
RY2 is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and more preferably an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the group represented by RY2 are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which the substituent which RY2 optionally has optionally further has are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
The combination of two groups RY2 in the group represented by —C(RY2)2— as XY1 is preferably a combination in which both represent an alkyl group or a cycloalkyl group, both represent an aryl group, both represent a monovalent heterocyclic group, or one represents an alkyl group or a cycloalkyl group and the other represents an aryl group or a monovalent heterocyclic group, more preferably a combination in which both represent an alkyl group or a cycloalkyl group, both represent an aryl group, or one represents an alkyl group or a cycloalkyl group and the other represents an aryl group, and further preferably a combination in which one represents an alkyl group or a cycloalkyl group and the other represents an aryl group, and the foregoing groups optionally have a substituent.
Two groups RY2 may be combined together to form a ring together with atoms to which they are attached, and when RY2 forms a ring, the group represented by —C(RY2)2— is preferably a group represented by the formula (Y-A1) to the formula (Y-A5), and more preferably a group represented by the formula (Y-A4), and the foregoing groups optionally have a substituent.
The combination of two groups RY2 in the group represented by —C(RY2)═C(RY2)— as XY1 is preferably a combination in which both represent an alkyl group or a cycloalkyl group, or one represents an alkyl group or a cycloalkyl group and the other represents an aryl group, and the foregoing groups optionally have a substituent.
Four groups RY2 in the group represented by —C(RY2)2—C(RY2)2— as XY1 represent preferably an alkyl group optionally having a substituent or a cycloalkyl group optionally having a substituent.
A plurality of RY2 may be combined together to form a ring together with atoms to which they are attached, and when RY2 forms a ring, the group represented by —C(RY2)2—C(RY2)2— is preferably a group represented by the following formula (Y-B1) to formula (Y-B5), and more preferably a group represented by the formula (Y-B3), and the foregoing groups optionally have a substituent.
[wherein, RY2 represents the same meaning as described above.]
XY1 is preferably a group represented by —C(RY2)2—. The constitutional unit represented by the formula (Y-1) is preferably a constitutional unit represented by the following formula (Y-1′). The constitutional unit represented by the formula (Y-2) is preferably a constitutional unit represented by the following formula (Y-2′). The constitutional unit represented by the formula (Y-3) is preferably a constitutional unit represented by the following formula (Y-3*). The constitutional unit represented by the formula (Y-4) is preferably a constitutional unit represented by the following formula (Y-4′).
[wherein,
RY1 and XY1 represent the same meaning as described above.
RY11 represents a fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group or a substituted amino group, and the foregoing groups optionally have a substituent. A plurality of RY11 may be the same or different.]
Rm 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 further preferably an alkyl group or a cycloalkyl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the group represented by RY11 are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have, respectively.
Examples and preferable examples of the substituent which RY11 optionally has are the same as the examples and preferable examples of the substituent which the groups represented by ArX1 to ArX4 and RX1 to RX3 optionally have.
The constitutional unit represented by the formula (Y) includes, for example, constitutional units represented by the formula (Y-11) to the formula (Y-49).
The phosphorescent compound contained in the first organic layer in the light emitting device according to the present invention will be described.
The phosphorescent compound usually means a compound exhibiting a phosphorescent property at room temperature (25° C.), and is preferably a metal complex which emits light from the triplet excited state at room temperature. This metal complex which emits light from the triplet excited state has a central metal atom and a ligand.
The central metal atom includes, for example, a metal atom having an atomic number of 40 or more, which has spin-orbit interaction in the complex and can cause intersystem crossing between the singlet state and the triplet state. The metal atom includes, for example, a ruthenium atom, a rhodium atom, a palladium atom, an iridium atom and a platinum atom, and from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention, is preferably an iridium atom or a platinum atom
The ligand includes, for example, a neutral or anionic monodentate ligand or a neutral or anionic polydentate ligand, which forms at least one bond selected from the group consisting of a coordination bond and a covalent bond, between the central metal atom. The bond between the central metal atom and the ligand includes, for example, a metal-nitrogen bond, a metal-carbon bond, a metal-oxygen bond, a metal-phosphorus bond, a metal-sulfur bond and a metal-halogen bond. The polydentate ligand usually means a bidentate or more and 6-dentate or less ligand.
The phosphorescent compound is preferably a phosphorescent compound represented by the above-described formula (1) from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
M is preferably an iridium atom or a platinum atom, and more preferably an iridium atom from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
When M is a ruthenium atom, a rhodium atom or an iridium atom, n1 is preferably 2 or 3, and more preferably 3.
When M is a palladium atom or a platinum atom, n1 is preferably 2.
(Ring L1 and Ring L2)
E1 contained in Ring L1 and E2 contained in Ring L2 are preferably carbon atoms.
The number of carbon atoms of the aromatic hetero ring represented by Ring L1, not including the number of carbon atoms of the substituent, is usually 2 or more and 60 or less, preferably 3 or more and 30 or less, and more preferably 4 or more and 15 or less. Ring L1 is preferably a 5-membered aromatic hetero ring or a 6-membered aromatic hetero ring, and more preferably a 5-membered aromatic hetero ring having 2 or more and 4 or less nitrogen atoms as the constituent atom or a 6-membered aromatic hetero ring having 1 or more and 4 or less nitrogen atoms as the constituent atom, and the foregoing rings optionally have a substituent. However, when Ring L1 is a 6-membered aromatic hetero ring, E1 is preferably a carbon atom.
Ring L1 includes, for example, a diazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a diazabenzene ring, a triazine ring, an azanaphthalene ring and a diazanaphthalene ring, and is preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, a triazole ring or a diazole ring, more preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring or a diazole ring, further preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring or a diazanaphthalene ring, and particularly preferably a pyridine ring, a quinoline ring or an isoquinoline ring, and the foregoing rings optionally have a substituent.
The number of carbon atoms of the aromatic hydrocarbon ring represented by Ring L2, not including the number of carbon atoms of the substituent, is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.
The aromatic hydrocarbon ring represented by Ring L2 includes, for example, a benzene ring, a naphthalene ring, an indene ring, a fluorene ring, a phenanthrene ring, a dihydrophenanthrene ring, and a ring in which two or more and five or less of these rings are condensed, and is preferably a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring or a dihydrophenanthrene ring, more preferably a benzene ring, a fluorene ring or a dihydrophenanthrene ring, and further preferably a benzene ring, and the foregoing rings optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
The number of carbon atoms of the aromatic hetero ring represented by Ring L2, not including the number of carbon atoms of the substituent, is usually 2 to 60, preferably 3 to 30, and more preferably 4 to 15.
The aromatic hetero ring represented by Ring L2 includes, for example, a pyrrole ring, a diazole ring, a furan ring, a thiophene ring, a pyridine ring, a diazabenzene ring, and a ring in which one or more and five or less aromatic rings are condensed with these rings, and is preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring, an indole ring, a benzofuran ring, a benzothiophene ring, a carbazole ring, an azacarbazole ring, a diazacarbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, and further preferably a pyridine ring or a diazabenzene ring, and the foregoing rings optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device. When Ring L2 is a 6-membered aromatic hetero ring, E2 is preferably a carbon atom.
Ring L2 is preferably a benzene ring, a fluorene ring, a dihydrophenanthrene ring, a pyridine ring, a diazabenzene ring, a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, more preferably a benzene ring, a pyridine ring or a diazabenzene ring, and further preferably a benzene ring, and the foregoing rings optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
The substituent which Ring L1 and Ring L2 optionally have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, more preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, further preferably an alkyl group, an aryl group or a monovalent hetero group, and particularly preferably an aryl group, and the foregoing groups optionally further have a substituent.
In the phosphorescent compound represented by the formula (1), at least one of Ring L1 and Ring L2 preferably has a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
The aryl group as the substituent which Ring L1 and Ring L2 optionally have is preferably a phenyl group, a naphthyl group, a phenanthrenyl group, a dihydrophenanthrenyl group or a fluorenyl group, more preferably a phenyl group or a fluorenyl group, and further preferably a phenyl group, and the foregoing groups optionally have a substituent.
The monovalent heterocyclic group as the substituent which Ring L1 and Ring L2 optionally have is preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an azacarbazolyl group, a diazacarbazolyl group, a phenoxazinyl group or a phenothiazinyl group, more preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothienyl group or a carbazolyl group, and further preferably a pyridyl group, a pyrimidinyl group or a triazinyl group, and the foregoing groups optionally have a substituent.
The substituent which the amino group has in the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have is preferably an aryl group or a monovalent heterocyclic group, and more preferably an aryl group, and the foregoing groups optionally further have a substituent. The examples and preferable examples of the aryl group as the substituent which the amino group has are the same as the examples and the preferable examples of the aryl group as the substituent which Ring L1 and Ring L2 optionally have. Examples and preferable examples of the monovalent heterocyclic group as the substituent which the amino group has are the same as the examples and preferable examples of the monovalent heterocyclic group as the substituent which Ring L1 and Ring L2 optionally have.
The substituent which the substituent which Ring L1 and Ring L2 optionally have optionally further has is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and further preferably an alkyl group, and the foregoing groups optionally further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the substituent which Ring L1 and Ring L2 optionally have optionally further has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which L1 and Ring L2 optionally have.
The aryl group, the monovalent heterocyclic group or the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have is preferably a group represented by the formula (D-A), the formula (D-B) or the formula (D-C), more preferably a group represented by the formula (D-A) or the formula (D-B), and further preferably a group represented by the formula (D-A), from the standpoint of advantage for an improvement in the luminance life of the light emitting device.
[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 the foregoing groups optionally have a substituent.
ArDA1, ArDA2 and ArDA3 each independently represent an arylene group or a divalent heterocyclic group, and the foregoing groups 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 the foregoing groups 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 the foregoing groups optionally have a substituent. The plurality of GDAs 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 the foregoing groups 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 the foregoing groups optionally have a substituent. The plurality of TDA may be the same or different.]
[wherein,
mDA1 represents an integer of 0 or more.
ArDA1 represents an arylene group or a divalent heterocyclic group, and the foregoing groups optionally have a substituent. When a plurality of ArDA1 are present, they may be the same or different.
TDA represents an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent.]
mDA1, mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 are usually integers of 10 or less, preferably 5 or less, more preferably 2 or less, and further preferably 0 or 1. mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 are preferably the same integers, and mDA1, mDA2, mDA3, mDA4, mDA5, mDA6 and mDA7 are more preferably the same integer.
GDA is preferably an aromatic hydrocarbon group or a heterocyclic group, more preferably a group obtained by removing from a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring or a carbazole ring three hydrogen atoms bonding directly to carbon atoms or nitrogen atoms constituting the ring, and the foregoing groups optionally have a substituent.
The substituent which GCA optionally has is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen, more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, further preferably an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy, and particularly preferably an alkyl group or a cycloalkyl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which GDA optionally has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
The substituent which the substituent which GDA optionally has further has preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably an alkyl group or a cycloalkyl group, and the foregoing groups optionally further have a substituent, but it is preferable that they do not further have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which the substituent which GDA optionally has optionally further has are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which Ring L1 and Ring L2, optionally have, respectively.
GDA is preferably a group represented by the following formula (GDA-11) to formula (GDA-15), more preferably a group represented by the following formula (GDA-11) to formula (GDA-14), further preferably a group represented by the following formula (GDA-11) or formula (GDA-14), particularly preferably a group represented by the following formula (GDA-11).
[wherein,
* represents a bond with 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 bond with 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 bond with 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 the foregoing groups optionally further 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 a cycloalkyl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by RDA are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which RDA optionally has are the same as the examples and preferable examples of the substituent which the substituent which GDA optionally has optionally further has.
ArDA1, ArDA2, ArDA3, ArDA4, ArDA5, ArDA6 and ArDA7 are each preferably a phenylene group, a fluorenediyl group or a carbazolediyl group, more preferably a group represented by the following formula (ArDA-1) to formula (ArDA-5), further preferably a group represented by the following formula (ArDA-1) to formula (ArDA-3), and particularly preferably a group represented by the following formula (ArDA-2), and the foregoing groups optionally have a substituent.
[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 the foregoing groups 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, and further preferably an aryl group, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by RDB are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which RDB optionally has are the same as the examples and preferable examples of the substituent which the substituent which GDA optionally has optionally further has.
Examples and preferable examples of the substituent which ArDA1, ArDA2, ArDA3, ArDA4, ArDA5, ArDA6 and ArDA7 optionally have are the same as the examples and preferable examples of the substituent which optionally has.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by TDA are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which TDA optionally has are the same as the examples and the preferable examples of the substituent which GDA optionally has.
TDA is preferably a group represented by the following formula (TDA-1) to formula (TDA-3), and more preferably a group represented by the following formula (TDA-1).
[wherein, RDA and RDB represent the same meaning as described above.]
The group represented by the formula (D-A) is preferably a group represented by the following formula (D-A1) to formula (D-A5), more preferably a group represented by the following formula (D-A1) or the formula (D-A3) to the formula (D-A5), and further preferably a group represented by the following formula (D-A1).
[wherein,
Rp1, Rp2, Rp3 and Rp4 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When a plurality of Rp1, Rp2 and Rp4 are present, they may be the same or different at each occurrence.
np1 represents an integer of 0 or more and 5 or less, np2 represents an integer of 0 or more and 3 or less, np3 represents 0 or 1, and np4 represents an integer of 0 or more and 4 or less. A plurality of np1 may be the same or different.]
The group represented by the formula (D-B) is preferably a group represented by the following formula (D-B1) to formula (D-B3), more preferably a group represented by the following formula (D-B1).
[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 or more and 5 or less, np2 represents an integer of 0 or more and 3 or less, 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.]
The group represented by the formula (D-C) is preferably a group represented by the following formula (D-C1) to formula (D-C4), more preferably a group represented by the following formula (D-C1) to formula (D-C3), and further preferably a group represented by the formula (D-C1).
[wherein,
Rp4, Rp5 and Rp6 each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom. When a plurality of Rp4, Rp5 and Rp6 are present, they may be the same or different at each occurrence.
np4 represents an integer of 0 or more and 4 or less, np5 represents an integer of 0 or more and 5 or less, and np6 represents an integer of 0 or more and 5 or less.]
np1 is preferably an integer of 0 or more and 2 or less, and more preferably 1. np2 is preferably 0 or 1, and more preferably 0. np3 is preferably 0.
np4 is preferably an integer of 0 or more and 2 or less, and more preferably 0. np5 is preferably an integer of 0 or more and 3 or less, and more preferably 0 or 1. np6 is preferably an integer of 0 or more and 2 or less, and more preferably 0 or 1.
The alkyl group or the cycloalkyl group represented by Rp1, Rp2, Rp3, Rp4, Rp5, and Rp6 is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a cyclohexyl group or a tert-octyl group.
The alkoxy group or cycloalkoxy group represented by Rp1, Rp2, Rp3, Rp4, Rp5 and Rp6 is preferably a methoxy group, a 2-ethylhexyloxy group or a cyclohexyloxy group.
Rp1, Rp2, Rp3, Rp4, Rp5 and Rp6 are each preferably an alkyl group which optionally has a substituent or a cycloalkyl group which optionally has a substituent, more preferably an alkyl group which optionally has a substituent, and further preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group or a tert-octyl group.
When a plurality of substituents which Ring L1 optionally has are present, it is preferable that they are not combined together to form a ring together with atoms to which they are attached. When a plurality of substituents which Ring L2 optionally has are present, it is preferable that they are not combined together to form a ring together with atoms to which they are attached. It is preferable that the substituent which Ring L1 optionally has and the substituent which Ring L2 optionally has are not combined together to form a ring together with atoms to which they are attached.
The anionic bidentate ligand represented by A1-G1-A2 in the formula (1) includes, for example, ligands represented by the following formulae. However, the anionic bidentate ligand represented by A1-G1-A2 is different from the ligand whose number is defined by the subscript n1.
[wherein, * represents a site binding to M.]
The phosphorescent compound represented by the formula (1) is preferably a phosphorescent compound represented by the above-described formula (1-A), from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
Ring L1A is preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring, a diazanaphthalene ring or a diazole ring, more preferably a pyridine ring, a diazabenzene ring, an azanaphthalene ring or a diazanaphthalene ring, and further preferably a pyridine ring, a quinoline ring or an isoquinoline ring, and the foregoing rings optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
Examples and preferable examples of the substituent which the Ring L1A optionally has are the same as the examples and preferable examples of the substituent which Ring L1 and Ring L2 optionally have.
When a plurality of substituents which Ring L1A optionally has are present, it is preferable that they are not combined together to form a ring together with atoms to which they are attached.
When Ring L2A is a pyridine ring, preferable is a pyridine ring in which E21A is a nitrogen atom, a pyridine ring in which E22A is a nitrogen atom or a pyridine ring in which E23A is a nitrogen atom, and more preferable is a pyridine ring in which E22A is a nitrogen atom.
When Ring L2A is a diazabenzene ring, preferable is a pyrimidine ring in which E21A and E23A are nitrogen atoms or a pyrimidine ring in which E22A and E24A are nitrogen atoms, and more preferable is a pyrimidine ring in which E22A and E24A are nitrogen atoms.
Ring L2A is preferably a benzene ring.
E21A, E22A, E23A and E24A are preferably carbon atoms.
R21A, R22A, R23A, and R24A are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an aryl group, a monovalent heterocyclic group or a substituted amino group, and further preferably a hydrogen atom or an aryl group, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device.
R21A, R23A and R24A are particularly preferably hydrogen atoms.
In the phosphorescent compound represented by the formula (1-A), it is preferable that at least one Ring L1A has a substituent or at least one of R21A, R22A, R23A and R24A is an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group represented by R21A, R22A, R23A and R24A are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which R21A, R22A, R23A and R24A optionally have are the same as the examples and preferable examples of the substituent which the substituent which Ring L1 and Ring L2 optionally have optionally further has.
It is preferable that R21A and R22A, R22A and R23A, R23A and R24A, and the substituent which Ring L1A optionally has and R21A each are not combined together to form a ring together with atoms to which they are attached.
The phosphorescent compound represented by the formula (1-A) is preferably a phosphorescent compound represented by the above-described formula (1-A1) to formula (1-A4) (preferably a phosphorescent compound represented by the above-described formula (1-A1) or formula (1-A3), and more preferably a phosphorescent compound represented by the above-described formula (1-A1)) or a phosphorescent compound represented by the above-described formula (1-B1) to formula (1-B5) (preferably a phosphorescent compound represented by the above-described formula (1-B1) to formula (1-B3), more preferably a phosphorescent compound represented by the above-described formula (1-B1) to formula (1-B5), further preferably a phosphorescent compound represented by the above-described formula (1-B1) to formula (1-B3), and particularly preferably a phosphorescent compound represented by the above-described formula (1-B1), from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
In the formula (1-A1) and the formula (1-A3), R11A 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, and further preferably an aryl group, and the foregoing groups optionally have a substituent.
In the formula (1-A3), R12A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an alkyl group or an aryl group, and further preferably a hydrogen atom, and the foregoing groups optionally have a substituent.
In the formula (1-A2) and the formula (1-A4), R12A 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, and further preferably an aryl group, and the foregoing groups optionally have a substituent.
In the formula (1-A4), R11A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an alkyl group or an aryl group, and further preferably a hydrogen atom, and the foregoing groups optionally have a substituent.
In the formula (1-A1) to the (1-A4), R13A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, more preferably a hydrogen atom, an alkyl group or an aryl group, and further preferably a hydrogen atom, and the foregoing groups optionally have a substituent.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group represented by R11A, R12A and R13A are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which R11A, R12A and R13A optionally have are the same as the examples and preferable examples of the substituent which the substituent which Ring L1 and Ring L2 optionally have optionally further has.
In the formula (1-A1) to the formula (1-A4), it is preferable that R11A and R12A, R12A and R13A, and R11A and R21A each are not combined together to form a ring together with atoms to which they are attached.
R11B, R12B, R13B, R14B, R15B, R16B, R17B and R13B are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and more preferably a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
R11B, R14B, R15B, R16B, R17B and R18B are each preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
R12B and R13B are each preferably a hydrogen atom, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom or a monovalent heterocyclic group, and further preferably a hydrogen atom, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
Examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group represented by R11B, R12B, R13B, R14B, R15B, R16B, R17B and R18B are the same as the examples and preferable examples of the aryl group, the monovalent heterocyclic group and the substituted amino group as the substituent which Ring L1 and Ring L2 optionally have, respectively.
Examples and preferable examples of the substituent which R11B, R12B, R13B, R14B, R15B, R16B, R17B and R18B optionally have are the same as the examples and preferable examples of the substituent which the substituent which Ring L1 and Ring L2 optionally have optionally further has.
In the formula (1-B1) to the formula (1-B5), at least one of R11B, R12B, R13B, R14B, R11B, R12B, R13B, R14B, R15B, R16B, R17B, R18B, R21A, R22A, R23A and R24A is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, at least one of R12B, R13B, R22A and R23A is more preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a substituted amino group or a halogen atom, at least one of R13B and R22A is further preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and at least one R22A is particularly preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a substituted amino group, and the foregoing groups optionally have a substituent, from the standpoint of advantage for an improvement in the luminance life of the light emitting device according to the present invention.
In the formula (1-B1) to the formula (1-B5), it is preferable that R11B and R12B, R12B and R13B, R13B and R14B, R11B and R21A, R133 and R15B, R15B and R16B, R16B and R17B, R17B and R18B, R18B and R21A, R11B and R13B, R14B and R15B, and R12B and R18B each are not combined together to form a ring together with atoms to which they are attached.
The phosphorescent compound includes, for example, phosphorescent compounds represented by the following formulae.
The phosphorescent compounds are available from Aldrich, Luminescence Technology Corp., American Dye Source, and the like.
In addition, the phosphorescent compounds can also be produced by known methods described in literatures such as “Journal of the American Chemical Society, Vol. 107, 1431-1432 (1985)”, “Journal of the American Chemical Society, Vol. 106, 6647-6653 (1984)”, Japanese Translation of International Publication (JP-T) No. 2004-530254, JP-A No. 2008-179617, JP-A No. 2011-105701, JP-T No. 2007-504272, International Publication WO 2006/121811, JP-A No. 2013-147450, JP-A No. 2014-224101, and the like.
The block copolymer according to the present invention is a block copolymer containing an end group, a block that binds to the end group (hereinafter, also referred to as “terminal block”), and a block that does not bind to the end group (hereinafter, also referred to as “non-terminal block”). That is, the block copolymer according to the present invention is a block copolymer containing an end group, a terminal block and a non-terminal block in this order.
The block copolymer according to the present invention preferably contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. In the block copolymer according to the present invention, the two end groups may be the same or different, but from the standpoint of easiness of production of the block copolymer according to the present invention, it is preferable that they are the same. In the block copolymer according to the present invention, the two terminal blocks may be the same or different, but it is preferable that they are the same from the standpoint of easy production of the block copolymer according to the present invention.
The block copolymer according to the present invention may contain a constitutional unit other than an end group, a terminal block and a non-terminal block, but from the standpoint of easiness of production of the block copolymer according to the present invention, it is preferable that the block copolymer according to the present invention is composed only of an end group, a terminal block and a non-terminal block.
Examples of the constitutional unit other than the end group, the terminal block and the non-terminal block include a joining unit and a branching unit.
The block copolymer according to the present invention may or may not contain a crosslinkable group, but the block copolymer according to the present invention preferably contains a crosslinkable group, since the light emitting device according to the present invention can be formed by a wet method, and in production of the light emitting device, lamination of layers is easy.
The polystyrene-equivalent number-average molecular weight (Mn) of the block copolymer according to the present invention is, for example, 2×103 or more and 5×106 or less, preferably 5×103 or more and 1×106 or less, more preferably 1×104 or more and 5×105 or less, and further preferably 2×104 or more and 1×105 or less.
The polystyrene-equivalent weight-average molecular weight (Mw) of the block copolymer according to the present invention is, for example, 5×103 or more and 1×107 or less, preferably 1×104 or more and 5×106 or less, more preferably 5×104 or more and 1×106 or less, further preferably 1×105 or more and 5×105 or less, and particularly preferably 1×105 or more and 3×105 or less.
[End group]
The “end group” is a group that is arranged at the end of the block copolymer according to the present invention and bonded directly to the terminal block, and is preferably an atomic group as a residue in the reagent (end-capping agent) used when introducing the end group into the block copolymer according to the present invention after the reagent is introduced.
From the standpoint of the stability of the block copolymer according to the present invention, the end groups are preferably arranged at all ends of the block copolymer. When a plurality of end groups are present, they may be the same or different, but are preferably the same from the standpoint of easiness of production of the block copolymer according to the present invention.
From the standpoint of the stability of the block copolymer according to the present invention, the end group is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group. At the end group, the aryl group and the monovalent heterocyclic group optionally have a substituent, but preferably, have no substituent.
Since the crosslinkability of the block copolymer according to the present invention can be enhanced, the end group preferably contains a crosslinkable group, and more preferably is a crosslinkable group. Examples and preferable examples of the crosslinkable group are the same as the examples and preferable examples mentioned in the explanation for the above-described crosslinkable group.
Examples and preferable examples of the aryl group and monovalent heterocyclic group in the end group are the same as the examples and preferable examples of the aryl group and monovalent heterocyclic group represented by RX1 to RX3, respectively.
The substituent which the aryl group and the monovalent heterocyclic group in the end group optionally have is preferably an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a crosslinkable group, more preferably an alkyl group, a cycloalkyl group, an aryl group or a crosslinkable group, further preferably an alkyl group or a crosslinkable group, particularly preferably an alkyl group, and the foregoing groups optionally further have a substituent, but it is especially preferable that it has no further substituent.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group as the substituent which the aryl group and the monovalent heterocyclic group at the end group optionally have are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by RX1 to RX3, respectively.
Examples and preferable examples of the crosslinkable group as the substituent which the aryl group and the monovalent heterocyclic group at the end group optionally have are the same as the examples and preferable examples mentioned in the explanation for the above-described crosslinkable group.
The non-terminal block is a block that does not bind directly to the end group, and consisting of one or more constitutional units. The number of the type of the constitutional unit contained in the non-terminal block is usually 1 or more and 10 or less, and from the standpoint of easy synthesis of the block copolymer according to the present invention, preferably 1 or more and 7 or less, more preferably 2 or more and 5 or less, further preferably 2 or more and 4 or less, and particularly preferably 3 or 4.
In the block copolymer according to the present invention, only one type of non-terminal block may be contained, or two or more types may be contained. The number of the type of the non-terminal block contained in the block copolymer according to the present invention is usually 1 or more and 10 or less, and from the standpoint of easy production of the block copolymer according to the present invention, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or more, further preferably 1 or 2, and particularly preferably 1.
Cases wherein the types of the non-terminal blocks are different include, for example, a case wherein the types of the constitutional units constituting the block are different and a case wherein the content ratios and chain distributions of constitutional units are different. When a plurality of non-terminal blocks are present, they may be the same or different.
It is preferable that at least one non-terminal block is a block formed before forming the terminal block in production of the block copolymer according to the present invention.
The non-terminal block contains at least one constitutional unit selected from the group consisting of constitutional units represented by the formula (X) and the constitutional units represented by the formula (Z). In the non-terminal block, each of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) may be contained singly or in combination of two or more, and one or more constitutional units represented by the formula (X) and one or more constitutional units represented by the formula (Z) may be contained.
The non-terminal block preferably contains a constitutional unit represented by the formula (X).
The non-terminal block preferably further contains at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, more preferably further contains a constitutional unit represented by the formula (Y), or a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, and further preferably further contains only a constitutional unit represented by the formula (Y), or only a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In the non-terminal block, each of the constitutional unit represented by the formula (Y) and the constitutional unit having a crosslinkable group may be contained singly or in combination of two or more.
From the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferable that at least one of constitutional units contained in the terminal block is not contained in the non-terminal block and/or at least one of constitutional units contained in the non-terminal block is not contained in the terminal block, and it is more preferable that at least one of constitutional units contained in the terminal block is not contained in the first non-terminal block and at least one of constitutional units contained in the non-terminal block is not contained in the terminal block, in the block copolymer according to the present invention.
The polystyrene-equivalent number-average molecular weight (Mn) of the non-terminal block contained in the block copolymer according to the present invention is, for example, 1×103 or more and 1×106 or less, preferably 2×103 or more and 5×105 or less, more preferably 3×103 or more and 1×105 or less, and further preferably 5×103 or more and 5×104 or less.
The polystyrene-equivalent weight-average molecular weight (Mw) of the non-terminal block contained in the block copolymer according to the present invention is, for example, 2×103 or more and 2×106 or less, preferably 3×103 or more and 1×106 or less, more preferably 5×103 or more and 5×103 or less, and further preferably 1×104 or more and 2×105 or less.
The terminal block is a block that binds directly to the end group and consisting of one or more constitutional units. The number of the type of the constitutional unit contained in the terminal block is usually 1 or more and 10 or less, and from the standpoint of easy production of the block copolymer according to the present invention and from the standpoint of improving the luminance life of the light emitting device according to the present invention, preferably 1 or more and 7 or less, more preferably 2 or more and 5 or less, and further preferably 2 or 3.
In the block copolymer according to the present invention, only one type of terminal block may be contained, or two or more types thereof may be contained. The number of the type of the terminal block contained in the block copolymer according to the present invention is generally 1 or more and 10 or less, and from the standpoint of easiness of production of the block copolymer according to the present invention, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1.
Examples of cases wherein the types of terminal blocks are different are the same as the examples wherein the types of non-terminal blocks are different.
The terminal block is preferably a block formed, in the production of the block copolymer according to the present invention, before forming the end group (preferably, before reacting with the end-capping agent).
The terminal block preferably contain at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X), a constitutional unit represented by the formula (Y), a constitutional unit represented by the formula (Z) and a constitutional unit having a crosslinkable group, more preferably contains at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X), a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, further preferably contains at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, particularly preferably contains a constitutional unit represented by the formula (Y), or a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, and especially preferably contains only a constitutional unit represented by the formula (Y), or only a constitutional unit represented by the formula (Y) and a constitutional unit having a crosslinkable group, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the terminal block, the constitutional unit represented by the formula (X), the constitutional unit represented by the formula (Y), and the constitutional unit represented by the formula (Z) and the constitutional unit having a crosslinkable group may each be contained singly or in combination of two or more.
The terminal block preferably does not contain a constitutional unit represented by the formula (X) or does not contain a constitutional unit represented by the formula (Z), more preferably does not contain a constitutional unit represented by the formula (Z), and further preferably does not contain a constitutional unit represented by the formula (X) and a constitutional unit represented by the formula (Z), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the terminal block and the non-terminal block each independently may be any of a homopolymer, a block copolymer, a random copolymer, an alternating copolymer and a graft copolymer, or may be other form, but are preferably copolymers.
The block copolymer according to the present invention contains at least one constitutional unit selected from the group consisting of a non-crosslinkable constitutional unit represented by the formula (X) and a non-crosslinkable constitutional unit represented by the formula (Z).
The block copolymer according to the present invention is preferably a block copolymer containing 2 or more and 15 or less constitutional units selected from the group consisting of a constitutional unit represented by the formula (X), a constitutional unit represented by the formula (Y), a constitutional unit represented by the formula (Z) and a constitutional unit having a crosslinkable group, more preferably a block copolymer containing 2 or more and 10 or less constitutional units, further preferably a block copolymer containing 3 or more and 7 or less constitutional units, and particularly preferably a block copolymer containing 4 or more and 6 or less constitutional units, from the standpoint of easy production of the block copolymer and from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the constitutional unit represented by the formula (X), the constitutional unit represented by the formula (Z), the constitutional unit represented by the formula (Y) and the constitutional unit having a crosslinkable group may each be contained singly or in combination of two or more.
The block copolymer according to the present invention preferably contains a constitutional unit represented by the formula (Y) from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The block copolymer according to the present invention is preferably a block copolymer containing a constitutional unit represented by the formula (Y) and at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X) and a constitutional unit represented by the formula (Z), and more preferably a block copolymer containing a constitutional unit represented by the formula (Y) and a constitutional unit represented by the formula (X), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The sum of the types of constitutional units contained in the block copolymer according to the present invention is preferably 2 or more and 20 or less, more preferably 2 or more and 15 or less, further preferably 2 or more and 10 or less, particularly preferably 3 or more and 7 or less, and especially preferably 4 or more and 6 or less, from the standpoint of easy production of the block copolymer and from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device according to the present invention, when the second organic layer contains a crosslinked product of the block copolymer according to the present invention, the light emitting device according to the present invention can be formed by a wet method, and in production of the light emitting device according to the present invention, lamination of layers is easy. The crosslinked product of the block copolymer according to the present invention is a crosslinked product of the block copolymer containing a crosslinkable group.
When the block copolymer according to the present invention is a block copolymer further containing a crosslinkable group, the block copolymer according to the present invention is preferably a block copolymer containing at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X) and a polymer compound represented by the formula (Z) (preferably a constitutional unit represented by the formula (X)), and a crosslinkable group, more preferably a block copolymer containing at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X) and a polymer compound represented by the formula (Z) (preferably a constitutional unit represented by the formula (X)), and a constitutional unit having a crosslinkable group, further preferably a block copolymer containing at least one constitutional unit selected from the group consisting of a constitutional unit represented by the formula (X) and a polymer compound represented by the formula (Z) (preferably a constitutional unit represented by the formula (X)), and a constitutional unit having a crosslinkable group, and a constitutional unit represented by the formula (Y), and particularly preferably a block copolymer containing a constitutional unit represented by the formula (X), a constitutional unit having a crosslinkable group and a constitutional unit represented by the formula (Y).
When the block copolymer according to the present invention is a block copolymer further containing a crosslinkable group, at least one selected from the group consisting of an end group, a terminal block and a non-terminal block preferably contains a crosslinkable group, at least one selected from the group consisting of a terminal block and a non-terminal block more preferably contains a crosslinkable group, and at least one selected from the group consisting of a terminal block and a non-terminal block further preferably contains a constitutional unit having a crosslinkable group. This makes it easier to increase the introduction amount of the crosslinkable group, and thus, the crosslinkability of the block copolymer according to the present invention can be easily increased to a sufficient extent.
Examples and preferable ranges of the block copolymer in the crosslinked product of the block copolymer according to the present invention are the same as the examples and preferable ranges explained in the section of the block copolymer according to the present invention.
In this specification, the total number of the constitutional units contained in the polymer compound means the average number of the constitutional units per 1000 of the molecular weight of the polymer compound. The total number of the crosslinkable groups contained in the polymer compound means the average number of the crosslinkable groups per 1000 of the molecular weight the polymer compound.
The total number of each constitutional units and crosslinkable groups contained in the polymer compound can be determined, for example, by the following method.
For each constitutional unit constituting the polymer compound, if the sum of the values obtained by multiplying the molar ratio of the constitutional unit to the total moles of all the constitutional units excluding the end group and the molecular weight of the constitutional unit is expressed as D2, the sum of the molar ratios determined for each constitutional unit is expressed as E3, and the sum of the values obtained by multiplying the molar ratio and the number of crosslinkable groups of the constituent unit is expressed as E4, then, the total number of the respective constitutional units contained in the polymer compound shall be (E3×1000)/D2, and the total number of the crosslinkable group contained in the polymer compound shall be (E4×1000)/D2.
The molecular weight of each of the constitutional units constituting the polymer compound can be calculated using, for example, the value of Molecular Weight according to ChemDraw (manufactured by HULINKS INC.).
Specific methods for calculating the total number of each constitutional unit and the total number of the crosslinkable group will be described in detail by taking the block copolymer HTL-1 synthesized in Synthesis Example 1 as an example.
The block copolymer HTL-1 has a non-terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M2, and a constitutional unit derived from the compound M3 at a molar ratio of 40:30:2.5, and a terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M4, and a constitutional unit derived from the compound M5 at a molar ratio of 10:10:7.5.
The molecular weight of a constitutional unit derived from the compound M1 is 653.05, the molecular weight of a constitutional unit derived from the compound M2 is 751.12, the molecular weight of a constitutional unit derived from the compound M3 is 388.64, the molecular weight of a constitutional unit derived from the compound M4 is 176.22, and the molecular weight of a constitutional unit derived from the compound M5 is 368.48.
The number of the crosslinkable group contained in a constitutional unit derived from the compound M1 is 0, the number of the crosslinkable group contained in a constitutional unit derived from the compound M2 is 0, the number of the crosslinkable group contained in a constitutional unit derived from the compound M3 is 0, the number of the crosslinkable group contained in a constitutional unit derived from the compound M4 is 0, and the number of the crosslinkable group contained in a constitutional unit derived from the compound M5 is 2.
A constitutional unit derived from the compound M1 is a constitutional unit represented by the formula (Y), a constitutional unit derived from the compound M2 is a constitutional unit represented by the formula (X), a constitutional unit derived from the compound M3 is a constitutional unit represented by the formula (Y), a constitutional unit derived from the compound M4 is a constitutional unit represented by the formula (Y), and a constitutional unit derived from the compound M5 is a constitutional unit having a crosslinkable group.
D2 is determined as follows.
(653.05×0.40)+(751.12*0.30)+(388.64×0.025)+(653.05×0.10)+(176.22*0.10)+(368.48×0.075)=606.835
In the block copolymer HTL-1, E3 of each constitutional unit is determined as follows.
(E3 of the constitutional unit represented by the formula (Y) in the non-terminal block)=0.40+0.025=0.425
(E3 of the constitutional unit represented by the formula (X) in the non-terminal block)=0.30
(E3 of the constitutional unit represented by the formula (Z) in the non-terminal block)=0
(E3 of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the non-terminal block)=0.30+0=0.30
(E3 of the constitutional unit having a crosslinkable group in the non-terminal block)=0
(E3 of the constitutional unit represented by the formula (Y) in the terminal block)=0.10+0.10=0.20
(E3 of the constitutional unit represented by the formula (X) in the terminal block)=0
(E3 of the constitutional unit represented by the formula (Z) in the terminal block)=0
(E3 of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the terminal block)=0
(E3 of the constitutional unit having a crosslinkable group in the terminal block)=0.075
(E3 of the constitutional unit represented by the formula (Y) in the block copolymer)=0.40+0.025+0.10+0.10=0.625
(E3 of the constitutional unit represented by the formula (X) in the block copolymer)=0.30
(E3 of the constitutional unit represented by the formula (Z) in the block copolymer)=0
(E3 of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the block copolymer)=0.30+0=0.30
(E3 of the constitutional unit having a crosslinkable group in the block copolymer)=0.075
E4 is determined as follows.
(E4 in non-terminal block) (0.40×0)+(0.30×0)+(0.025×0)=0
(E4 in terminal block)=(0.10×0)+(0.10×0)+(0.075×2)=0.15
(E4 in block copolymer) (0.40×0)+(0.30×0)+(0.025×0)+(0.10×0)+(0.10×0)+(0.075×2)=0.15
In the block copolymer HTL-1, the total number of each constitutional unit and crosslinkable group is determined as follows.
(Total number of the constitutional unit represented by the formula (Y) in the non-terminal block)=(0.425×1000)/606.835=0.700
(Total number of the constitutional unit represented by the formula (X) in the non-terminal block)=XI=(0.30×1000)/606.835=0.494
(Total number of the constitutional unit represented by the formula (Z) in the non-terminal block)=ZI=(0×1000)/606.835=0
(Total number of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the non-terminal block)=XI+ZI=(0.30×1000)/606.835=0.494
(Total number of the constitutional unit having a crosslinkable group in the non-terminal block) (0×1000)/606.835=0
(Total number of the crosslinkable group in the non-terminal block)=(0×1000)/606.835=0
(Total number of the constitutional unit represented by the formula (Y) in the terminal block) (0.20×1000)/606.835=0.330
(Total number of the constitutional unit represented by the formula (X) in the terminal block)=XII=(0×1000)/606.835=0
(Total number of the constitutional unit represented by the formula (Z) in the terminal block)=ZII=(0×1000)/606.835=0
(Total number of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the terminal block)=XII+ZII=(0×1000)/606.835=0
(Total number of the constitutional unit having a crosslinkable group in the terminal block) (0.075×1000)/606.835=0.124
(Total number of the crosslinkable group in the terminal block)=(0.15×1000)/606.835=0.247
(Total number of the constitutional unit represented by the formula (Y) in the block copolymer) (0.625×1000)/606.835=1.030
(Total number of the constitutional unit represented by the formula (X) in the block copolymer) (0.30×1000)/606.835=0.494
(Total number of the constitutional unit represented by the formula (Z) in the block copolymer)=(0×1000)/606.835=0
(Total number of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) in the block copolymer)=(0.30×1000)/606.835=0.494
(Total number of the constitutional unit having a crosslinkable group in the block copolymer)=(0.075×1000)/606.835=0.124
(Total number of the crosslinkable group in the block copolymer)=(0.15×1000)/606.835=0.247
In the block copolymer according to the present invention, the total number of the constitutional unit represented by the formula (Y) contained in the non-terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the non-terminal block contains a constitutional unit represented by the formula (Y), the total number of the constitutional unit represented by the formula (Y) contained in the non-terminal block is preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, especially preferably 0.1 or more and 2 or less, and may also be 0.5 or more and 2 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the total number (XI) of the constitutional unit represented by the formula (X) contained in the non-terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the non-terminal block contains the constitutional unit represented by the formula (X), the total number (XI) of the constitutional unit represented by the formula (X) contained in the non-terminal block is preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 3 or less, particularly preferably 0.2 or more and 2 or less, especially preferably 0.3 or more and 2 or less, and may also be 0.2 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the total number (ZI) of the constitutional unit represented by the formula (Z) contained in the non-terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the non-terminal block contains the constitutional unit represented by the formula (Z), the total number (ZI) of the constitutional unit represented by the formula (Z) contained in the non-terminal block is preferably 0 or more and 20 or less, more preferably 0 or more and 3 or less, further preferably 0 or more and 1 or less, and particularly preferably 0, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the total number (XI+ZI) of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) contained in the non-terminal block is usually 0.001 or more and 50 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 3 or less, particularly preferably 0.2 or more and 3 or less, especially preferably 0.3 or more and 2 or less, and may also be 0.2 or more and 1 or less.
In the block copolymer according to the present invention, the total number of the constitutional unit having a crosslinkable group contained in the non-terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the non-terminal block contains a constitutional unit having a crosslinkable group, the total number of the constitutional unit having a crosslinkable group contained in the non-terminal block is preferably 0.001 or more and 20 or less, more preferably 0.005 or more and 10 or less, further preferably 0.01 or more and 5 or less, further preferably 0.01 or more and 2 or less, especially preferably 0.05 or more and 1 or less, and especially more preferably 0.05 or more and 0.5 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
In the block copolymer according to the present invention, the total number of the crosslinkable group contained in the non-terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the non-terminal block contains a crosslinkable group, the total number of the crosslinkable group contained in the non-terminal block is preferably 0.001 or more and 20 or less, more preferably 0.01 or more and 10 or less, further preferably 0.05 or more and 5 or less, particularly preferably 0.1 or more and 2 or less, and especially preferably 0.1 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the invention.
In the block copolymer according to the present invention, the total number of the constitutional unit represented by the formula (Y) contained in the terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the terminal block contains the constitutional unit represented by the formula (Y), the total number of the constitutional unit represented by the formula (Y) contained in the terminal block (Y) is preferably 0.005 or more and 20 or less, more preferably 0.01 or more and 10 or less, further preferably 0.05 or more and 5 or less, and particularly preferably 0.1 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the block copolymer according to the present invention, the total number (XII) of the constitutional units represented by the formula (X) contained in the terminal block is usually 0 or more and 10 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferably 0 or more and 5 or less, more preferably 0 or more and 1 or less, further preferably 0 or more and 0.5 or less, particularly preferably 0 or more and 0.3 or less, may be 0 or more and 0.1 or less, and particularly preferably may also be 0.
In the block copolymer according to the present invention, the total number (Zn) of the constitutional unit represented by the formula (Z) contained in the terminal block is usually 0 or more and 10 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferably 0 or more and 5 or less, more preferably 0 or more and 1 or less, further preferably 0 or more and 0.1 or less, and particularly preferably 0.
In the block copolymer according to the present invention, the total number (XII+ZII) of the constitutional unit represented by the formula (X) and the constitutional unit represented by the formula (Z) contained in the terminal block is usually 0 or more and 10 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferably 0 or more and 5 or less, more preferably 0 or more and 1 or less, further preferably 0 or more and 0.5 or less, particularly preferably 0 or more and 0.3 or less, may be 0 or more and 0.1 or less, and may also be 0.
In the block copolymer according to the present invention, the total number of the constitutional unit having the crosslinkable group contained in the terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the terminal block contains a constitutional unit having a crosslinkable group, the total number of the constitutional unit having a crosslinkable group contained in the terminal block is preferably 0.01 or more and 20 or less, more preferably 0.005 or more and 10 or less, further preferably 0.01 or more and 5 or less, particularly preferably 0.01 or more and 2 or less, especially preferably 0.05 or more and 1 or less, especially more preferably 0.05 or more and 0.5 or less, and especially further preferably 0.1 or more and 0.5 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
In the block copolymer according to the present invention, the total number of the crosslinkable group contained in the terminal block is usually 0 or more and 50 or less. In the block copolymer according to the present invention, when the terminal block contains a crosslinkable group, the total number of the crosslinkable group contained in the terminal block is preferably 0.001 or more and 20 or less, more preferably 0.01 or more and 10 or less, further preferably 0.05 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, especially preferably 0.1 or more and 1 or less, and especially more preferably 0.2 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
The total number of the constitutional unit represented by the formula (Y) contained in the block copolymer according to the present invention is usually 0 or more and 50 or less, and when the block copolymer according to the present invention contains the constitutional unit represented by the formula (Y), the total number of the constitutional unit represented by the formula (Y) contained in the block copolymer according to the present invention is preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, and may also be 0.5 or more and 2 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The total number of the constitutional unit represented by the formula (X) contained in the block copolymer according to the present invention is usually 0 or more and 50 or less. When the block copolymer according to the present invention contains the constitutional unit represented by the formula (X), the total number of the constitutional unit represented by the formula (X) contained in the block copolymer according to the present invention is preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, especially preferably 0.2 or more and 2 or less, and may also be 0.2 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The total number of the constitutional unit represented by the formula (Z) contained in the block copolymer according to the present invention is usually 0 or more and 50 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferably 0 or more and 20 or less, more preferably 0 or more and 3 or less, further preferably 0 or more and 1 or less, and particularly preferably 0, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The total number of the constitutional unit represented by the formula (X) and the constitutional units represented by the formula (Z) contained in the block copolymer according to the present invention is usually 0.01 or more and 50 or less, and from the standpoint of improving the luminance life of the light emitting device according to the present invention, it is preferably 0.01 or more and 20 or less, more preferably 0.05 or more and 10 or less, further preferably 0.1 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, especially preferably 0.2 or more and 2 or less, and may also be 0.2 or more and 1 or less.
The total number of the constitutional unit having the crosslinkable group contained in the block copolymer according to the present invention is usually 0 or more and 50 or less. When the block copolymer according to the present invention contains a constitutional unit having a crosslinkable group, the total number of the constitutional unit having a crosslinkable group contained in the block copolymer according to the present invention is preferably 0.001 or more and 20 or less, more preferably 0.005 or more and 10 or less, further preferably 0.01 or more and 5 or less, particularly preferably 0.01 or more and 2 or less, especially preferably 0.05 or more and 1 or less, especially more preferably 0.1 or more and 1 or less, and may also be 0.05 or more and 0.5 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
The total number of the crosslinkable group contained in the block copolymer according to the present invention is usually 0 or more and 50 or less. When the block copolymer according to the present invention contains a crosslinkable group, the total number of the crosslinkable group contained in the block copolymer according to the present invention is preferably 0.001 or more and 20 or less, more preferably 0.01 or more and 10 or less, further preferably 0.05 or more and 5 or less, particularly preferably 0.1 or more and 3 or less, especially preferably 0.1 or more and 2 or less, and may also be 0.1 or more and 1 or less, from the standpoint of improving the luminance life of the light emitting device according to the present invention and from the standpoint of improving the crosslinkability of the block copolymer according to the present invention.
When the block copolymer according to the present invention satisfies at least one of the formulae (i) to (iii), it is possible to obtain a light emitting device excellent in luminance life. It is preferable for the block copolymer according to the present invention to satisfy at least two of the formulae (i) to (iii), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
Further, the block copolymer according to the present invention preferably satisfies the formula (i) or the formula (iii), more preferably satisfies the formula (i), further preferably satisfies the formula (i) and the formula (ii), or the formula (i) and the formula (iii), particularly preferably satisfies the formula (i) and the formula (iii), from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The block copolymer according to the present invention can be suitably produced by a method including the following steps.
[a] A step of polymerizing one or more compounds (monomers) forming a non-terminal block, to form a non-terminal block,
[b] A step of polymerizing one or more compounds (monomers) forming a terminal block, in the presence of the non-terminal block, to bond the terminal block to the non-terminal block, and
[c] A step of reacting a reagent (end-capping agent) for introducing an end group with the terminal block, to introduce the end group into the terminal block.
The above-described step [a] preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) described below to form a non-terminal block, more preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below, a compound represented by the formula (M-3) described below and a compound represented by the formula (M-4) described below and at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) described below to form a non-terminal block, further preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-4) described below and at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) described below to form a non-terminal block, and particularly preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-4) described below and at least one compound represented by the formula (M-5) described below to form a non-terminal block.
In the above step [a], when the non-terminal block of the block copolymer according to the present invention contains a crosslinkable group, a non-terminal block containing a crosslinkable group can be formed by polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below.
When the non-terminal block of the block copolymer according to the present invention contains a crosslinkable group, the above-described step [a] preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) described below and at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below, to form a non-terminal block, more preferably includes a step of polymerizing at least one compound represented by the formula (M-5) described below and at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound presented by the formula (M-3) described below, to form a non-terminal block, further preferably includes a step of polymerizing at least one compound represented by the formula (M-5) described below, at least one selected from the group consisting of a compound presented by the formula (M-2) described below a compound represented by the formula (M-3) described below, and at least one compound represented by the formula (M-4) described below, to form a non-terminal block, and particularly preferably includes a step of polymerizing at least one compound represented by the formula (M-5) described below, at least one compound represented by the formula (M-2) described below and at least one compound represented by the formula (M-4) described below, to form a non-terminal block.
The above-described step [b] preferably includes a step of polymerizing, in the presence of the non-terminal block, at least one selected from the group consisting of a compound represented by the formula (M-1) described below, a compound represented by the formula (M-2) described below, a compound represented by the formula (M-3) described below, a compound represented by the formula (M-4) described below and a compound represented by the formula (M-5) described below to bind the terminal block to the non-terminal block, and more preferably includes a step of polymerizing, in the presence of the non-terminal block, at least one selected from the group consisting of a compound represented by the formula (M-2) described below, a compound represented by the formula (M-3) described below, a compound represented by the formula (M-4) described below and a compound represented by the formula (M-5) described below to bind the terminal block to the non-terminal block.
In the above-described step [b], when the terminal block of the block copolymer according to the present invention contains a crosslinkable group, it is possible to polymerize at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below to form a terminal block containing a crosslinkable group.
When the terminal block of the block copolymer according to the present invention contains a crosslinkable group, the above-described step [b] preferably includes a step of polymerizing, in the presence of the non-terminal block, at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below to bind the terminal block to the non-terminal block, more preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below and at least one selected from the group consisting of a compound represented by the formula (M-1) described below, a compound represented by the formula (M-4) described below and a compound represented by the formula (M-5) described below to bind the terminal block to the non-terminal block, and further preferably includes a step of polymerizing at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below and at least one selected from the group consisting of a compound represented by the formula (M-4) described below and a compound represented by the formula (M-5) described below to bind the terminal block to the non-terminal block.
The above-described step [c] preferably includes a step of reacting a compound (end-capping agent) represented by the formula (M-6) described below with the terminal block to introduce the end group into the terminal block. In the above-described step [c], when the end group of the block copolymer according to the present invention contains a crosslinkable group, for example, a compound having a crosslinkable group among compounds (end-capping agents) represented by the formula (M-6) described below (preferably, a compound represented by the formula (M-6) described below in which ArT is a crosslinkable group) can be reacted with the terminal block to form an end group containing the crosslinkable group.
In the present specification, the compounds used for producing the block copolymer according to the present invention are collectively referred to as “raw material monomer” in some cases.
In each of the above steps, the raw material monomers, that is, the compound forming the non-terminal block, the compound forming the terminal block, and the end capping agent can be selected, respectively, so that each block contains a desired constitutional unit and the end group is constituted of a desired group, in the light of the description in the above section [Production method of block copolymer].
In one embodiment of the method for producing a block copolymer according to the present invention,
the above-described step [a] is a step of polymerizing at least one compound represented by the formula (M-4) described below and at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) to form a non-terminal block,
the above-described step [b] is a step of polymerizing, in the presence of the non-terminal block, at least one compound represented by the formula (M-4) described below, to bind the terminal block to the non-terminal block, and
the above-described step [c] is a step of reacting a compound (end-capping agent) represented by the formula (M-6) described below with the terminal block to introduce the end group into the terminal block.
When the non-terminal block contains a crosslinkable group, in the above-described step [a] in the production method according to the above-described one embodiment, a non-terminal block containing a crosslinkable group can be formed by polymerizing at least one compound represented by the formula (M-4) described below, at least one selected from the group consisting of a compound represented by the formula (M-5) described below and a compound represented by the formula (M-1) describe below, and at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below. When the terminal block contains a crosslinkable group, in the above-described step [b] in the production method according to the above-described one embodiment, a terminal block containing a crosslinkable group can be formed by polymerizing at least one compound presented by the formula (M-4) described below, and at least one selected from the group consisting of a compound represented by the formula (M-2) described below and a compound represented by the formula (M-3) described below. When the end group contains a crosslinkable group, in the above-described step [c] in the production method according to the above-described one embodiment, an end group containing a crosslinkable group can be formed by reacting a compound represented by the following formula (M-6) in which ArT is a crosslinkable group with a terminal block.
Ar2, Ar3, LA, nA, X, n, Ar4, Ar5, Ar6, KA, mA, X′, m, c, ArY1, ArX1, ArX2, ArX3, ArX4, RX1, RX2, RX3, aX1 and aX2 represent the same meaning as described above.
ArT represents an aryl group, a monovalent heterocyclic group or a crosslinkable group, and the foregoing groups optionally have a substituent.
ZC1 to ZC11 are each a reactive group, and each independently represent a group selected from the group consisting of Group B and Group C.].
The compound represented by the formula (M-1) is a compound capable of forming the constitutional unit represented by the formula (Z).
The compound represented by the formula (M-2) is a compound capable of forming the constitutional unit represented by the formula (2).
The compound represented by the formula (M-3) is a compound capable of forming the constitutional unit represented by the formula (2′).
The compound represented by the formula (M-4) is a compound capable of forming the constitutional unit represented by the formula (Y).
The compound represented by the formula (M-5) is a compound capable of forming the constitutional unit represented by the formula (X).
The compound represented by the formula (M-6) is a compound capable of forming an end group.
From the standpoint of stability of the block copolymer, ArT is preferably an aryl group or a monovalent heterocyclic group, and more preferably an aryl group, and the foregoing groups optionally have a substituent. Further, ArT is preferably a crosslinkable group because the crosslinkability of the block copolymer can be enhanced.
Examples and preferable examples of the aryl group and the monovalent heterocyclic group represented by ArT are the same as the examples and preferable examples of the aryl group and the monovalent heterocyclic group in the end group.
Examples and preferable examples of the crosslinkable group represented by ArT are the same as the examples and the preferable examples of the crosslinkable group in the end group.
Group B and Group C are as follows, respectively.
A chlorine atom, a bromine atom, an iodine atom, a group represented by —O—S(═O)2RC1 (wherein, RC1 represents an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally have a substituent.).
A group represented by —B (ORC2)2 (wherein, RC2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally have a substituent. A plurality of RC2 may be the same or different, and may be combined together to form a ring structure together with oxygen atoms to which they are attached);
a group represented by —BF3Q′ (wherein, Q′ represents Li, Na, K, Rb or Cs);
a group represented by —MgY′ (wherein, Y′ represents a chlorine atom, a bromine atom or an iodine atom);
a group represented by —ZnY″ (wherein, Y″ represents a chlorine atom, a bromine atom or an iodine atom); and
a group represented by —Sn(RC3)3 (wherein, RC3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the foregoing groups optionally have a substituent. A plurality of RC3 may be the same or different, and may be combined together to form a ring structure together with tin atoms to which they are attached.).
Examples of the group represented by —B(ORC2)2 include groups represented by the following formulae in addition to —B(OH)2.
The raw material monomers for forming each block can have two reactive groups selected from Group B or Group C, as is the case with the compounds represented by the formulae (M-1) to (M-5) described above. It is preferable that the two reactive groups which each of the raw material monomer for forming each block has are both selected from Group B or both selected from Group C, since production of the raw material monomer is easy.
For example, a compound having a group selected from Group B and a compound having a group selected from Group C are subjected to a known coupling reaction, to generate a bond between a carbon atom bonded to a group selected from Group B and a carbon atom bonded to a group selected from Group C. Hence, if a compound having two groups selected from Group B and a compound having two groups selected from Group C are subjected to a known coupling reaction, a condensation polymer of these compounds can be obtained by condensation polymerization.
By the condensation polymerization, formation of a non-terminal block and binding of a terminal block to a non-terminal block (formation of a terminal block) can be performed.
When the production method according to the above-mentioned embodiment is taken as an example, for example, when ZC1, ZC2, ZC3, ZC4, ZC5, ZC6, ZC9, and ZC10 are groups selected from Group B, if a group selected from Group C is selected as ZC7 and ZC8, formation of a non-terminal block and binding of a terminal block to a non-terminal block (formation of a terminal block) can be performed by condensation polymerization. When ZC1, ZC2, ZC3, ZC4, ZC5, ZC6, ZC9 and ZC10 are groups selected from the C group, if a group selected from Group B is selected as ZC7 and ZC8, formation of a non-terminal block and binding of a terminal block to a non-terminal block (formation of a terminal block) can be performed by condensation polymerization.
Further, one embodiment in which two or more compounds represented by the formula (M-1) to the formula (M-5) are used in the production method according to the above-mentioned embodiment will be explained with reference to the case where two or more compounds represented by the formula (M-4) are used. For example, when performing formation of a terminal block using two or more compounds represented by the formula (M-4), if ZC7 and ZC8 of any at least one compound among at least two compounds represented by the formula (M-4) are selected from Group C and ZC7 and ZC8 of the other compound are selected from Group B, formation of a terminal block can be performed by condensation polymerization.
Introduction of an end group into a terminal block can be carried out by utilizing the same reaction. That is, when the end of the terminal block is a group selected from Group B, an end group can be introduced by a coupling reaction if a group selected from Group C is selected as ZC11. When the end of a terminal block is a group selected from Group C, an end group can be introduced by a coupling reaction if a group selected from Group B is selected as ZC11.
In the case of producing a block copolymer by the above condensation polymerization in which a non-terminal block and a terminal block are each formed using a compound having two groups selected from Group B and a compound having two groups selected from Group C as raw material monomers, it is preferable to appropriately control the amount ratio of the raw material monomers used in each of the step of forming a non-terminal block (step [a] described above) and the step of forming a terminal block (step [b] described above).
That is, in the step [a], it is preferable to use one of the compound having two groups selected from Group B and the compound having two groups selected from Group C in excess on a molar basis. This makes it possible to reliably produce a non-terminal block having a group selected from Group B or a group selected from Group C at the end. When the compound used in excess is a compound having two groups selected from Group B, a non-terminal block having a group selected from Group B at the end is produced, while when the compound used in excess is a compound having two groups selected from Group C, a non-terminal block having a group selected from Group C at the end is produced.
In the subsequent step [b], it is preferable that a compound not used in excess in the step [a], among the compound having two groups selected from Group B and the compound having two groups selected from Group C, is used in excess on a molar basis. This makes it possible to reliably produce a terminal block which is bonded to the non-terminal block and has a group selected from Group C or a group selected from Group B at the end. When the compound used in excess is a compound having two groups selected from Group B, a terminal block having a group selected from Group B at the end is produced, while when the compound used in excess is a compound having two groups selected from Group C, a terminal block having a group selected from Group C at the end is produced.
When a terminal block having a group selected from Group B at the end is produced in the step [b], an end-capping agent having a group selected from Group C is used in the step [c]. In the step [b], when a terminal block having a group selected from Group C at the end is produced, an end-capping agent having a group selected from Group B is used in the step [c].
The control of the use amount ratio of the raw material monomer in production of the block copolymer according to the present invention will be described in detail with reference to the block copolymer HTL-1 fabricated in Synthesis Example 1 in the examples.
In Synthesis Example 1, the mixture HTL-1a was used for the formation of a non-terminal block, and this mixture contains a compound M1 which is a compound having two groups selected from Group C, a compound M2 which is a compound having two groups selected from Group B and a compound M3 which is a compound having two groups selected from Group B at a molar ratio of 40:30:2.5. As described, for the mixture HTL-1a, the use amount ratio is controlled so that the compound having two groups selected from Group C is excess on a molar basis. Hence, the non-terminal block to be formed has a group selected from Group C at the end.
Further, the mixture HTL-1b is used for forming a terminal block, and this mixture contains a compound M1 which is a compound having two groups selected from Group C, a compound M4 which is a compound having two groups selected from Group B and a compound M5 which is a compound having two groups selected from Group B at a molar ratio of 10:10:7.5. As described above, for the mixture HTL-1b, the use amount ratio is controlled so that the compound having two groups selected from Group B is in excess on a molar basis. Thus, a terminal block which binds to a non-terminal block having a group selected from Group C at the end, and has a group selected from Group B at the end, is formed.
Phenylboronic acid, which is the end-capping agent used in Synthesis Example 1, is a compound having one group selected from Group C. Therefore, phenylboronic acid is bonded to a terminal block having a group selected from Group B at the end, to seal the end of the block copolymer and to form a phenyl group as the end group.
The above-described condensation polymerization (coupling reaction) is usually carried out in the presence of a catalyst, a base and a solvent, but it may be carried out in the co-existence of a phase transfer catalyst, if necessary.
The catalyst includes, for example, transition metal complexes such as palladium complexes such as bis(triphenylphosphine)palladium(II) dichloride, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride, tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), palladium acetate and the like, nickel complexes such as tetrakis(triphenylphosphine)nickel(0), [1,3-bis(diphenylphosphino)propane)nickel(II) dichloride, bis(1,4-cyclooctadiene)nickel(0) and the like; these transition metal complexes further having a ligand such as triphenylphosphine, tri(o-tolyl)phosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, 1,3-bis(diphenylphosphino)propane, bipyridyl and the like. The catalyst may be used singly or in combination of two or more.
The amount of the catalyst used is usually 0.00001 molar equivalent or more and 3 molar equivalent or less as the amount of the transition metal with respect to the sum of the number of moles of the raw material monomers.
The base and the phase transfer catalyst include, for example, inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate and the like; organic bases such as tetrabutylammonium fluoride, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like; phase transfer catalysts such as tetrabutylammonium chloride, tetrabutylammonium bromide and the like. The base and the phase transfer catalyst may each be used singly or in combination of two or more.
Each of the use amounts of the base and the phase transfer catalyst is usually 0.001 molar equivalent or more and 100 molar equivalent or less with respect to the total number of moles of the raw material monomers.
The solvent includes, for example, organic solvents such as toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N,N-dimethylacetamide, N,N-dimethylformamide and the like, and water. The solvent may be used singly or in combination of two or more.
The amount of the solvent used is usually 10 parts by mass or more and 100000 parts by mass or less with respect to 100 parts by mass of the sum of the raw material monomers.
The reaction temperature of the condensation polymerization is usually −100° C. or higher and 200° C. or lower. The reaction time of the condensation polymerization is usually 1 hour or more.
For the post-treatment of the condensation polymerization reaction (coupling reaction), known methods, for example, a method for removing water-soluble impurities by liquid separation, a method in which the reaction liquid after the reaction is added to a lower alcohol such as methanol or the like, the deposited precipitate is filtered, then, dried, and other methods, can be used singly or in combination.
When the purity of the block copolymer according to the present invention is low, it can be purified by a usual method such as, for example, crystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography and the like.
The light emitting device according to the present invention is a light emitting device having an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode, wherein the first organic layer is a layer containing a phosphorescent compound, the second organic layer is a layer containing at least one of a block copolymer containing an end group, a block that binds to the end group and a block that does not bind to the end group, and a crosslinked product of the block copolymer, the block that does not bind to the end group contains at least one constitutional unit selected from the group consisting of a non-crosslinkable constitutional unit represented by the formula (X) and a non-crosslinkable constitutional unit represented by the formula (Z), and at least one of the above-described formulae (i) to (iii) is satisfied.
The method for forming the first organic layer and the second organic layer includes, for example, dry methods such as a vacuum vapor-deposition method and the like, and wet methods such as a spin coating method, an inkjet printing method and the like, and wet methods are preferable.
When the first organic layer is formed by a wet method, it is preferable to use a first ink described later.
When the second organic layer is formed by a wet method, it is preferable to use a second ink or a 2′-nd ink described later, and it is more preferable to use a 2′-nd ink.
When the block copolymer according to the present invention contains a crosslinkable group, the block copolymer according to the present invention containing a crosslinkable group contained in the second organic layer can be crosslinked by heating or irradiating with light (preferably, heating) after forming the second organic layer. Since the block copolymer according to the present invention containing a crosslinkable group is contained in a crosslinked state [in the form of a crosslinked product of the block copolymer according to the present invention containing a crosslinkable group] in this second organic layer, the second organic layer is substantially insolubilized in a solvent. Hence, such a second organic layer can be suitably used for laminating layers in production of a light emitting device.
In a preferable embodiment of the light emitting device according to the present invention, the second organic layer contains a crosslinked product of the block copolymer according to the present invention.
The heating temperature for crosslinking the film is usually 25° C. or higher and 300° C. or lower, preferably 50° C. or higher and 260° C. or lower, more preferably 130° C. or higher and 230° C. or lower, and further preferably 180° C. or higher and 210° C. or lower.
The time of heating is usually 0.1 minutes or more and 1000 minutes or less, preferably 0.5 minutes or more and 500 minutes or less, more preferably 1 minute or more and 120 minutes or less, and further preferably 10 minutes or more and 60 minutes or less.
The type of the light used for light irradiation is, for example, ultraviolet light, near-ultraviolet light, or visible light.
The method for analyzing the components contained in the first organic layer or the second organic layer includes, for example, chemical separation and analysis methods such as extraction and the like, instrumental analysis methods such as infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and the like, and analytical methods in which a chemical separation and analysis method and an instrumental analysis method are combined.
By performing solid-liquid extraction using an organic solvent such as toluene, xylene, chloroform, tetrahydrofuran and the like on the first organic layer or the second organic layer, the components can be separated into components substantially insoluble in an organic solvent (insoluble component) and components soluble in an organic solvent (soluble component). The insoluble components can be analyzed by infrared spectroscopy or nuclear magnetic resonance spectroscopy, and the soluble components can be analyzed by nuclear magnetic resonance spectroscopy or mass spectrometry.
The first organic layer may contain one type of the phosphorescent compound alone or two or more types of the phosphorescent compounds.
The content of the phosphorescent compound in the first organic layer may be within the range in which the function as the first organic layer is performed. For example, the total content of the phosphorescent compound may be 0.01 to 100% by mass, preferably 0.1 to 70% by mass, more preferably 1 to 50% by mass, further preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass, based on the total amount of the first organic layer.
The first organic layer is preferably a layer containing a phosphorescent compound and a host material having at least one function selected from hole injectability, hole transportability, electron injectability and electron transportability, since the light emitting device of the present invention is more excellent in luminance life. The first organic layer may contain one type of the host material alone or two or more types of the host materials.
When the first organic layer is a layer containing a phosphorescent compound and a host material, the content of the host material is usually 1 to 99 parts by mass, preferably 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, further preferably 30 to 96 parts by mass, and particularly preferably 50 to 95 parts by mass, when the sum of the phosphorescent compound and the host material is taken as 100 parts by mass. When the first organic layer is a layer containing a phosphorescent compound and a host material, the content of the host material may be 10 to 90 parts by mass, may be 30 to 85 parts by mass, may be 50 to 80 parts by mass when the sum of the phosphorescent compound and the host material is taken as 100 parts by mass.
It is preferable that the lowest excited triplet state (Ti) of the host material has higher energy level than the lowest excited triplet state (Ti) of the phosphorescent compound, since the light emitting device according to the present invention is more excellent in luminance life.
The host material is preferably one which exhibits solubility in a solvent capable of dissolving the phosphorescent compound since the light emitting device according to the present invention can be produced by a wet method.
The host material is classified into a low molecular weight compound (hereinafter, also referred to as “low molecular weight host”) and a polymer compound (hereinafter, also referred to as “polymer host”), and the first organic layer may contain any host material. As the host material that may be contained in the first organic layer, a polymer host is preferable.
The low molecular weight host is preferably a compound represented by the formula (H-1).
ArH1 and ArH2 are each preferably a phenyl group, a fluorenyl group, a spirobifluorenyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a furyl group, a benzofuryl group, a dibenzofuryl group, a pyrrolyl group, an indolyl group, an azaindolyl group, a carbazolyl group, an azacarbazolyl group, a diazacarbazolyl group, a phenoxazinyl group or a phenothiazinyl group, more preferably a phenyl group, a fluorenyl group, a spirobifluorene group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group or an azacarbazolyl group, further preferably a fluorenyl group, a spirobifluorenyl group, a dibenzothienyl group, a dibenzofuryl group or a carbazolyl group, and particularly preferably a group represented by the formula (TDA-3), and the foregoing groups optionally have a substituent.
The substituent which ArH1 and ArK2 optionally have is preferably a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkoxy group, an alkoxy group or a cycloalkoxy group, and further preferably an alkyl group or a cycloalkoxy group, and the foregoing groups optionally further have a substituent.
nH1 is preferably 1. nH2 is preferably 0.
nH3 is generally an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1.
nH11 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and further preferably 1.
RH11 is 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 or a cycloalkyl group, and further preferably a hydrogen atom or an alkyl group, and the foregoing groups optionally have a substituent.
LH1 is preferably an arylene group or a divalent heterocyclic group, and the foregoing groups optionally further have a substituent.
LH1 is preferably a group represented by the formula (A-1) to the formula (A-3), the formula (A-8) to the formula (A-10), the formula (AA-1) to the formula (AA-6), the formula (AA-10) to the formula (AA-21) or the formula (AA-24) to the formula (AA-34), more preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-8), the formula (A-9), the formula (AA-1) to the formula (AA-4), the formula (AA-10) to the formula (AA-15), the formula (AA-33) or the formula (AA-34), further preferably a group represented by the formula (A-1), the formula (A-2), the formula (A-8), the formula (AA-2), the formula (AA-4), the formula (AA-10), the formula (AA-12), the formula (AA-14) or the (AA-33), particularly preferably a group represented by the formula (A-8), the formula (AA-10), the formula (AA-12) or the formula (AA-14), and especially preferably a group represented by the formula (AA-14).
The substituent which LH1 optionally has is preferably a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group, further preferably an alkyl group, an aryl group or a monovalent heterocyclic group, and particularly preferably a monovalent heterocyclic group, and the foregoing groups optionally further have a substituent.
LH21 is preferably a single bond or an arylene group, more preferably a single bond, and the arylene group optionally has a substituent.
The definition and examples of the arylene group or the divalent heterocyclic group represented by LH21 are the same as the definition and examples of the arylene group or the divalent heterocyclic group represented by LH1.
RH21 is preferably an aryl group or a monovalent heterocyclic group, and the foregoing groups optionally have a substituent.
The definition and examples of the aryl group and the monovalent heterocyclic group represented by RH21 are the same as the definition and examples of the aryl group and the monovalent heterocyclic group represented by ArH1 and ArH2.
The definition and examples of the substituent which RH21 optionally has are the same as the definition and examples of the substituent which ArH1 and ArH2 optionally have.
The compound represented by the formula (H-1) is preferably a compound represented by the formula (H-2).
[wherein, ArH1, ArH2, nH3 and LH1 represent the same meaning as described above.]
The compound represented by the formula (H-1) includes, for example, compounds represented by the following formulae.
The polymer host includes, for example, a polymer compound which is a hole transporting material described later, a polymer compound which is an electron transporting material described later, and the like.
The polymer host is preferably a polymer compound containing a constitutional unit represented by the formula (Y) and/or a constitutional unit represented by the formula (Z), and more preferably a polymer compound containing a constitutional unit represented by the formula (Y) and a constitutional unit represented by the formula (Z).
When the polymer host contains a constitutional unit represented by the formula (Y), the amount of the constitutional unit represented by the formula (Y) is preferably 1 to 99?. by mol, more preferably 30 to 95?. by mol, and further preferably 50 to 90% by mol with respect to the total amount of the constitutional unit contained in the polymer host, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
When the polymer host contains a constitutional unit represented by the formula (Z), the amount of the constitutional unit represented by the formula (Z) is preferably 0.1 to 40% by mol, more preferably 1 to 30% by mol, and further preferably 5 to 20% by mol with respect to the total amount of the constitutional unit contained in the polymer host, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
Each of the constitutional unit represented by the formula (Y) and the formula (Z) may be contained either singly or in combination of two or more in the polymer host.
It is preferable that the polymer host further contains a constitutional unit represented by the following formula (X) since it is excellent in charge transportability (especially, hole transportability).
When the polymer host contains a constitutional unit represented by the formula (X), the amount of the constitutional unit represented by the formula (X) is preferably 0.1 to 50% by mol, and more preferably 1 to 30% by mol with respect to the total amount of the constitutional unit contained in the polymer host since it is excellent in charge transportability (especially, hole transportability).
The constitutional unit represented by the formula (X) may be contained singly or in combination of two or more in the polymer host.
The polymer host containing a constitutional unit represented by the formula (Y) includes, for example, polymer compounds P-1 to P-6 shown in Table 1 and the like.
[In the table, p, q, r, s and t represent the molar ratio of each constitutional unit, p+q+r+s+t=100 and 100≥p+q+r+s≥70. The other constitutional unit means a constitutional unit other than the constitutional unit represented by the formula (Y), the constitutional unit represented by the formula (Z) and the constitutional unit represented by the formula (X).]
The polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer and a graft copolymer, or may be another mode.
The polystyrene-equivalent number-average molecular weight of the polymer host is preferably 2×103 to 1×106, more preferably 3×103 to 5×105, and further preferably 5×103 to 1.5×105.
The polystyrene-equivalent weight-average molecular weight of the polymer host is preferably 3×103 to 2×106, more preferably 5×103 to 1×106, and further preferably 1×104 to 5×105.
The polymer host can be produced by using a known polymerization method described in Chemical Review (Chem. Rev.), Vol. 109, pp. 897-1091 (2009) and the like, and exemplified are methods for polymerizing 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, the Kumada reaction and the like.
In the above-described polymerization method, the method of charging monomers includes a method of charging the whole amount of monomers into the reaction system at once, a method of charging a part of monomers and reacting them, then, charging the remaining monomers at once, continuously or dividedly, a method of charging monomers continuously or dividedly, and the like.
The transition metal catalyst includes a palladium catalyst, a nickel catalyst and the like.
The post-treatment of the polymerization reaction is conducted by known methods, for example, a method of removing water-soluble impurities by liquid separation, a method of adding the reaction liquid after the polymerization reaction to a lower alcohol such as methanol and the like, filtrating the deposited precipitate, then, drying it, and the like, singly or in combination. When the purity of the polymer host is low, it can be purified by a usual method such as, for example, recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography and the like.
The first organic layer may be a layer containing a composition containing a phosphorescent compound and the other component other than the phosphorescent compound (hereinafter, also referred to as “first composition”).
The other component is preferably at least one component selected from the group consisting of the host material, the hole transporting material, the hole injection material, the electron transporting material, the electron injection material, the light emitting material (but different from the phosphorescent compound) and the antioxidant described above.
The hole transporting material is classified into a low molecular weight compound and a polymer compound, and is preferably a polymer compound having a crosslinkable group.
The low molecular weight compound includes, for example, aromatic amine compounds such as triphenylamine and its derivatives, N,N′-di-1-naphthyl-N,N′-diphenylbenzidine (α-NPD), and N,N′-diphenyl-N,N′-di(m-tolyl)benzidine (TPD) and the like.
The polymer compound includes, for example, polyvinylcarbazole and its derivatives; and polyarylene having an aromatic amine structure in its side chain or main chain and its derivatives. The polymer compound may be a compound to which an electron accepting site such as fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone and the like is bonded.
In the first composition, the content of the hole transporting material is usually 1 to 400 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The hole transporting materials may be used singly or in combination of two or more.
The electron transporting material is classified into a low molecular weight compound and a polymer compound. The electron transporting material may have a crosslinkable group.
The low molecular weight compound includes, for example, a metal complex having 8-hydroxyquinoline as a ligand; oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene and diphenoquinone, and derivatives thereof.
The polymer compound includes, for example, polyphenylene, polyfluorene, and derivatives thereof. The polymer compound may be doped with a metal.
In the first composition, the content of the electron transporting material is usually 1 to 400 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The electron transporting material may be used singly or in combination of two or more.
The hole injection material and the electron injection material are each classified into a low molecular weight compound and a polymer compound. The hole injection material and the electron injection material may have a crosslinkable group.
The low molecular weight compound includes, for example, metal phthalocyanines such as copper phthalocyanine and the like; carbon; oxides of metals such as molybdenum, tungsten and the like; metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, potassium fluoride and the like.
The polymer compound includes, for example, polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; conductive polymers such as polymers containing an aromatic amine structure in its main chain or side chain.
In the first composition, the content of each of the hole injection material and the electron injection material is usually 1 to 400 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The hole injection material and the electron injection material may each be used singly or in combination of two or more.
When the hole injection material or the electron injection material contains a conductive polymer, the electrical conductivity of the conductive polymer is preferably 1×10−5 S/cm or more and 1×103 S/cm or less.
In order to set the electric conductivity of the conductive polymer within the above range, the conductive polymer can be doped with an appropriate amount of ions. The types of ions to be doped are anions for hole injection materials and cations for electron injection materials. 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 ions to be doped may be used singly or in combination of two or more.
The light emitting material is classified into a low molecular weight compound and a polymer compound. The light emitting material may have a crosslinkable group.
The low molecular weight compound includes, for example, naphthalene and its derivatives, anthracene and its derivatives, and perylene and its derivatives.
The polymer compound includes, for example, polymer compounds containing an arylene group such as a phenylene group, a naphthalenediyl group, a fluorenediyl group, a phenanthrenediyl group, a dihydrophenanthrendiyl group, an anthracenediyl group, a pyrenediyl group or the like; an aromatic amine residue such as a group obtained by removing two hydrogen atoms from the aromatic amine, and the like; and a divalent heterocyclic group such as a carbazolediyl group, a phenoxazinediyl group, a phenothiazinediyl group and the like.
In the first composition, the content of the light emitting material is usually 1 to 400 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The light emitting material may be used only singly or in combination of two or more.
The antioxidant may be a compound that is soluble in the same solvent as for the phosphorescent compound and does not inhibit light emission and charge transportation, and includes, for example, a phenol-based antioxidant and a phosphorus-based antioxidant.
In the first composition, the content of the antioxidant is usually 0.001 to 10 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The antioxidant may be used only singly or in combination of two or more.
The composition containing a phosphorescent compound and a solvent (hereinafter, also referred to as “first ink”) can be suitably used when the first organic layer is formed by a wet method such as a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method, a capillary coating method, a nozzle coating method and the like (hereinafter, also simply referred to as “wet method”).
The viscosity of the first ink may be adjusted according to the type of the wet method, but when applied to a printing method in which a solution passes through an ejection device such as an inkjet printing method and the like, it is preferably 1 to 20 mPa·s at 25° C., since it is difficult for clogging and flight bending during discharge to occur.
The solvent contained in the ink is preferably a solvent capable of dissolving or uniformly dispersing the solid content in the ink. The solvent includes, for example, chlorine-based solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and the like; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methylanisole and the like; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene and the like; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, bicyclohexyl and the like; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone and the like; ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, phenyl acetate and the like; polyhydric alcohol solvents such as ethylene glycol, glycerin, 1,2-hexanediol and the like; alcohol solvents such as isopropyl alcohol, cyclohexanol and the like; sulfoxide solvents such as dimethyl sulfoxide and the like; amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide and the like. The solvent may be used only singly or in combination of two or more.
In the first ink, the content of the solvent is usually 1000 to 100000 parts by mass, and preferably 2000 to 20000 parts by mass when the amount of the phosphorescent compound is taken as 100 parts by mass.
The first ink can further contain at least one component selected from the group consisting of the host material, the hole transporting material, the hole injection material, the electron transporting material, the electron injection material, the light emitting material and the antioxidant described above.
In the second organic layer, the block copolymer according to the present invention may be contained singly or in combination of two or more. In the second organic layer, the crosslinked product of the block copolymer according to the present invention may be contained singly or in combination of two or more.
In the second organic layer, the total content of the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention may be within a range in which the function as the second organic layer is performed. For example, the total content of the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention may be 0.1% by mass or more and 100% by mass or less, and is preferably 10% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 100% by mass or less, further preferably 50% by mass or more and 100% by mass or less, and particularly preferably 80% by mass or more and 100% by mass or less, based on the total amount of the second organic layer.
The second organic layer may be a layer containing the second composition.
The second composition contains at least one selected from the group consisting of the block copolymer according to the present invention and a crosslinked product of the block copolymer according to the present invention, and other components other than the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention.
The other component contained in the second composition is preferably at least one component 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, and more preferably at least one component 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 and an antioxidant. The hole transporting material, the hole injection material, the electron transporting material, the electron injection material and the light emitting material herein referred to are different from the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention.
In the second composition, the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention may each be contained only singly or in combination of two or more.
Examples and preferable ranges 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 second composition are the same as the examples and preferable examples 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 first composition.
In the second composition, the content 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 mass when the total amount of the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention is taken as 100 parts by mass.
The examples and preferable examples of the antioxidant contained in the second composition are the same as the examples and preferable examples of the antioxidant contained in the first composition. In the second composition, the content of the antioxidant is usually 0.001 parts by mass or more and 10 parts by mass or less when the total amount of the block copolymer according to the present invention and the crosslinked product of the block copolymer according to the present invention is taken as 100 parts by mass.
The composition containing the block copolymer according to the present invention and a solvent (hereinafter, also referred to as “second ink”) can be suitably used for the wet method described in the section of the first ink. The preferable examples of the viscosity of the second ink are the same as the preferable examples of the viscosity of the first ink. Examples and preferable examples of the solvent contained in the second ink are the same as the examples and preferable examples of the solvent contained in the first ink.
When the second organic layer contains a crosslinked product of the block copolymer according to the present invention, the second organic layer containing a crosslinked product of the block copolymer according to the present invention can be formed by crosslinking the crosslinkable group contained in the block copolymer according to the present invention by the above-described conditions, methods and the like using a composition containing the block copolymer containing a crosslinkable group according to the present invention, and a solvent (hereinafter, also referred to as “2′-nd ink”).
In the second ink, the content of the solvent is usually 1000 to 100000 parts by mass, and preferably 2000 to 20000 parts by mass when the amount of the block copolymer according to the present invention is taken as 100 parts by mass. In the 2′-nd ink, the content of the solvent is usually 1000 to 100000 parts by mass, preferably 2000 to 20000 parts by mass when the amount of the block copolymer according to the present invention containing a crosslinkable group is taken as 100 parts by mass.
The second and 2′-nd inks can further contain at least one component selected from the group consisting of the hole transporting material, the hole injection material, the electron transporting material, the electron injection material, the light emitting material and the antioxidant described above.
The light emitting device according to the present invention is a light emitting device having an anode, a cathode, and a first organic layer and a second organic layer provided between the anode and the cathode, and, from the standpoint of improving the luminance life of the light emitting device according to the present invention, preferably a layer in which the second organic layer is provided between the anode and the first organic layer.
The light emitting device 10 may have layers other than the electrode 11, the electrode 14, the first organic layer 13, and the second organic layer 12.
In the light emitting device 10, one of the electrode 11 and the electrode 14 is an anode and the other is a cathode. In the light emitting device 10, it is preferable that the electrode 11 is an anode and the electrode 14 is a cathode, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device 10, the first organic layer 13 is usually a light emitting layer (hereinafter, also referred to as “first light emitting layer”).
In the light emitting device 10, when the electrode 11 is an anode, the second organic layer 12 is usually a hole transporting layer or a second light emitting layer, preferably a hole transporting layer.
In the light emitting device 10, when the electrode 11 is a cathode, the second organic layer 12 is an electron transporting layer or a second light emitting layer, and preferably an electron transporting layer.
In the light emitting device 10, the first organic layer 13 and the second organic layer 12 are preferably arranged adjacent to each other from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device 10, the second organic layer 12 is more preferably a hole transporting layer or a second light emitting layer provided between the electrode 11 and the first organic layer 13, and further preferably a hole transporting layer provided between the electrode 11 and the first organic layer 13, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In this case, the electrode 11 is an anode.
In the light emitting device 10, when the electrode 11 is an anode and the second organic layer 12 is a hole transporting layer provided between the electrode 11 and the first organic layer 13, it is preferable that a hole injection layer is further contained between the electrode 11 and the second organic layer 12, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In contrast, when the electrode 11 is an anode and the second organic layer 12 is a hole transporting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of an electron injection layer and the electron transporting layer is further contained between the electrode 14 and the first organic layer 13, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device 10, when the electrode 11 is an anode and the second organic layer 12 is a second light emitting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of a hole injection layer and a hole transporting layer is further contained between the electrode 11 and the second organic layer 12, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In contrast, when the electrode 11 is an anode and the second organic layer 12 is a second light emitting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of an electron injection layer and an electron transporting layer is further contained between the electrode 14 and the first organic layer 13, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device 10, when the electrode 11 is a cathode and the second organic layer 12 is an electron transporting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of a hole injection layer and a hole transporting layer is further contained between the electrode 14 and the first organic layer 13, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In contrast, when the electrode 11 is a cathode and the second organic layer 12 is an electron transporting layer provided between the electrode 11 and the first organic layer 13, it is preferable that an electron injection layer is further contained between the electrode 11 and the second organic layer 12, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
In the light emitting device 10, when the electrode 11 is a cathode and the second organic layer 12 is a second light emitting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of a hole injection layer and a hole transporting layer is further contained between the electrode 14 and the first organic layer 13, from the standpoint of improving the luminance life of the light emitting device according to the present invention. In contrast, when the electrode 11 is a cathode and the second organic layer 12 is a second light emitting layer provided between the electrode 11 and the first organic layer 13, it is preferable that at least one of an electron injection layer and an electron transporting layer is further contained between the electrode 11 and the second organic layer 12, from the standpoint of improving the luminance life of the light emitting device according to the present invention.
The specific layer constitution of the light emitting device according to the present invention includes, for example, layer constitutions represented by (D1) to (D15). The light emitting device according to the present invention usually has a substrate, and lamination may be performed on the substrate first from the anode, or may be performed on the substrate first from the cathode.
(D1) Anode/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/cathode
(D2) Anode/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/cathode
(D3) Anode/hole injection layer/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/cathode
(D4) Anode/hole injection layer/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/electron transporting layer/cathode
(D5) Anode/hole injection layer/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/electron injection layer/cathode
(D6) Anode/hole injection layer/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D7) Anode/hole injection layer/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/cathode
(D8) Anode/hole injection layer/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/electron transporting layer/cathode
(D9) Anode/hole injection layer/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/electron injection layer/cathode
(D10) Anode/hole injection layer/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D11) Anode/hole injection layer/hole transporting layer/second light emitting layer (second organic layer)/first light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D12) Anode/hole injection layer/hole transporting layer (second organic layer)/first light emitting layer (first organic layer)/second light emitting layer/electron transporting layer/electron injection layer/cathode
(D13) Anode/hole injection layer/hole transporting layer (second organic layer)/second light emitting layer/first light emitting layer (first organic layer)/electron transporting layer/electron injection layer/cathode
(D14) Anode/hole injection layer/hole transporting layer/first light emitting layer (first organic layer)/electron transporting layer (second organic layer)/electron injection layer/cathode
(D15) Anode/hole injection layer/hole transporting layer/first light emitting layer (first organic layer)/second light emitting layer (second organic layer)/electron transporting layer/electron injection layer/cathode
In (D1) to (D15), “/” means that the layers before and after that are adjacently laminated. For example, “second light emitting layer (second organic layer)/first light emitting layer (first organic layer)” means that the second light emitting layer (second organic layer) and the first light emitting layer (first organic layer) are laminated adjacently.
From the standpoint of improving the luminance life of the light emitting device according to the present invention, layer constitutions represented by (D3) to (D12) are preferable, and layer constitutions represented by (D7) to (D10) are more preferable.
In the light emitting device according to the present invention, two or more layers of each of the anode, the hole injection layer, the hole transporting layer, the second light emitting layer, the electron transporting layer, the electron injection layer and the cathode may be provided, if necessary.
When a plurality of anodes, hole injection layers, hole transporting layers, second light emitting layers, electron transporting layers, electron injection layers and cathodes are present, they may be the same or different at each occurrence.
The thickness of each of the anode, the hole injection layer, the hole transporting layer, the first light emitting layer, the second light emitting layer, the electron transporting layer, the electron injection layer and the cathode is usually 1 nm or more and 1 μm or less, preferably 2 nm or more and 500 nm or less, and more preferably 5 nm or more and 150 nm or less.
In the light emitting device according to the present invention, the order, the number and the thickness of the layers to be laminated may be adjusted in consideration of the light emission efficiency, the driving voltage and the device life of the light emitting device.
The second light emitting layer is usually a layer containing a second organic layer or a light emitting material, and preferably a layer containing a light emitting material. When the second light emitting layer is a layer containing a light emitting material, the light emitting material contained in the second light emitting layer includes, for example, light emitting materials which the phosphorescent compound and the first composition described above may contain. The phosphorescent compound and the light emitting material contained in the second light emitting layer may be contained each singly or in combination of two or more.
When the light emitting device according to the present invention has a second light emitting layer and the hole transporting layer described later is not a second organic layer, it is preferable that the second light emitting layer is the second organic layer.
The hole transporting layer is usually a layer containing a second organic layer or a hole transporting material, and preferably a second organic layer. When the hole transporting layer is a layer containing a hole transporting material, the hole transporting material includes, for example, hole transporting materials which the first composition described above may contain. The hole transporting material contained in the hole transporting layer may be contained singly or in combination of two or more.
When the light emitting device according to the present invention has a hole transporting layer and the above-described second light emitting layer is not a second organic layer, it is preferable that the hole transporting layer is the second organic layer.
The electron transporting layer is usually a layer containing a second organic layer or an electron transporting material, preferably a layer containing an electron transporting material. When the electron transporting layer is a layer containing an electron transporting material, the electron transporting material contained in the electron transporting layer includes, for example, electron transporting materials which the first composition described above may contain. The electron transporting material contained in the electron transporting layer may be contained singly or in combination of two or more.
The hole injection layer is a layer containing a hole injection material. The hole injection material contained in the hole injection layer includes, for example, hole injection materials which the first composition described above may contain. The hole injection material contained in the hole injection layer may be contained singly or in combination of two or more.
The electron injection layer is a layer containing an electron injection material. The electron injection material contained in the electron injection layer includes, for example, electron injection materials which the first composition described above may contain. The electron injection material contained in the electron injection layer may be contained singly or in combination of two or more.
The substrate in the light emitting device may be a substrate that can form an electrode and does not chemically change when forming the organic layer, and is a substrate made of a material such as, for example, glass, plastic, silicon and the like. When an opaque substrate is used, it is preferable that the electrode farthest from the substrate is transparent or semitransparent.
The material for the anode includes, for example, conductive metal oxides and semitransparent metals, preferably, indium oxide, zinc oxide, tin oxide; conductive compounds such as indium·tin·oxide (ITO), indium·zinc·oxide, and the like; a complex of argentine, 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, indium and the like; alloys composed of two or more metals selected from the above metal group; alloys composed of one or more metals selected from the above metal group and one or more metals selected from the group consisting 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.
The anode and the cathode each may take a laminated structure composed of two or more layers.
In the light emitting device according to the present invention, at least one of the anode and the cathode is usually transparent or semitransparent, but it is preferable that the anode is transparent or semitransparent.
The method for forming the anode and the cathode includes, for example, a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method and a laminating method.
The method of forming each layer such as a first 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 the like in the light emitting device according to the present invention includes, for example, a vacuum vapor deposition method from a powder, and a method by film formation from a solution or melted state when a low molecular weight compound is used, and for example, a method by film formation from a solution or melted state when a polymer compound is used.
The first light emitting layer, the second light emitting layer, the hole transporting layer, the electron transporting layer, the hole injection layer and the electron injection layer can be formed by a wet method using inks containing the first ink, the second ink, the 2′-nd ink, and the light emitting material, the hole transporting material, the electron transporting material, the hole injection material and the electron injection material described above, respectively.
In order to obtain planar light emission using a light emitting device, a planar anode and a planar cathode are arranged so that they overlap with each other.
In order to obtain a patterned light emission, there are a method of providing a mask with a patterned window on the surface of a planar light emitting device, a method of forming a layer to be a non-light emitting portion with an extremely large thickness to make it substantially non-luminescent, and a method of forming an anode or a cathode, or both electrodes in a pattern.
By forming a pattern by any of the above-mentioned methods and arranging some electrodes so that they can be turned ON/OFF independently, a segment type display device capable of displaying numbers, characters and the like can be obtained.
In order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other.
Partial color display and multi-color display become possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method of using a color filter or a fluorescence conversion filter.
The dot matrix display device can be passively driven or can be actively driven in combination with TFT or the like. These display devices can be used for displays of computers, televisions, mobile terminals and the like.
The planar light emitting device can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar light source for illumination. If a flexible substrate is used, it can be used as a curved light source and a curved display device.
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples, the polystyrene-equivalent number-average molecular weight (Mn) and the polystyrene-equivalent weight-average molecular weight (Mw) of the polymer compound and its intermediate were determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase.
The polymer compound to be measured or its intermediate was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 μL of the solution was injected into SEC. The mobile phase was run at a flow rate of 1.0 mL/min. PLgel MIXED-B (manufactured by Polymer Laboratories Ltd.) was used as a column. A UV-VIS detector (manufactured by Tosoh Corporation, trade name: UV-8320GPC) was used as a detector.
In the present example, the molecular weight of the constitutional unit in the polymer compound was calculated using the value of Molecular Weight of ChemDraw Pro 13.0 (manufactured by HULINKS INC.).
The compound M1 was synthesized according to a method described in JP-A No. 2011-174062.
The compound M2 was synthesized according to a method described in WO 2005/049546.
The compound M3, the compound M7 and the compound M15 were synthesized according to a method described in WO 2002/045184.
As the compound M4 and the compound M21, commercially available products were used.
The compound M5 was synthesized according to a method described in JP-A No. 2008-106241.
The compounds M6 and M17 to M19 were synthesized according to a method described in JP-A No. 2010-189630.
The compound M8 was synthesized according to a method described in JP-A No. 2010-215886.
The compound M9 was synthesized according to a method described in WO 2011/049421.
The compound M10 was synthesized according to a method described in WO 2015/145871.
The compound M11 was synthesized according to a method described in WO 2009/157424.
The compound M12 was synthesized according to a method described in WO 2016/047536.
The compound M13 was synthesized according to a method described in WO 2013/191088.
The compound M14 and the compound M20 were synthesized according to a method described in WO 2012/086671.
The compound M16 was synthesized according to a method described in JP-A No. 2003-226744.
The compound M22 was synthesized according to a method described in JP-A No. 2012-144722.
The compound M23 was synthesized according to a method described in JP-A No. 2004-143419.
The compound M24 was synthesized according to a method described in WO 2004/060970.
The compound M25 was synthesized according to a method described in JP-A No. 2012-33845.
The compound HM-1 was purchased from Luminescence Technology.
The phosphorescent compound B1 was synthesized according to a method described in WO 2006/121811.
The phosphorescent compound G1 was synthesized according to a method described in WO 2009/131255.
The phosphorescent compound R1 was synthesized according to a method described in JP-A No. 2006-188673.
The phosphorescent compound R2 was synthesized according to a method described in JP-A No. 2008-179617.
The phosphorescent compounds B1, G1, R1 and R2 are represented by the following chemical formulae.
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HTL-1a [compound M1 (2.39 g), compound M2 (1.81 g) and compound M3 (91.4 mg)] shown in Table 2 below and toluene (23 mL) were added and the mixture was heated at 80° C. To this were added bis(tris-o-methoxyphenylphosphine)palladium (II) dichloride (1.9 mg) and a 20% by mass tetraethylammonium hydroxide aqueous solution (23.4 g), then, the mixture was heated at 100° C. and stirred under reflux for 2.5 hours, to form a non-terminal block.
The polymer compound (non-terminal block) present in the reaction liquid had an Mn of 7.6×103 and an Mw of 1.7×104.
To the reaction liquid obtained in the above-described (1) were added a mixture HTL-1b [compound M1 (0.45 g), compound M4 (0.22 g) and compound M5 (0.26 g)] shown in Table 2 below and toluene (22 mL) and a 20% by mass tetraethylammonium hydroxide aqueous solution (26.6 g), and the mixture was heated at 80° C. To this was added bis(tris-o-methoxyphenylphosphine)palladium (II) dichloride (1.0 mg), then, the mixture was heated at 100° C. and stirred under reflux for 4.5 hours, thereby binding the terminal block to the non-terminal block, to form a terminal block.
To the reaction liquid obtained in the above-described (2) was added phenylboronic acid (160 mg) which is an end-capping agent, then, the mixture was heated at 100° C. and stirred under reflux for 16 hours, thereby introducing the end group into the terminal block, to form an end group.
The reaction liquid obtained in the above-described (3) was cooled to room temperature, the aqueous layer was removed, then, washed once with 10% by mass hydrochloric acid, once with a 3% by mass aqueous ammonia solution, and once with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a block copolymer HTL-1 (3.2 g).
The block copolymer HTL-1 had an Mn of 4.9×104 and an Mw of 1.4×105.
The block copolymer HTL-1 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M2 and a constitutional unit derived from the compound M3 at a molar ratio of 40:30:2.5, having a terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M4 and a constitutional unit derived from the compound M5 at a molar ratio of 10:10:7.5, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The block copolymer HTL-1 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-1 satisfies the above-described formulae (i) and (iii).
The block copolymer HTL-2 was synthesized according to a method described in JP-A No. 2012-144722 using a mixture HTL-2a (compound M1, compound M2, compound M3 and compound M5) and a mixture HTL-2b (compound M1 and compound M4) shown in Table 3.
In the synthesis of the block copolymer HTL-2, the non-terminal block had an Mn of 4.1×104 and an Mw of 1.2×105.
The block copolymer HTL-2 had an Mn of 5.4×104 and an Mw of 1.8×105.
The block copolymer HTL-2 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M2, a constitutional unit derived from the compound M3 and a constitutional unit derived from the compound M5 at a molar ratio of 40:30:2.5:7.5, having a terminal block containing a constitutional unit derived from the compound M1 and a constitutional unit derived from the compound M4 at a molar ratio of 10:10, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The block copolymer HTL-2 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-2 satisfies the above-described formulae (i) and (iii).
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HTL-3a [compound M6 (1.46 g) and compound M7 (1.20 g)] shown in Table 4 below, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (2.3 mg) and toluene (30 mL) were added, and the mixture was heated at 80° C. To this was added a 16% by mass tetramethylammonium hydroxide aqueous solution (20.6 g), then, the mixture was stirred at 100° C. for 2.5 hours, to form a non-terminal block.
The polymer compound (non-terminal block) present in the reaction liquid had an Mn of 8.4×103 and an Mw of 1.8×104.
To the reaction liquid obtained in the above-described (1) were added a mixture HTL-3b [compound M6 (0.146 g), compound M5 (0.174 g) and compound M8 (0.150 g)] shown in Table 4 below, bis(tris-o-methoxyphenylphosphine)palladium (II) dichloride (0.57 mg) and toluene (10 mL), and the mixture was stirred at 100° C. for 4.5 hours, thereby binding the terminal block to the non-terminal block, to form a terminal block.
To the reaction liquid obtained in the above-described (2) were added phenylboronic acid (160 mg) which is an end-capping agent and bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (2.9 mg), then, the mixture was heated at 100° C. and stirred under reflux for 16 hours, thereby introducing the end group into the terminal block, to form an end group.
The reaction liquid obtained in the above-described (3) was cooled to room temperature, the aqueous layer was removed, and washed once with 10% by mass hydrochloric acid, once with a 3% by mass aqueous ammonia solution, and once with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a block copolymer HTL-3 (0.81 g).
The block copolymer HTL-3 had an Mn of 5.5×104 and an Mw of 3.7×105.
The block copolymer HTL-3 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M6 and a constitutional unit derived from the compound M7 at a molar ratio of 45:40, having a terminal block containing a constitutional unit derived from compound M6, a constitutional unit derived from compound M5 and a constitutional unit derived from compound M8 at a molar ratio of 5:5:5, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The block copolymer HTL-3 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-3 satisfies the above-described formulae (i) and (iii).
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HTL-4a [compound M1 (2.08 g) and compound M2 (1.75 g)] shown in Table 5 below, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.17 mg) and toluene (35 mL) were added, and the mixture was heated at 80° C. To this was added a 20% by mass tetraethylammonium hydroxide aqueous solution (23.4 g), then, the mixture was stirred at 100° C. for 2.5 hours, to form a non-terminal block.
The polymer compound (non-terminal block) present in the reaction liquid had an Mn of 7.4×103 and an Mw of 1.7×104.
To the reaction liquid obtained in the above-described (1) were added a mixture HTL-4b [compound M1 (1.35 g), compound M9 (0.328 g) and compound M2 (1.05 g)] shown in Table 5 below, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.17 mg), a 20% by mass tetraethylammonium hydroxide aqueous solution (26.6 g) and toluene (40 mL), and the mixture was stirred at 100° C. for 4.5 hours, thereby binding the terminal block to the non-terminal block, to form a terminal block.
To the reaction liquid obtained in the above-described (2) were added M12 (352 mg) which is an end-capping agent and bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.16 mg), then, the mixture was heated at 100° C. and stirred under reflux for 16 hours, thereby introducing the end group into the terminal block, to form an end group.
The reaction liquid obtained in the above-described (3) was cooled to room temperature, the aqueous layer was removed, and washed once with 10% by mass hydrochloric acid, once with a 3% by mass aqueous ammonia solution, and once with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a block copolymer HTL-4 (4.47 g).
The block copolymer HTL-4 had an Mn of 3.3×104 and an Mw of 1.6×105.
The block copolymer HTL-4 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1 and a constitutional unit derived from the compound M2 at a molar ratio of 30:25, having a terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M9 and a constitutional unit derived from the compound M2 at a molar ratio of 20:10:15, and having a crosslinkable group derived from the compound M12 as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The block copolymer HTL-4 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-4 satisfies the above-described formulae (i) and (iii).
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HTL-5a [compound M1 (0.407 g), compound M10 (1.39 g), and compound M2 (1.37 g)] shown in Table 6 below, bis(tris-o-methoxyphenylphosphine)palladium (II) dichloride (0.29 mg) and toluene (23 mL) were added, and the mixture was heated at 80° C. To this was added a 20% by mass tetraethylammonium hydroxide aqueous solution (15.4 g), then, the mixture was stirred at 100° C. for 2.5 hours, to form a non-terminal block.
The polymer compound (non-terminal block) present in the reaction liquid had an Mn of 6.6×103 and an Mw of 1.8×104.
To the reaction liquid obtained in the above-described (1) were added a mixture HTL-5b [compound M13 (0.241 g), compound M2 (0.556 g) and compound M11 (0.248 g)] shown in Table 6 below, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.33 mg), a 20% by mass tetraethylammonium hydroxide aqueous solution (14.5 g) and toluene (29 mL), and the mixture was stirred at 100° C. for 4.5 hours, thereby binding the terminal block to the non-terminal block, to form a terminal block.
To the reaction liquid obtained in the above-described (2) were added phenylboronic acid (109 mg) which is an end capping agent and bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.07 mg), and the mixture was heated at 100° C. and stirred under reflux for 16 hours, thereby introducing the end group into the terminal block, to form an end group.
The reaction liquid obtained in the above-described (3) was cooled to room temperature, the aqueous layer was removed, then, washed once with 10% by mass hydrochloric acid, once with a 3% by mass aqueous ammonia solution, and once with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a block copolymer HTL-5 (2.72 g).
The block copolymer HTL-5 had an Mn of 3.2×104 and an Mw of 1.6×105.
The block copolymer HTL-5 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M10 and a constitutional unit derived from the compound M2 at a molar ratio of 10:30:33.4, having a terminal block containing a constitutional unit derived from the compound M13, a constitutional unit derived from the compound M2 and a constitutional unit derived from the compound M11 at a molar ratio of 10:13.6:3, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials. The block copolymer HTL-5 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-5 satisfies the above-described formulae (i) and (iii).
The polymer compound HTL-C1 was synthesized according to a method described in JP-A No. 2013-131995 using a mixture HTL-C1a (compound M15, compound M3, compound M16 and compound M9) shown in Table 7. The polymer compound HTL-C1 had an Mn of 7.8×104 and an Mw of 2.6×105.
The polymer compound HTL-C1 is a random copolymer (a copolymer not having terminal block and non-terminal block) containing a constitutional unit derived from the compound M15, a constitutional unit derived from the compound M3, a constitutional unit derived from the compound M16 and a constitutional unit derived from the compound M9 at a molar ratio of 50:12.5:30:7.5, and has a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The polymer compound HTL-C2 was synthesized according to a method described in JP-A No. 2015-110751 using a mixture HTL-C2a (compound M6, compound M7, compound M5 and compound M8) shown in Table 8 below.
The polymer compound HTL-C2 had an Mn of 5.9×104 and an Mw of 1.8×105.
The polymer compound HTL-C2 is a random copolymer (a copolymer not having terminal block and non-terminal block) containing a constitutional unit derived from the compound M6, a constitutional unit derived from the compound M7, a constitutional unit derived from the compound M5 and a constitutional unit derived from the compound M8 at a molar ratio of 50:40:5:5, and has a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
(1) Formation of non-terminal block
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HTL-C3a [compound M1 (0.694 g) and compound M2 (1.05 g)] shown in Table 9 below, bis(tris-o-methoxyphenylphosphine)palladium (II) dichloride (0.10 mg) and toluene (35 mL) were added, and the mixture was heated at 80° C. To this was added a 20% by mass tetraethylammonium hydroxide aqueous solution (23.4 g), then, the mixture was stirred at 100° C. for 2.5 hours, to form a non-terminal block.
The polymer compound (non-terminal block) present in the reaction liquid had an Mn of 3.2×103 and an Mw of 7.8×103.
To the reaction liquid obtained in the above-described (1) were added a mixture HTL-C3b [compound M1 (2.38 g), compound M9 (0.328 g) and compound M2 (1.75 g)] shown in Table 9 below, bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.24 mg), a 20% by mass tetraethylammonium hydroxide aqueous solution (26.6 g) and toluene (40 mL), and the mixture was stirred at 100° C. for 4.5 hours, thereby binding the terminal block to the non-terminal block, to form a terminal block.
To the reaction liquid obtained in the above-described (2) were added M12 (352 mg) which is an end-capping agent and bis(tris-o-methoxyphenylphosphine)palladium(II) dichloride (0.24 mg), and the mixture was heated at 100° C. and stirred under reflux for 16 hours, thereby introducing the end group into the terminal block, to form an end group.
(4) Post treatment
The reaction liquid obtained in the above-described (3) was cooled to room temperature, the aqueous layer was removed, then, washed once with 10% by mass hydrochloric acid, once with a 3% by mass aqueous ammonia solution, and once with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a block copolymer CP3 (4.55 g).
The block copolymer HTL-C3 had an Mn of 3.4×104 and an Mw of 1.3×105.
The block copolymer HTL-C3 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1 and a constitutional unit derived from the compound M2 at a molar ratio of 10:15, having a terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M9 and a constitutional unit derived from the compound M2 at a molar ratio of 40:10:25, and having a crosslinkable group derived from the compound M12 as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The block copolymer HTL-C3 does not satisfy the above-described formulae (i), (ii) and (iii).
(1) Synthesis of block copolymer HTL-C4
The block copolymer HTL-C4 was synthesized according to a method described in JP-A No. 2016-111355 using a mixture HTL-C4a (compound M1, compound M2 and compound M11) shown in Table 10 below, and a mixture HTL-C4b (compound M10, compound M13 and compound M2) shown in Table 10 below.
In the synthesis of the block copolymer HTL-C4, the non-terminal block had an Mn of 2.8×103 and an Mw of 5.8×103. The block copolymer HTL-C4 had an Mn of 3.3×104 and an Mw of 1.7×105.
The block copolymer HTL-C4 is a block copolymer having a non-terminal block containing a constitutional unit derived from the compound M1, a constitutional unit derived from the compound M2, and a constitutional unit derived from the compound M11 at a molar ratio of 10:13.6:3, having a terminal block containing a constitutional unit derived from the compound M10, a constitutional unit derived from the compound M13, and a constitutional unit derived from the compound M2 at a molar ratio of 30:10:33.4, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials. The block copolymer CP4 contains an end group, a terminal block, a non-terminal block, a terminal block and an end group in this order. The block copolymer HTL-C4 does not satisfy the above-described formulae (i), (ii) and (iii).
An inert gas atmosphere was prepared in the reaction vessel, then, a mixture HP-1a [compound M6 (1.04 g) and compound M17 (2.11 g)] shown in Table 11 below and toluene (170 g) were added, and the mixture was heated at 80° C. To this were added palladium acetate (0.77 mg), tris(2-methoxyphenyl)phosphine (4.7 mg) and a 20% by mass tetraethylammonium hydroxide aqueous solution (58 g), and the mixture was stirred under reflux for 3 hours, to obtain a reaction liquid.
The temperature of the resultant reaction liquid was adjusted to 55° C., then, a mixture HP-1b [compound M6 (7.00 g) and compound M14 (8.53 g)] shown in Table 11 below and toluene (39 g) were added, and the mixture was heated at 80° C. To this were added palladium acetate (1.5 mg) and tris(2-methoxyphenyl)phosphine (9.3 mg), then, the mixture was stirred under reflux for 6 hours, to obtain a reaction liquid. To this were added phenylboronic acid (0.81 g) which is an end capping agent, palladium acetate (1.9 mg), tris(2-methoxyphenyl)phosphine (12 mg), and a 20% by mass tetraethylammonium hydroxide aqueous solution (58 g), then, the mixture was stirred under reflux for 15 hours, to form an end group.
The temperature of the resultant reaction liquid was adjusted to 40° C., then, to this was added an aqueous sodium diethyldithiocarbamate solution, and the mixture was stirred at 80° C. for 2 hours. The reaction liquid was cooled to room temperature, the aqueous layer was removed, then, washed twice with 3.6% by mass hydrochloric acid, twice with a 2.5% by mass aqueous ammonia solution, and twice with ion-exchanged water. When the resultant solution was added dropwise to methanol, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column in series through which toluene had been passed previously. When the purified liquid was added dropwise to methanol and stirred, a precipitate was generated, so the precipitate was collected by filtration and dried, to obtain a polymer compound HP-1 (8.4 g). The polymer compound HP-1 had an Mn of 4.4×104 and an Mw of 1.1×105.
The polymer compound HP-1 is a polymer compound having a block constituted of a constitutional unit derived from the compound M6 and a constitutional unit derived from the compound M17 at a molar ratio of 6.5:10, having a block constituted of a constitutional unit derived from the compound M6 and a constitutional unit derived from the compound M14 at a molar ratio of 43.5:40, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The polymer compound HP-2 was synthesized according to a method described in JP-A No. 2012-131995 using a mixture HP-2a (compound M18, compound M3 and compound M17) and a mixture HP-2b (compound M18, compound M19 and compound M3) shown in Table 12. The polymer compound HP-2 had an Mn of 9.0×103 and an Mw of 2.5×104.
The polymer compound HP-2 is a polymer compound having a block containing a constitutional unit derived from the compound M18, a constitutional unit derived from the compound M3 and a constitutional unit derived from the compound M17 at a molar ratio of 25:10:10, having a block constituted of a constitutional unit derived from the compound M18, a constitutional unit derived from the compound M19 and a constitutional unit derived from the compound M3 at a molar ratio of 15:10:30, and having a phenyl group as an end group, according to the theoretical values determined from the amounts of the charging raw materials.
The polymer compound HP-3 was synthesized according to a method described in JP-A No. 2012-036388 using a mixture HP-3a (compound M6, compound M14 and compound M17) shown in Table 13. The polymer compound HP-3 had an Mn of 9.6×104 and an Mw of 2.2×105.
The polymer compound HP-3 is a random copolymer containing a constitutional unit derived from the compound M6, a constitutional unit derived from the compound M14 and a constitutional unit derived from the compound M17 at a molar ratio of 50:40:10 according to the theoretical values determined from the amounts of the charging raw materials, and it has a phenyl group as an end group.
The polymer compound HP-4 was synthesized according to a method described in JP-A No. 2010-189630 using a mixture HP-4a (compound M18, compound M19, compound M3 and compound M17) shown in Table 14. The polymer compound HP-4 had an Mn of 9.2×104 and an Mw of 2.8×105.
The polymer compound HP-4 is a random copolymer containing a constitutional unit derived from the compound M18, a constitutional unit derived from the compound M19, a constitutional unit derived from the compound M3 and a constitutional unit derived from the compound M17 at a molar ratio of 40:10:40:10 according to the theoretical values determined from the amounts of the charging raw materials, and it has a phenyl group as an end group.
The polymer compound HP-5 was synthesized according to a method described in JP-A No. 2015-35600 using a mixture HP-5a (compound M20, compound M21, compound M22, compound M23 and compound M24) shown in Table 15.
The polymer compound HP-5 had an Mn of 1.0×105 and an Mw of 2.4×105.
The polymer compound HP-5 is a random copolymer (a copolymer not having terminal block and non-terminal block) containing a constitutional unit derived from the compound M20, a constitutional unit derived from the compound M21, a constitutional unit derived from the compound M22, a constitutional unit derived from the compound M23 and a constitutional unit derived from the compound M24 at a molar ratio of 36:14:45:4:1 according to the theoretical values determined from the amounts of the charging raw materials, and it has a phenyl group as an end group.
An inert gas atmosphere was prepared in the reaction vessel, then, the compound M25 (9.23 g), the compound M6 (4.58 g), dichlorobis(tris-o-methoxyphenylphosphine)palladium (8.6 mg), methyltrioctyl ammonium chloride (manufactured by Sigma Aldrich, trade name: Aliquat336 (registered trademark)) (0.098 g) and toluene (175 mL) were added, and the mixture was heated at 105° C. Then, to this was added dropwise a 12% by mass sodium carbonate aqueous solution (40.3 mL), and the mixture was refluxed for 29 hours. Then, to this were added phenylboronic acid (0.47 g) and dichlorobis(tris-o-methoxyphenylphosphine)palladium (8.7 mg), and the mixture was refluxed for 14 hours. Then, to this was added an aqueous sodium diethyldithiocarbamate solution, and the mixture was stirred at 80° C. for 2 hours. When the resultant reaction liquid was cooled and then added dropwise to methanol, a precipitate was generated. The resultant precipitate was collected by filtration, washed with methanol and water, and dried. The resultant solid was dissolved in chloroform and purified by passing through an alumina column and a silica gel column in series through which chloroform had been passed previously. When the resultant purified liquid was added dropwise to methanol and stirred, a precipitate was generated. The resultant precipitate was collected by filtration and dried, to obtain a polymer compound ETL-1a (7.15 g). The polymer compound ETL-1a had an Mn of 3.2×104 and an Mw of 6.0×104.
The polymer compound ETL-1a is a random copolymer containing a constitutional unit derived from the compound M25 and a constitutional unit derived from the compound M6 at a molar ratio of 50:50 according to the theoretical values determined from the amounts of the charging raw materials, and it has a phenyl group as an end group.
An argon gas atmosphere was prepared in the reaction vessel, then, the polymer compound ETL-1a (3.1 g), tetrahydrofuran (130 mL), methanol (66 mL), cesium hydroxide monohydrate (2.1 g) and water (12.5 mL) were added, and the mixture was stirred at 60° C. for 3 hours. Then, to this was added methanol (220 mL) and the mixture was stirred for 2 hours. The resultant reaction mixture was concentrated, then added dropwise to isopropyl alcohol and stirred, to generate a precipitate. The resultant precipitate was collected by filtration and dried, to obtain a polymer compound ETL-1 (3.5 g). According to 1H-NMR analysis of the polymer compound ETL-1, the signal of an ethyl ester moiety in the polymer compound ETL-1 disappeared, confirming that the reaction was completed.
The polymer compound ETL-1 is a random copolymer containing a constitutional unit represented by the following formula and a constitutional unit derived from the compound M6 at a molar ratio of 50:50 according to the theoretical values determined from the amounts of the charging raw materials of the polymer compound ETL-1, and it has a phenyl group as an end group.
Table 16 shows the calculation results of the total number of each constitutional unit in the block copolymers HTL-1 to 5 and HTL-C1 to C4.
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, AQ-1200 (manufactured by Plectronics) as a hole injection material was spin-coated to form a film with a thickness of 50 nm. The film was heated at 170° C. for 15 minutes on a hot plate under an air atmosphere, to form a hole injection layer.
The block copolymer HTL-1 was dissolved in xylene at a concentration of 0.7% by mass. The resultant xylene solution was spin-coated on the hole injection layer to form a film having a thickness of 20 nm which was then heated at 180° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere, to form a second organic layer (hole transporting layer). By this heating, the block copolymer HTL-1 became a crosslinked product.
The polymer compound HP-1 and the phosphorescent compound G1 (polymer compound HP-1/phosphorescent compound G1=70% by mass/30% by mass) were dissolved in xylene at a concentration of 2% by mass. The resultant xylene solution was spin-coated on the second organic layer to form a film having a thickness of 80 nm which was then heated at 180° C. for 10 minutes under a nitrogen gas atmosphere, to form a first organic layer (first light emitting layer).
The substrate carrying the first organic layer formed thereon was placed in a vapor deposition machine and its inner pressure was reduced to 1.0×10−4 Pa or less, then, sodium fluoride was vapor-deposited with a thickness of about 4 nm on the first organic layer, then, aluminum was vapor-deposited with a thickness of about 80 nm on the sodium fluoride layer, as a cathode. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D3 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order.
EL light emission was observed by applying voltage to the light emitting device D3. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 473.9 hours.
A light emitting device D1 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D1 except that the “polymer compound HP-3” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D4. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and was found to be 71.5 hours.
A light emitting device D2 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “block copolymer HTL-2” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3, and further, the “polymer compound HP-3” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D2. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 37.4 hours.
A light emitting device D4 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “block copolymer HTL-2” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D4. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 361.6 hours.
A light emitting device D5 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “polymer compound HP-2” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D5. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 108.6 hours.
A light emitting device D6 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “block copolymer HTL-2” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3, and further, the “polymer compound HP-2” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D6. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 95.5 hours.
A light emitting device D7 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “polymer compound HP-4” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D7. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 24.9 hours.
A light emitting device D8 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “block copolymer HTL-2” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3, and further, the “polymer compound HP-4” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device D8. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current and the time until the luminance reached 95% of the initial luminance was measured and found to be 29.1 hours.
A light emitting device CD1 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “polymer compound HTL-C1” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3, and further, the “polymer compound HP-2” was used instead of the “polymer compound HP-1” in (Formation of first organic layer) of Example D3. EL light emission was observed by applying voltage to the light emitting device CD1. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.30, 0.64). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current, and the time until the luminance reached 95% of the initial luminance was measured and found to be 4.6 hours.
A light emitting device D9 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D3 except that the “block copolymer HTL-4” was used instead of the “block copolymer HTL-1” in (Formation of second organic layer) of Example D3, and further, (Formation of first organic layer) of Example D3 was changed to (Formation-D9 of first organic layer) describe below. EL light emission was observed by applying voltage to the light emitting device D9. The CIE chromaticity coordinates at 3000 cd/m2 were (x, y)=(0.66, 0.32). After setting the current value so that the initial luminance was 3000 cd/m2, the device was driven at constant current, and the time until the luminance reached 65% of the initial luminance (hereinafter, also referred to as “LT65”) was measured. The results are shown in Table 18.
The polymer compound HP-5 and the phosphorescent compound R1 (polymer compound HP-5/phosphorescent compound R1=92.5% by mass/7.5% by mass) were dissolved in xylene at a concentration of 2% by mass. The resultant xylene solution was spin-coated on the second organic layer to form a film having a thickness of 60 nm which was then heated at 180° C. for 10 minutes under a nitrogen gas atmosphere, to form a first organic layer (first light emitting layer).
A light emitting device CD2 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer) and a cathode are laminated in this order was fabricated in the same manner as in Example D9 except that the “block copolymer HTL-C3” was used instead of the “block copolymer HTL-4” in (Formation of second organic layer) of Example D9. EL light emission was observed by applying voltage to the light emitting device CD2. The CIE chromaticity coordinates at 3000 cd/m2 were (x, y)=(0.66, 0.32). The device was driven at constant current at an initial luminance of 3000 cd/m2, and LT65 was measured. The results are shown in Table 18.
The results of Example D9 and Comparative Example CD2 are shown in Table 18. The relative value of LT65 of the light emitting device D9 when the LT65 of the light emitting device CD2 is taken as 1.0 is shown.
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, AQ-1200 (manufactured by Plectronics) as a hole injection material was spin-coated to form a film with a thickness of 50 nm. The film was heated at 170° C. for 15 minutes on a hot plate under an air atmosphere, to form a hole injection layer.
The block copolymer HTL-3 was dissolved in xylene at a concentration of 0.7% by mass. The resultant xylene solution was spin-coated on the hole injection layer to form a film having a thickness of 20 nm which was then heated at 180° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere, to form a second organic layer (hole transporting layer). By this heating, the block copolymer HTL-3 became a crosslinked product.
The compound HM-1 and the phosphorescent compound R2 (compound HM-1/phosphorescent compound R2=92.5% by mass/7.5% by mass) were dissolved in xylene at a concentration of 2% by mass. The resultant xylene solution was spin-coated on the second organic layer to form a film having a thickness of 60 nm which was then heated at 180° C. for 10 minutes under a nitrogen gas atmosphere, to form a first organic layer (first light emitting layer).
The polymer compound ETL-1 was dissolved at a concentration of 0.25% by mass 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 first organic layer to form a film having a thickness of 10 nm which was then 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 its inner pressure was reduced to 1.0×10−4 Pa or less, then, sodium fluoride was vapor-deposited with a thickness of about 4 nm on the electron transporting layer, then, aluminum was vapor-deposited with a thickness of about 80 nm on the sodium fluoride layer, as a cathode. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D10 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order.
EL light emission was observed by applying voltage to the light emitting device D10. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.61, 0.40). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current, and the time until the luminance reached 80% of the initial luminance (hereinafter, also referred to as “LT80”) was measured. The results are shown in Table 19.
A light emitting device CD3 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order was fabricated in the same manner as in Example D10 except that the “polymer compound HTL-C2” was used instead of the “block copolymer HTL-3” in (Formation of second organic layer) of Example D10.
EL light emission was observed by applying voltage to the light emitting device CD3. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.61, 0.40). The device was driven at constant current at an initial luminance of 1000 cd/m2, and LT80 was measured. The results are shown in Table 19.
The results of Example D10 and Comparative Example CD3 are shown in Table 19. The relative value of LT80 of the light emitting device D10 when the LT80 of the light emitting device CD3 is taken as 1.00 is shown.
A light emitting device D11 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order was fabricated in the same manner as in Example D10 except that the “compound HM-1 and phosphorescent compound B1 (compound HM-1/phosphorescent compound B1=75% by mass/25% by mass)” were used instead of the “compound HM-1 and phosphorescent compound R2 (compound HM-1/phosphorescent compound R2=92.5% by mass/7.5% by mass)” in (Formation of first organic layer) of Example D10.
EL light emission was observed by applying voltage to the light emitting device D11. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.23, 0.42). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current, and the time until the luminance reached 90% of the initial luminance (hereinafter, also referred to as “LT90”) was measured. The results are shown in Table 20.
A light emitting device CD4 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order was fabricated in the same manner as in Example D10 except that the “polymer compound HTL-C2” was used instead of the “block copolymer HTL-3” in (Formation of second organic layer) of Example D10, and further, the “compound HM-1 and phosphorescent compound B1 (compound HM-1/phosphorescent compound B1=75% by mass/25% by mass)” were used instead of the “compound HM-1 and phosphorescent compound R2 (compound HM-1/phosphorescent compound R2=92.5% by mass/7.5% by mass)” in (Formation of first organic layer) of Example D10.
EL light emission was observed by applying voltage to the light emitting device CD4. The CIE chromaticity coordinates (x, y) at 1000 cd/m2 were (0.24, 0.43). The device was driven at constant current at an initial luminance of 1000 cd/m2, and LT90 was measured. The results are shown in Table 20.
The results of Example D11 and Comparative Example CD4 are shown in Table 20. The relative value of LT90 of the light emitting device D11 when the LT90 of the light emitting device CD4 is taken as 1.0 is shown.
A light emitting device D12 in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order was fabricated in the same manner as in Example D10 except that the “compound HM-1, phosphorescent compound B1, phosphorescent compound G1 and phosphorescent compound R1 (compound HM-1/phosphorescent compound B1/phosphorescent compound G1/phosphorescent compound R1=73.9% by mass/25% by mass/1% by mass/0.1% by mass)” were used instead of the “compound HM-1 and phosphorescent compound R2 (compound HM-1/phosphorescent compound R2=92.5% by mass/7.5% by mass) in (Formation of first organic layer) of Example D10.
EL light emission was observed by applying voltage to the light emitting device D12. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.26, 0.47). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current, and the time until the luminance reached 95% of the initial luminance (hereinafter, also referred to as “LT95”) was measured. The results are shown in Table 21.
A light emitting device CDS in which an anode, a hole injection layer, a hole transporting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order was fabricated in the same manner as in Example D10 except that the “polymer compound HTL-C2” was used instead of the “block copolymer HTL-3” in (Formation of second organic layer) of Example D10, and further, the “compound HM-1, Phosphorescent compound B1, phosphorescent compound G1 and phosphorescent compound R1 (compound HM-1/phosphorescent compound B1/phosphorescent compound G1/phosphorescent compound R1=73.9% by mass/25% by mass/1% by mass/0.1% by mass)” were used instead of the “compound HM-1 and phosphorescent compound R2 (compound HM-1/phosphorescent compound R2=92.5% by mass/7.5% by mass)” in (Formation of first organic layer) of Example D10.
EL light emission was observed by applying voltage to the light emitting device CDS. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.26, 0.47). The device was driven at constant current at an initial luminance of 1000 cd/m2, and LT95 was measured. The results are shown in Table 21.
The results of Example D12 and Comparative Example CDS are shown in Table 21. The relative value of LT95 of the light emitting device D12 when the LT95 of the light emitting device CDS is taken as 1.0 is shown.
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, AQ-1200 (manufactured by Plectronics) as a hole injection material was spin-coated to form a film with a thickness of 50 nm. The film was heated at 170° C. for 15 minutes on a hot plate under an air atmosphere, to form a hole injection layer.
The block copolymer HTL-5 was dissolved in xylene at a concentration of 0.7% by mass. The resultant xylene solution was spin-coated on the hole injection layer to form a film having a thickness of 20 nm which was then heated at 180° C. for 60 minutes on a hot plate under a nitrogen gas atmosphere, to form a second organic layer (second light emitting layer). By this heating, the block copolymer HTL-5 became a crosslinked product.
The compound HM-1 and the phosphorescent compound B1 (compound HM-1/phosphorescent compound B1=75% by mass/25% by mass) were dissolved in xylene at a concentration of 2% by mass. The resultant xylene solution was spin-coated on the second organic layer to form a film having a thickness of 60 nm which was then heated at 180° C. for 10 minutes under a nitrogen gas atmosphere, to form a first organic layer (first light emitting layer).
The polymer compound ETL-1 was dissolved at a concentration of 0.25% by mass 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 first organic layer to form a film having a thickness of 10 nm which was then 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 its inner pressure was reduced to 1.0×10−4 Pa or less, then, sodium fluoride was vapor-deposited with a thickness of about 4 nm on the electron transporting layer, then, aluminum was vapor-deposited with a thickness of about 80 nm on the sodium fluoride layer, as a cathode. After vapor deposition, sealing was performed using a glass substrate, to fabricate a light emitting device D13 in which an anode, a hole injection layer, a second light emitting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer and a cathode are laminated in this order.
EL light emission was observed by applying voltage to the light emitting device D13. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.49, 0.46). After setting the current value so that the initial luminance was 1000 cd/m2, the device was driven at constant current, and the time until the luminance reached 98% of the initial luminance (hereinafter, also referred to as “LT98”) was measured. The results are shown in Table 22.
A light emitting device CD6 in which an anode, a hole injection layer, a second light emitting layer (second organic layer), a first light emitting layer (first organic layer), an electron transporting layer, and a cathode are laminated in this order was fabricated in the same manner as in Example D13 except that “block copolymer HTL-C4” was used instead of “block copolymer HTL-5” in (Formation of second organic layer) of Example D13.
EL light emission was observed by applying voltage to the light emitting device CD6. The CIE chromaticity coordinates at 1000 cd/m2 were (x, y)=(0.50, 0.45). LT98 was measured when driving at constant current at an initial luminance of 1000 cd/m2. The results are shown in Table 22.
The results for Example D13 and Comparative Example CD6 are shown in Table 22. The relative value of LT98 of the light emitting device D13 when the LT98 of the light emitting device CD6 is taken as 1.0 is shown.
According to the present invention, it is possible to provide a light emitting device excellent in luminance life.
10: light emitting device, 11: anode, 12: second organic layer, 13: first organic layer, 14: cathode.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-085560 | Apr 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/017476 | 4/24/2019 | WO | 00 |
