WO2018216799A1 - Composition, material for organic electroluminescent element, composition film, organic electroluminescent element, and electronic equipment - Google Patents
Composition, material for organic electroluminescent element, composition film, organic electroluminescent element, and electronic equipment Download PDFInfo
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- WO2018216799A1 WO2018216799A1 PCT/JP2018/020142 JP2018020142W WO2018216799A1 WO 2018216799 A1 WO2018216799 A1 WO 2018216799A1 JP 2018020142 W JP2018020142 W JP 2018020142W WO 2018216799 A1 WO2018216799 A1 WO 2018216799A1
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- AYVWUPXIMBDBSX-UHFFFAOYSA-N Cc(cc1)cc(-c2ccccc2)c1-c1ccccc1 Chemical compound Cc(cc1)cc(-c2ccccc2)c1-c1ccccc1 AYVWUPXIMBDBSX-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- ZTCVMWVDVXVZPL-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c(cc2)ccc2-[n]2c(ccc(-c3ccc(c4ccccc4[n]4-c5ccccc5)c4c3)c3)c3c3c2cccc3)n1 Chemical compound c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c(cc2)ccc2-[n]2c(ccc(-c3ccc(c4ccccc4[n]4-c5ccccc5)c4c3)c3)c3c3c2cccc3)n1 ZTCVMWVDVXVZPL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present invention relates to a composition, a material for an organic electroluminescence element, a composition film, an organic electroluminescence element, and an electronic apparatus.
- Patent Document 1 uses a compound having both a carbazolyl group derivative structure and a nitrogen-containing heteroaromatic ring as a first host, and a specific having a condensed aryl group, dibenzofuranyl group, or dibenzothienyl group as a second host
- An organic electroluminescent device using a biscarbazole derivative having a structure is described. According to this organic electroluminescence element, Patent Document 1 describes that it has a long life while maintaining high efficiency.
- An object of the present invention is to provide a composition capable of stably depositing a ratio of materials from one vapor deposition source while maintaining the performance of the organic electroluminescence element, and an organic electroluminescence element including the composition Providing a material for use, providing a composition film containing the composition, providing an organic electroluminescence device containing the composition, and providing an electronic device including the organic electroluminescence device. .
- Compositions containing a second compound are provided.
- R 1 , R 2 , R 3 and R 4 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- a is 0, 1, 2, 3 or 4.
- b is 0, 1, 2 or 3.
- c is 0, 1, 2 or 3.
- d is 0, 1, 2, 3 or 4.
- the plurality of R 1 are the same as or different from each other.
- the plurality of R 2 are the same as or different from each other.
- the plurality of R 3 are the same as or different from each other.
- the plurality of R 4 are the same as or different from each other.
- One of A 1 and A 2 is a substituent represented by the following general formula (1a), and the other is a substituent including a partial structure represented by the following general formula (1b).
- X 1, X 2, X 3, X 4 and X 5 are each independently, .R X indicating the CR X or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R X are the same as or different from each other.
- X 6, X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group. At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- R Z is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R Z are the same as or different from each other. )
- R 5 , R 6 , R 7 and R 8 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- g 0, 1, 2 or 3.
- h 0, 1, 2, 3 or 4.
- the plurality of R 5 are the same as or different from each other.
- the plurality of R 6 are the same as or different from each other.
- the plurality of R 7 are the same as or different from each other.
- the plurality of R 8 are the same as or different from each other.
- One of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b).
- R 9 represents a halogen atom, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- i is 0, 1, 2, 3, 4 or 5.
- R 10 , R 11 , R 12 and R 13 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- l is 0, 1, 2, 3, 4 or 5.
- m is 0, 1, 2, 3, 4 or 5.
- the plurality of R 10 are the same as or different from each other.
- the plurality of R 11 are the same as or different from each other.
- the plurality of R 12 are the same as or different from each other.
- the plurality of R 13 are the same as or different from each other.
- a material for an organic electroluminescence device comprising the composition according to one aspect of the present invention.
- composition film including the composition according to the above-described aspect of the present invention.
- An organic electroluminescent device comprising:
- the electron transport zone is provided with an organic electroluminescence device including the composition according to one embodiment of the present invention.
- an electronic device equipped with the organic electroluminescence element according to one aspect of the present invention described above.
- a composition capable of stably depositing a ratio of materials from one deposition source while maintaining the performance of the organic electroluminescence device, and to provide an organic including the composition.
- composition is a composition in which two or more compounds are mixed.
- the composition according to this embodiment contains at least a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2).
- the form of the composition according to the present embodiment is not particularly limited.
- Examples of the form of the composition according to this embodiment include solids, powders, solutions, and films.
- the composition according to this embodiment is a solid, it may be formed into a pellet.
- the first compound is represented by the following general formula (1).
- R 1 , R 2 , R 3 and R 4 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- a is 0, 1, 2, 3 or 4.
- b is 0, 1, 2 or 3.
- c is 0, 1, 2 or 3.
- d is 0, 1, 2, 3 or 4.
- the plurality of R 1 are the same as or different from each other.
- the plurality of R 2 are the same as or different from each other.
- the plurality of R 3 are the same as or different from each other.
- the plurality of R 4 are the same as or different from each other.
- One of A 1 and A 2 is a substituent represented by the following general formula (1a), and the other is a substituent including a partial structure represented by the following general formula (1b).
- X 1, X 2, X 3, X 4 and X 5 are each independently, .R X indicating the CR X or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R X are the same as or different from each other.
- X 6, X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group. At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- R Z is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R Z are the same as or different from each other. )
- X 1 , X 2 , X 3 , X 4 and X 5 are preferably CR X.
- R X is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group;
- the plurality of R X are the same as or different from each other.
- a, b, c, and d are preferably 0.
- the first compound is represented by the following general formula (1A).
- one of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is a substituent represented by the following general formula (1c). Is preferred.
- X 6, X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group. At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 21 , X 22 and X 23 are each independently shows a CR Z or a nitrogen atom.
- R Z is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R Z are the same as or different from each other. At least one of X 19 , X 20 , X 21 , X 22 and X 23 is CR Z , and at least one R Z is a single bond bonded to *. )
- X 6 , X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom, Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group. At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 22 and X 23 are Each independently represents CR 2 Z or a nitrogen atom.
- X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 20 , X 21 , X 22 and X 23 each independently represents CRZ or a nitrogen atom.
- X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 21 , X 22 and X 23 each independently represents CRZ or a nitrogen atom.
- R Z is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- the plurality of R Z are the same as or different from each other. )
- the first compound is a compound represented by the following general formula (3).
- R 1 , R 2 , R 3 , R 4 , R 14 and R 15 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- a is 0, 1, 2, 3 or 4.
- b is 0, 1, 2 or 3.
- c is 0, 1, 2 or 3.
- d is 0, 1, 2, 3 or 4.
- p is 0, 1, 2, 3, 4 or 5.
- q is 0, 1, 2, 3, 4 or 5.
- the plurality of R 1 are the same as or different from each other.
- the plurality of R 2 are the same as or different from each other.
- the plurality of R 3 are the same as or different from each other.
- the plurality of R 4 are the same as or different from each other.
- p is 2 or more
- the plurality of R 14 are the same as or different from each other.
- q is 2 or more
- the plurality of R 15 are the same as or different from each other.
- B 1 and B 2 represent a substituent represented by the following general formula (4). r is 0 or 1.
- X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom.
- R Y is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- R 16 and R 17 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
- t is 0, 1, 2, 3, 4 or 5.
- u is 0, 1, 2, 3, 4 or 5.
- the plurality of R 16 are the same as or different from each other.
- u is 2 or more, the plurality of R 17 are the same as or different from each other.
- the first compound is represented by the following general formula (3A).
- R 14 and R 15 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- p is 0, 1, 2, 3, 4 or 5.
- q is 0, 1, 2, 3, 4 or 5.
- the plurality of R 14 are the same as or different from each other.
- q 2 or more, the plurality of R 15 are the same as or different from each other.
- B 1 and B 2 represent a substituent represented by the general formula (4).
- r is 0 or 1.
- s is 0 or 1.
- r + s 1.
- a, b, c, d, p, and q are preferably 0.
- the first compound is represented by the following general formula (3B).
- B 1 and B 2 represent a substituent represented by the general formula (4).
- r is 0 or 1.
- s is 0 or 1.
- r + s 1.
- X 6 , X 7 and X 8 preferably represent a nitrogen atom.
- r is 1 and s is 0.
- the first compound is represented by the following general formula (3C).
- R 1 , R 2 , R 3 , R 4 , R 14 and R 15 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- a is 0, 1, 2, 3 or 4.
- b is 0, 1, 2 or 3.
- c is 0, 1, 2 or 3.
- d is 0, 1, 2, 3 or 4.
- p is 0, 1, 2, 3 or 4.
- q is 0, 1, 2, 3, 4 or 5.
- the plurality of R 1 are the same as or different from each other.
- the plurality of R 2 are the same as or different from each other.
- the plurality of R 3 are the same as or different from each other.
- the plurality of R 4 are the same as or different from each other.
- p is 2 or more, the plurality of R 14 are the same as or different from each other.
- q is 2 or more, the plurality of R 15 are the same as or different from each other.
- X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom.
- R Y is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group. At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- R 16 and R 17 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
- t is 0, 1, 2, 3, 4 or 5.
- u is 0, 1, 2, 3, 4 or 5.
- the plurality of R 16 are the same as or different from each other.
- u is 2 or more, the plurality of R 17 are the same as or different from each other.
- one of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is represented by the following general formula (1e).
- X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom.
- R Y is Hydrogen atom, Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- At least two of X 6 , X 7 and X 8 are nitrogen atoms.
- R 16 , R 17 and R 18 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
- t is 1, 2, 3, 4 or 5.
- u is 0, 1, 2, 3, 4 or 5.
- v is 0, 1, 2, 3, 4 or 5.
- alkyl group in the first compound examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (isomer group) ), Hexyl group (including isomer group), heptyl group (including isomer group), octyl group (including isomer group), nonyl group (including isomer group), decyl group (isomer group) ), Undecyl group (including isomer group), dodecyl group (including isomer group), and the like.
- a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a pentyl group are preferable.
- Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group are more preferable, and methyl group, ethyl group, isopropyl group, and t-butyl group are more preferable. More preferred are groups.
- the carbon number of the alkyl group in the first compound is 1 to 25, preferably 1 to 10.
- Examples of the cycloalkyl group in the first compound include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
- the number of carbon atoms of the cycloalkyl group in the first compound is 3 to 25, preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.
- halogen atom in the first compound examples include fluorine, chlorine, bromine and iodine, and a fluorine atom is preferable.
- aryl groups in the first compound include phenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c] phenanthryl, phenalenyl Group, fluorenyl group, picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl Group, benzo [b] triphenylenyl group, perylenyl group and the like.
- a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluoranthenyl group, and a fluorenyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is further preferable.
- the number of ring-forming carbon atoms of the aryl group in the first compound is 6 to 24, preferably 6 to 20, and more preferably 6 to 18.
- the heterocyclic group in the first compound includes a heterocyclic group having no aromaticity and an aromatic heterocyclic group having aromaticity (a heteroaryl group if monovalent, a heteroarylene group if bivalent). ).
- heterocyclic group having no aromaticity in the first compound examples include heterocyclic groups containing 3 to 30 ring-forming atoms, preferably 3 to 20 containing a nitrogen atom, oxygen atom or sulfur atom.
- Specific examples of the heterocyclic ring having no aromaticity include aziridine, oxirane, thiirane, azetidine, oxetane, trimethylene sulfide, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, and tetrahydrothiopyran.
- heterocyclic group in the first compound examples include a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and the ring-forming atom includes a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable to contain an atom selected from the group.
- a heteroaryl group having aromaticity is preferable.
- heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, imidazopyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl , Isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothienyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl Group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, a
- pyridyl group imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, substituted with aryl group or heterocyclic group at 9-position
- carbazolyl group substituted with aryl group or heterocyclic group at 9-position
- phenanthrolinyl group and quinazolinyl group.
- the number of ring-forming atoms of the heterocyclic group in the first compound is 3 to 30, preferably 5 to 24, and more preferably 5 to 18.
- the number of ring-forming atoms of the heteroaryl group in the first compound is 5 to 30, preferably 5 to 24, and more preferably 5 to 18.
- the ring-forming atom other than the carbon atom of the heteroaryl group in the first compound is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroarylene group in the first compound is a divalent group obtained by further removing one hydrogen atom or substituent from the heteroaryl group.
- Examples of silyl groups substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 25 carbon atoms and aryl groups having 6 to 24 ring carbon atoms in the first compound include mono-substituted silyl groups , Disubstituted silyl groups, and trisubstituted silyl groups.
- the mono-substituted silyl group in the first compound is represented by —SiH 2 (Y 10 ) or —SiH 2 (Y 20 ).
- the disubstituted silyl group in the first compound is represented by —SiH (Y 10 ) 2 , —SiH (Y 20 ) 2 , or —SiH (Y 10 ) (Y 20 ).
- the tri-substituted silyl group in the first compound is —Si (Y 10 ) 3 , —Si (Y 20 ) 3 , —Si (Y 10 ) 2 (Y 20 ), or —Si (Y 10 ) (Y 20 ). It is represented by 2 .
- Y 10 represents an alkyl group having 1 to 25 carbon atoms
- Y 20 represents an aryl group having 6 to 24 ring carbon atoms. If Y 10 there are a plurality, the plurality of Y 10 can be the same as each other or may be different. If Y 20 there are a plurality, the plurality of Y 20 can be the same as each other or may be different.
- R 1 , R 2 , R 3 and R 4 each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, or a substituted or unsubstituted ring forming carbon number. It preferably represents a cycloalkyl group having 3 to 25, a silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- a 1st compound can be manufactured combining a conventionally well-known synthesis method (For example, the method of the international publication 2011/132684 etc.). Examples of the first compound according to this embodiment are shown below. The first compound in the present invention is not limited to these specific examples.
- R 5 , R 6 , R 7 and R 8 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- g 0, 1, 2 or 3.
- h 0, 1, 2, 3 or 4.
- the plurality of R 5 are the same as or different from each other.
- the plurality of R 6 are the same as or different from each other.
- the plurality of R 7 are the same as or different from each other.
- the plurality of R 8 are the same as or different from each other.
- One of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b).
- R 9 is Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- i is 0, 1, 2, 3, 4 or 5.
- R 10 , R 11 , R 12 and R 13 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- l is 0, 1, 2, 3, 4 or 5.
- m is 0, 1, 2, 3, 4 or 5.
- the plurality of R 10 are the same as or different from each other.
- the plurality of R 11 are the same as or different from each other.
- the plurality of R 12 are the same as or different from each other.
- the plurality of R 13 are the same as or different from each other.
- R 9 is A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, It is preferably a silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
- one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the following general formula (5). Is preferred.
- R 10 , R 11 , R 12 and R 13 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- l is 0, 1, 2, 3, 4 or 5.
- m is 0, 1, 2, 3, 4 or 5.
- the plurality of R 10 are the same as or different from each other.
- the plurality of R 11 are the same as or different from each other.
- the plurality of R 12 are the same as or different from each other.
- the plurality of R 13 are the same as or different from each other.
- one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the following general formula (2c), the following general formula (2d), or It is also preferable that it is a substituent represented by the following general formula (2e).
- R 10 , R 11 , R 12 and R 13 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- l is 0, 1, 2, 3, 4 or 5.
- m is 0, 1, 2, 3, 4 or 5.
- the plurality of R 10 are the same as or different from each other.
- the plurality of R 11 are the same as or different from each other.
- the plurality of R 12 are the same as or different from each other.
- the plurality of R 13 are the same as or different from each other.
- one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the following general formula (5a). Is preferred.
- R 10 , R 11 , R 12 and R 13 are each independently Halogen atoms, A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms, A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms; A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
- l is 0, 1, 2, 3, 4 or 5.
- m is 0, 1, 2, 3, 4 or 5.
- the plurality of R 10 are the same as or different from each other.
- the plurality of R 11 are the same as or different from each other.
- the plurality of R 12 are the same as or different from each other.
- the plurality of R 13 are the same as or different from each other.
- one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the general formula (5), the general formula (2c), or the general formula. It is preferable that it is a substituent represented by (2d) or general formula (2e). In the second compound, it is more preferable that one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the general formula (5a).
- e, f, g and h are preferably 0.
- j, k, l and m are preferably 0.
- i, j, k, l and m are more preferably 0.
- it is more preferable that e, f, g, h, i, j, k, l and m are 0.
- the second compound when e, f, g, h, i, j, k, l and m are 0, the second compound is represented by the following general formula (2B).
- a 2nd compound can be manufactured combining a conventionally well-known synthetic
- composition of the present embodiment contains a combination of the first compound and the second compound
- the composition of the present embodiment is a single vapor deposition while maintaining the performance of the organic electroluminescence device.
- the ratio of materials from the source can be stably deposited.
- the compounding ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine the compounding ratio of said 1st compound and said 2nd compound suitably according to the effect calculated
- the compounding ratio (mass ratio) of the compound represented by “first compound: second compound” is usually in the range of 1:99 to 99: 1, and in the range of 10:90 to 90:10. In the range of 40:60 to 60:40 is more preferable.
- the material for an organic electroluminescence element according to this embodiment includes the composition according to this embodiment. That is, the organic electroluminescent element material according to the present embodiment contains the first compound and the second compound. The material for an organic electroluminescence element according to this embodiment may further contain other compounds. When the organic electroluminescent element material according to the present embodiment further includes other compounds, the other compounds may be solid or liquid.
- composition film includes the composition according to the present embodiment. That is, the film (composition film) containing the composition according to the present embodiment means a film containing the first compound and the second compound.
- the composition film according to the present embodiment may further contain other compounds.
- the method for forming the composition film according to the present embodiment is not particularly limited unless otherwise specified in the present specification.
- known methods such as a dry film forming method and a wet film forming method can be employed.
- the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method.
- wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.
- the organic EL device includes an anode, a cathode, and an organic layer between the anode and the cathode.
- the organic layer includes at least one layer composed of an organic compound.
- the organic layer is formed by laminating a plurality of layers composed of organic compounds.
- the organic layer may further contain an inorganic compound.
- at least one of the organic layers is a light emitting layer. Therefore, the organic layer may be composed of, for example, a single light emitting layer, or may include a layer that can be employed in an organic EL element.
- the layer that can be employed in the organic EL element is not particularly limited. For example, at least one selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a barrier layer. Layer.
- the organic layer is preferably composed of a plurality of layers, and the composition according to the embodiment is preferably contained in one or more of the plurality of layers.
- the composition according to this embodiment in any one or more layers of the organic EL element according to this embodiment, high organic EL performance (for example, light emission performance of at least one of driving voltage, light emission efficiency, and lifetime) ) Can be obtained.
- the composition according to the present embodiment is formed using the method according to the present embodiment (for example, vacuum deposition method)
- the first compound and the second compound in the light emitting layer from the initial deposition stage to the final deposition stage.
- the material ratio with the compound is stable.
- the organic EL element can stably maintain high light emission performance regardless of the deposition time.
- the light emitting layer preferably contains the composition according to this embodiment.
- a hole transport layer is further provided between the anode and the light emitting layer.
- the composition according to an embodiment of the present invention is used in the electron transport zone.
- the structure of (d) is preferably used.
- the “light emitting layer” is an organic layer having a light emitting function.
- the “hole injection / transport layer” means “at least one of a hole injection layer and a hole transport layer”.
- the “electron injection / transport layer” means “at least one of an electron injection layer and an electron transport layer”.
- a hole injection layer is provided between the hole transport layer and the anode.
- an organic EL element has an electron injection layer and an electron carrying layer, it is preferable that the electron injection layer is provided between the electron carrying layer and the cathode.
- each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be composed of a single layer or a plurality of layers.
- FIG. 1 shows a schematic configuration of an example of the organic EL element according to this embodiment.
- the organic EL element 1 includes a translucent substrate 2, an anode 3, a cathode 4, and an organic layer 10 disposed between the anode 3 and the cathode 4.
- the organic layer 10 includes a hole injection layer 6, a hole transport layer 7, a light emitting layer 5, an electron transport layer 8, and an electron injection layer 9.
- a hole injection layer 6, a hole transport layer 7, a light emitting layer 5, an electron transport layer 8, and an electron injection layer 9 are laminated in this order from the anode 3 side.
- the light emitting layer 5 of the organic EL element 1 contains the composition according to the present embodiment. That is, the light emitting layer 5 includes the first compound and the second compound.
- the organic EL device of the present embodiment is driven at a low voltage by using the first compound and the second compound in combination in the organic layer. From the viewpoint of driving the organic EL element at a low voltage, an embodiment in which the first compound and the second compound are contained in one light emitting layer is preferable.
- the blending ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine suitably the compounding ratio of a 1st compound and a 2nd compound according to the effect calculated
- the compounding ratio (mass ratio) of the compound represented by “first compound: second compound” is usually in the range of 1:99 to 99: 1, and in the range of 10:90 to 90:10. In the range of 40:60 to 60:40 is more preferable.
- the light emitting layer preferably further contains a light emitting material.
- the light emitting layer contains a phosphorescent material as a light emitting material.
- the phosphorescent material is preferably an orthometalated complex of any metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt). Suitable phosphorescent materials will be described later.
- the content of the light emitting material in the light emitting layer is preferably 0.1% by mass or more and 50% by mass or less. % To 20% by mass is more preferable.
- each layer of the organic EL element which is one embodiment of the present invention is not particularly limited unless otherwise specified in the present specification.
- known methods such as a dry film forming method and a wet film forming method can be employed.
- the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method.
- the wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.
- the film thickness of each layer of the organic EL element which is one embodiment of the present invention is not limited except as specifically mentioned in the present specification.
- the film thickness of each layer is preferably set to an appropriate film thickness. If the film is too thick, a large applied voltage is required to obtain a constant light output, and the efficiency may deteriorate. If the film is too thin, pinholes and the like are generated, and there is a possibility that sufficient light emission luminance cannot be obtained even when an electric field is applied.
- the film thickness is suitably in the range of 5 nm to 10 ⁇ m, more preferably in the range of 10 nm to 0.2 ⁇ m.
- the substrate is used as a support for the light emitting element.
- glass, quartz, plastic, or the like can be used as the substrate.
- a flexible substrate may be used as the substrate.
- the flexible substrate is a substrate that can be bent (flexible), and examples thereof include a plastic substrate made of polycarbonate and polyvinyl chloride.
- anode For the anode formed on the substrate, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
- a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
- ITO indium tin oxide
- ITO indium oxide-tin oxide containing silicon or silicon oxide
- indium oxide-zinc oxide silicon oxide
- tungsten oxide and indium oxide containing zinc oxide.
- graphene graphene.
- gold (Au), platinum (Pt), a nitride of a metal material (for example, titanium nitride), or the like can be given.
- the hole injection layer is a layer provided for efficiently injecting holes from the anode into the organic layer.
- Substances used for the hole injection layer include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide
- An oxide, a tungsten oxide, a manganese oxide, an aromatic amine compound, an acceptor compound, a polymer compound (oligomer, dendrimer, polymer, etc.), or the like can also be used.
- the substance used for the hole injection layer is preferably an aromatic amine derivative or an acceptor compound, and more preferably an acceptor compound.
- a heterocyclic derivative substituted with an electron withdrawing group a quinone derivative substituted with an electron withdrawing group, an arylborane derivative, a heteroarylborane derivative, or the like is preferably used.
- hexacyanohexaazatriphenylene, F 4 TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or 1,2,3-tris [(cyano) (4-cyano-2,3 , 5,6-tetrafluorophenyl) methylene] cyclopropane or the like is preferably used.
- the layer containing an acceptor compound is preferably in a form further containing a matrix material.
- a wide variety of materials for organic EL can be used as the matrix material.
- a donor compound is preferably used, and an aromatic amine compound is more preferably used.
- the hole transport layer is a layer containing a substance having a high hole transport property.
- An aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used for the hole transport layer.
- a high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used.
- PVK N-vinylcarbazole
- PVTPA poly (4-vinyltriphenylamine
- any substance other than these may be used as long as it has a property of transporting more holes than electrons.
- the layer containing a substance having a high hole-transport property may be a single layer, or two or more layers containing the above substances may be stacked.
- the hole transport material is preferably a compound represented by the following general formula (H).
- Ar 1 to Ar 3 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms. Or a group composed of a combination of a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group.
- a substituent such as a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a triphenylenyl group is preferable.
- a substituent such as a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a triphenylenyl group is preferable.
- a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, or the like is preferable.
- the group composed of a combination of an aryl group and a heterocyclic group is preferably a dibenzofuran-substituted aryl group, a dibenzothiophene-substituted aryl group, a carbazole-substituted aryl group, or the like. These substituents may further have a substituent, and preferred substituents are as described below.
- at least one of Ar 1 to Ar 3 in the general formula (H) is preferably a compound further substituted with an arylamino group, and is a diamine derivative, a triamine derivative, or a tetraamine derivative. It is also preferable.
- tetraaryl-substituted benzidine derivatives and TPTE are preferably used as diamine derivatives.
- TPTE tetraaryl-substituted benzidine derivatives and TPTE (4,4′-bis [N-phenyl-N- [4′-diphenylamino-1,1′-biphenyl-4-yl] amino] -1,1 '-Biphenyl) and the like are preferably used.
- the hole transport material used for the layer in contact with the phosphorescent light emitting layer preferably has a high triplet level, and Ar 1 to Ar 3 in the general formula (H) are each independently a fluorenyl group or spirofluorenyl.
- the light emitting layer is a layer containing a substance having high light emitting property. Various materials can be used for the light emitting layer.
- the light emitting layer usually contains a light emitting material (dopant material) having high light emitting property and a host material for causing the light emitting material to emit light efficiently.
- a fluorescent compound that emits fluorescence or a phosphorescent compound that emits phosphorescence can be used as the substance having high light-emitting property.
- a fluorescent compound is a compound that can emit light from a singlet excited state.
- a phosphorescent compound is a compound that can emit light from a triplet excited state.
- the light emitting layer containing a fluorescent compound is called a fluorescent light emitting layer.
- the light emitting layer containing a phosphorescent compound is called a phosphorescent light emitting layer.
- Fluorescent compounds can be widely used as dopant materials for the fluorescent layer.
- the dopant material for the fluorescent light emitting layer among them, condensed polycyclic aromatic derivatives, styrylamine derivatives, condensed ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like are preferable. More preferable examples of the dopant material for the fluorescent light emitting layer include condensed ring amine derivatives and boron-containing compounds.
- Examples of the condensed ring amine derivative include diaminopyrene derivatives, diaminochrysene derivatives, diaminoanthracene derivatives, diaminofluorene derivatives, and diaminofluorene derivatives in which one or more benzofuro skeletons are condensed.
- Examples of the boron-containing compound include a pyromethene derivative and a triphenylborane derivative.
- the term “derivative” refers to a compound that includes the skeleton as a partial structure, a compound that has a further ring with the skeleton and forms a condensed ring, and a compound that has the skeleton that forms a ring with substituents. Also contains.
- a condensed polycyclic aromatic derivative it is a compound that contains a condensed polycyclic aromatic skeleton as a partial structure, a compound that further forms a condensed ring in the condensed polycyclic aromatic skeleton, and the condensed polycyclic aromatic Also included are compounds that form a ring with substituents of the skeleton.
- a general fluorescent material can be used as a host material used for the fluorescent light emitting layer.
- the host material used for the fluorescent light emitting layer is preferably a compound having a condensed polycyclic aromatic derivative as a main skeleton, and more preferably an anthracene derivative, a pyrene derivative, a chrysene derivative, a naphthacene derivative, or the like.
- a host suitable as a blue host material (a host material used with a blue fluorescent material dopant material) and a green host material (a host material used with a green fluorescent material dopant material) is represented by the following general formula (X). Anthracene derivatives.
- Ar X1 and Ar X2 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring atom having 3 to 50 ring atoms.
- a heterocyclic group is shown.
- Ar X1 and Ar X2 each independently preferably represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. .
- a metal complex such as an iridium complex, an osmium complex, or a platinum complex is used.
- the phosphorescent material that is an orthometalated complex of a metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt) is a complex represented by the following formula ( ⁇ ). preferable.
- M represents at least one metal selected from the group consisting of osmium, iridium and platinum, and n represents the valence of the metal.
- Ring A 1 represents a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms
- Ring A 2 forms a nitrogen heterocycle A substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms contained as an atom is represented.
- Examples of the aryl group having 6 to 24 ring carbon atoms in the ring A 1 of the formula ( ⁇ ) include the aryl groups in the general formula (1) described above.
- Examples of the heteroaryl group having 5 to 30 ring atoms in the ring A 1 and the ring A 2 of the formula ( ⁇ ) include the heteroaryl groups in the general formula (1) described above.
- the substituent that the ring A 1 and the ring A 2 of the formula ( ⁇ ) may have is the same as the substituent in the general formula (1) described above.
- the complex represented by the formula ( ⁇ ) is preferably a complex represented by the following formula (T) or (U).
- M represents a metal
- ring B and ring C each independently represent an aryl group or heteroaryl group having 5 or 6 ring atoms.
- Ring A-ring B represents a bond pair of a heteroaryl group and an aryl group or heteroaryl group.
- Ring A-ring B is coordinated to metal M via the nitrogen atom of ring A and the sp 2 hybrid atom of ring B.
- Ring A to ring C represent a bond pair of a heteroaryl group and an aryl group or heteroaryl group.
- R a , R b and R c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted group; Amino group, substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted This represents any one selected from the group consisting of an aryl group having 6 to 24 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, and R a is 1 or more and 4 or less R b is 1 or more and 4 or less, R c is 1 or more and 4 or less
- X 1 to X 9 each independently represents a carbon atom or a nitrogen atom.
- R d and R e are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted amino group, Substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted ring-forming carbon R c , R d and R e bonded to the ring C, each represented by any one selected from the group consisting of an aryl group having 6 to 24 and a substituted or unsubstituted heteroaryl group having 5 to 30 ring
- examples of M include osmium, iridium, and platinum, and iridium is particularly preferable.
- examples of the aryl group having 6 ring-forming carbon atoms represented by ring B and ring C include the aryl group in the general formula (1) described above.
- Examples of the heteroaryl group having 5 or 6 ring atoms represented by ring B and ring C include the heteroaryl group in the general formula (1) described above.
- Examples of the aralkyl group having 7 to 50 carbon atoms, the substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms and the substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms are the groups described above. The same group is mentioned.
- Examples of the monoanionic bidentate ligand represented by L ′ include a ligand represented by the following formula (L ′).
- X 4 ⁇ X 9, R a, and R b are the same as X 4 ⁇ X 9, R a , and R b in Formula (T), preferable embodiments thereof are also the same.
- the ligand represented by the formula (L ′) is represented by the formula (T) through a solid line extending from the ring X 9 to the outside of the ring B and a broken line extending from the nitrogen atom of the ring A to the outside of the ring A. Coordinates to metal M.
- X represents any one selected from the group consisting of NR, oxygen atom, sulfur atom, BR, and selenium atom
- R represents a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 25 It is an alkyl group.
- R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms.
- R 1 is 1 or more and 4 or less
- R 2 is 1 or more and 4 or less
- R 3 is 1 or more and 4 or less
- R 4 is 1 or more and 4 or less
- the numbers of R 1 , R 2 , R 3 and R 4 are independent of each other.
- examples of the alkyl group having 1 to 25 carbon atoms represented by R, R 1 , R 2 , R 3 and R 4 include the groups described above, and preferred embodiments thereof are also the same.
- examples of the aryl group having 6 to 24 ring carbon atoms represented by R 1 , R 2 , R 3, and R 4 include the groups described above, and preferred embodiments thereof are also the same.
- an iridium complex represented by the following formula ( ⁇ ) is also preferable.
- a 1 to A 8 contain a carbon atom or a nitrogen atom, at least one of A 1 to A 8 is a nitrogen atom, ring B is bonded to ring A by a C—C bond, and iridium (Ir) is bonded to ring A through an Ir—C bond.
- Ir iridium
- a 3 and A 4 are carbon atoms among A 1 to A 4 .
- a 5 is preferably a nitrogen atom
- a 1 to A 4 and A 6 to A 8 are preferably carbon atoms.
- a 6 is preferably CR (carbon atom to which R is bonded), and R is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms.
- R is preferably a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms.
- R 1 to R 4 are each independently mono-substituted, di-substituted, tri-substituted or tetra-substituted, or unsubstituted, and adjacent R 1 are bonded to each other to form a ring
- Adjacent R 2 may be bonded to each other to form a ring
- adjacent R 3 may be bonded to each other to form a ring
- adjacent R 4 may be bonded to each other.
- R 1 to R 4 each independently represent: hydrogen, deuterium, halogen, Substituted or unsubstituted alkyl having 1 to 25 carbon atoms, Substituted or unsubstituted cycloalkyl having 3 to 25 ring carbon atoms, Substituted or unsubstituted heteroalkyl having 2 to 25 atoms, Substituted or unsubstituted arylalkyl having 7 to 50 carbon atoms, Substituted or unsubstituted alkoxy having 1 to 25 carbon atoms, Substituted or unsubstituted aryloxy having 6 to 24 ring carbon atoms, Substituted or unsubstituted amino, Substituted silyl, Substituted or unsubstituted alkenyl having 2 to 25 carbon atoms, Substituted or unsubstituted cycloalkenyl having 3 to 25 ring
- the substituted carbonyl is a carbonyl substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms.
- R 1 to R 4 are preferably each independently selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 25 carbon atoms, and combinations thereof.
- At least one of R 2 and R 3 is preferably an alkyl group having 1 to 25 carbon atoms, more preferably the alkyl group is deuterated or partially deuterated.
- n is an integer of 1 to 3, and is preferably 1.
- the complex represented by the formula ( ⁇ ) in addition to the complex represented by the formula (T) or (U), the complex represented by the following formula (V), (X), (Y) or (Z) It can also be used.
- R 50 to R 54 are each independently a hydrogen atom or a substituent, k is an integer of 1 to 4, and 1 is 1 Is an integer from 4 to 4, and m is an integer from 1 to 2.
- M is Ir, Os, or Pt. Examples of the substituent represented by R 50 to R 54 include the same substituents as those described above.
- Formula (V) is preferably represented by the following formula (V-1), and formula (X) is preferably represented by the following formula (X-1) or formula (X-2).
- R 50 , k, and M are the same as R 50 , k, and M described above.
- the host material used for the phosphorescent light-emitting layer is preferably a material having a triplet level higher than that of the phosphorescent dopant, and a phosphorescent host material such as a general aromatic derivative, heterocyclic derivative, or metal complex is used. be able to.
- a phosphorescent host material such as a general aromatic derivative, heterocyclic derivative, or metal complex is used.
- aromatic derivatives and heterocyclic derivatives are preferable, and examples of aromatic derivatives include naphthalene derivatives, triphenylene derivatives, phenanthrene derivatives, and fluoranthene derivatives.
- Examples include indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, and dibenzothienyl derivatives.
- the derivative is defined as described above.
- One preferred form of the host material used for the phosphorescent light emitting layer is a composition according to an embodiment of the present invention.
- the electron transport layer is a layer containing a substance having a high electron transport property.
- one or more layers may be provided between the electron transport layer and the light emitting layer.
- This layer is called a second electron transport layer, a hole blocking layer, a triplet block layer, or the like.
- a material having a deep HOMO level In order to improve the triplet blocking property, it is preferable to use a material having a high triplet level.
- the electron transport layer includes metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, heterocyclic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, condensed aromatic hydrocarbon derivatives, and Polymeric compounds can be used.
- metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes
- heterocyclic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, condensed aromatic hydrocarbon derivatives, and Polymeric compounds can be used.
- imidazole derivatives for example, benzimidazole derivatives, imidazopyridine derivatives, benzimidazophenanthridine derivatives
- azine derivatives for example, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, phenanthroline derivatives, etc., and these heterocyclic rings Phosphine oxide-based substituents
- aromatic hydrocarbon derivatives for example, anthracene derivatives and fluoranthene derivatives.
- the composition according to one embodiment of the present invention can be used.
- the electron transport layer is formed of an alkali metal derivative (for example, lithium quinolinate complex) such as an alkali metal (Li, Cs, etc.), an alkaline earth metal (Mg, etc.), and an alloy containing these. And at least one selected from the group consisting of alkaline earth metal derivatives.
- an alkali metal derivative for example, lithium quinolinate complex
- the electron transport layer contains at least one of alkali metals, alkaline earth metals and alloys thereof, the content ratio in the electron transport layer is preferably 0.1 to 50% by mass, more preferably 0.1 to 20%.
- the content ratio in the electron transport layer is preferably It is 1 to 99% by mass, more preferably 10 to 90% by mass.
- the electron injection layer is a layer containing a substance having a high electron injection property.
- alkali metals such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), lithium oxide (LiO x ), and the like are used.
- Alkali metal derivatives for example, lithium quinolinate complexes
- alkaline earth metal derivatives such as metals or alloys containing them can be used.
- cathode For the cathode, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less).
- cathode materials include elements belonging to Group 1 or Group 2 of the Periodic Table of Elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and alkaline earth such as magnesium (Mg). And other rare earth metals such as alloys, alloys containing them (for example, MgAg, AlLi), and alloys containing these.
- the hydrogen atom includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (triuterium), and tritium.
- the number of ring-forming carbon atoms constitutes the ring itself of a compound having a structure in which atoms are bonded cyclically (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, or a heterocyclic compound). Represents the number of carbon atoms in the atom.
- the carbon contained in the substituent is not included in the number of ring-forming carbons.
- the “ring-forming carbon number” described below is the same unless otherwise specified.
- a benzene ring has 6 ring carbon atoms
- a naphthalene ring has 10 ring carbon atoms
- a pyridinyl group has 5 ring carbon atoms
- a furanyl group has 4 ring carbon atoms.
- the carbon number of the alkyl group is not included in the number of ring-forming carbons.
- the carbon number of the fluorene ring as a substituent is not included in the number of ring-forming carbons.
- the number of ring-forming atoms means a compound (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocycle) having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic ring, a condensed ring, or a ring assembly).
- a compound for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocycle
- a cyclic manner for example, a monocyclic ring, a condensed ring, or a ring assembly.
- Atoms that do not constitute a ring or atoms included in a substituent when the ring is substituted by a substituent are not included in the number of ring-forming atoms.
- the “number of ring-forming atoms” described below is the same unless otherwise specified.
- the pyridine ring has 6 ring atoms
- the quinazoline ring has 10 ring atoms
- the furan ring has 5 ring atoms.
- a hydrogen atom bonded to a carbon atom of a pyridine ring or a quinazoline ring or an atom constituting a substituent is not included in the number of ring-forming atoms.
- a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring)
- the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.
- carbon number XX to YY in the expression “substituted or unsubstituted ZZ group having XX to YY” represents the number of carbon atoms when the ZZ group is unsubstituted and substituted. The carbon number of the substituent in the case is not included.
- atom number XX to YY in the expression “a ZZ group having a substituted or unsubstituted atom number XX to YY” represents the number of atoms when the ZZ group is unsubstituted and substituted. The number of atoms of the substituent in the case is not included.
- unsubstituted in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the above substituent.
- the substituent (first substituent) in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, carbon
- the substituent (first substituent) in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, carbon Selected from the group consisting of an alkyl group having 1 to 25 (straight chain or branched alkyl group), an alkylsilyl group having 3 to 25 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, and a cyano group At least one kind of group is preferable, and specific substituents that are preferable in the description of each substituent are preferable.
- the substituent (first substituent) in the case of “substituted or unsubstituted” refers to an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, 1 to 25 alkyl groups (straight or branched chain alkyl groups), cycloalkyl groups having 3 to 25 carbon atoms, alkylsilyl groups having 3 to 25 carbon atoms, arylsilyl groups having 6 to 30 ring carbon atoms, carbon An alkoxy group having 1 to 25 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, a substituted amino group, an alkylthio group having 1 to 25 carbon atoms, an arylthio group having 6 to 30 ring carbon atoms, and 7 to 30 carbon atoms.
- the substituent (second substituent) further substituted with the substituent (first substituent) in the case of “substituted or unsubstituted” is an aryl group having 6 to 30 ring carbon atoms, It is at least one group selected from the group consisting of heteroaryl groups having 5 to 30 ring atoms, alkyl groups having 1 to 25 carbon atoms (straight chain or branched chain alkyl groups), halogen atoms, and cyano groups It is preferable that it is at least one group selected from the specific substituents preferred in the description of each substituent.
- alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl (including isomeric groups), hexyl Groups (including isomer groups), heptyl groups (including isomer groups), octyl groups (including isomer groups), nonyl groups (including isomer groups), decyl groups (including isomer groups), undecyl Groups (including isomer groups), dodecyl groups (including isomer groups), and the like.
- a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a pentyl group (all including an isomer group) are preferable.
- Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group are more preferable, and methyl group, ethyl group, isopropyl group and t-butyl group are further included. preferable.
- the carbon number of the alkyl group is 1 to 25, preferably 1 to 10.
- halogenated alkyl group in which the alkyl group is substituted with a halogen atom examples include a group in which the alkyl group having 1 to 25 carbon atoms is substituted with one or more halogen atoms, preferably a fluorine atom.
- Specific examples of the halogenated alkyl group having 1 to 25 carbon atoms in the present specification include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoromethylmethyl group, a trifluoroethyl group, And a pentafluoroethyl group.
- the alkenyl group is a group having a double bond in the alkyl group, and the alkenyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferably, it is a vinyl group.
- the alkynyl group is a group having a triple bond in the alkyl group, and the alkynyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferred is an ethynyl group.
- Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
- the number of carbon atoms forming the ring of the cycloalkyl group is 3 to 25, preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.
- the alkoxy group is a group represented by —OY 10 , and examples of Y 10 include the same groups as those described as the alkyl group and the cycloalkyl group.
- the number of carbon atoms of the alkoxy group is preferably 1 to 25, more preferably 1 to 10.
- the alkylthio group is a group represented by —SY 10 , and examples of Y 10 include the same groups as those described as the alkyl group and the cycloalkyl group.
- the alkylthio group has 1 to 25 carbon atoms, preferably 1 to 10 carbon atoms.
- halogen atom examples include fluorine, chlorine, bromine, iodine and the like, preferably a fluorine atom.
- aryl groups include phenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c] phenanthryl, phenalenyl, fluorenyl, Picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl group, benzo [b ] A triphenylenyl group, a perylenyl group, etc.
- a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluoranthenyl group, and a fluorenyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is further preferable.
- the aryl group has 6-30 ring-forming carbon atoms, preferably 6-24, more preferably 6-20, and even more preferably 6-18.
- the arylene group is a divalent group in which one hydrogen atom or substituent is further removed from the aryl group.
- the aralkyl group is represented as —Y 11 —Y 20 .
- Y 11 is a divalent group (an alkylene group or a cycloalkylene group) in which one hydrogen atom or substituent is further removed from the groups listed as the alkyl group and the cycloalkyl group.
- Examples of Y 20 include the aryl group.
- the aryloxy group is represented by —OY 20 and examples of Y 20 include the same groups as those mentioned as the aryl group.
- the heteroaryloxy group is represented as -OY 30. Examples of Y 30 include the same groups as those described above for the heteroaryl group.
- the arylthio group is represented by —SY 20 and examples of Y 20 include the same groups as those mentioned as the aryl group.
- the heteroarylthio group is represented by —SY 30 and examples of Y 30 include the same groups as those mentioned as the heteroaryl group.
- the arylcarbonyloxy group is represented by —O— (C ⁇ O) —Y 20, and examples of Y 20 include the same groups as those mentioned as the aryl group.
- a substituted carbonyl group having a substituent selected from an alkyl group and an aryl group is represented by — (C ⁇ O) —Y 10 or — (C ⁇ O) —Y 20, and examples of Y 10 include the alkyl group And the same groups as those exemplified above as the cycloalkyl group, and examples of Y 20 include the same groups as those exemplified as the aryl group.
- the heterocyclic group includes a heterocyclic group having no aromaticity and an aromatic heterocyclic group having aromaticity (a monoaryl is a heteroaryl group, and a bivalent is a heteroarylene group).
- heterocyclic group having no aromaticity examples include heterocyclic groups containing 3 to 30, preferably 3 to 20 ring-forming atoms, including a nitrogen atom, an oxygen atom or a sulfur atom.
- Specific examples of the heterocyclic ring having no aromaticity include aziridine, oxirane, thiirane, azetidine, oxetane, trimethylene sulfide, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, and tetrahydrothiopyran.
- heterocyclic group examples include a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and the ring-forming atom is an atom selected from the group consisting of a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable to contain.
- a heteroaryl group having aromaticity is preferable.
- heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, imidazopyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl , Isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothienyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl Group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, a
- pyridyl group imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, substituted with aryl group or heterocyclic group at 9-position
- carbazolyl group substituted with aryl group or heterocyclic group at 9-position
- phenanthrolinyl group and quinazolinyl group.
- the number of ring-forming atoms of the heterocyclic group is from 3 to 30, preferably from 5 to 24, more preferably from 5 to 18.
- the number of ring-forming atoms of the heteroaryl group is 5 to 30, preferably 5 to 24, more preferably 5 to 18.
- the ring-forming atom other than the carbon atom of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the heteroarylene group is a divalent group obtained by further removing one hydrogen atom or substituent from the heteroaryl group.
- the heterocyclic group may be a group derived from a partial structure represented by the following general formulas (XY-1) to (XY-18), for example.
- X A and Y A are each independently a hetero atom, and an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, or a germanium atom Is preferred.
- the partial structures represented by the general formulas (XY-1) to (XY-18) have a bond at an arbitrary position to be a heterocyclic group, and this heterocyclic group has a substituent. Also good.
- the mono-substituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —NH (Y 10 ) or —NH (Y 20 ), and Y 10 and Y 20 are as described above.
- the disubstituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —N (Y 10 ) 2 , —N (Y 20 ) 2 or —N (Y 10 ) (Y 20 ), and Y 10 And Y 20 are as described above.
- two Y 10 or Y 20 are present, they may be the same as or different from each other.
- the mono-substituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH 2 (Y 10 ) or —SiH 2 (Y 20 ).
- the disubstituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH (Y 10 ) 2 , —SiH (Y 20 ) 2 or —SiH (Y 10 ) (Y 20 ).
- the tri-substituted silyl group having a substituent selected from an alkyl group and an aryl group is -Si (Y 10 ) 3 , -Si (Y 20 ) 3 , -Si (Y 10 ) 2 (Y 20 ) or -Si (Y 10 ) (Y 20 ) 2 .
- Y 10 and Y 20 are as described above, and when there are a plurality of Y 10 or Y 20 s , they may be the same as or different from each other.
- the substituted sulfonyl group having a substituent selected from an alkyl group and an aryl group is represented by —S ( ⁇ O) 2 —Y 10 or —S ( ⁇ O) 2 —Y 20 , and Y 10 and Y 20 are the above-mentioned Street.
- Y 10 and Y 20 are as described above, and when two Y 10 or Y 20 are present, they may be the same as or different from each other.
- the alkylsulfonyloxy group having an alkyl group is represented by —O—S ( ⁇ O) 2 (Y 10 ), and Y 10 is as described above.
- the arylsulfonyloxy group having a substituent selected from an aryl group is represented by —O—S ( ⁇ O) 2 (Y 20 ), and Y 20 is as described above.
- An electronic device which is one embodiment of the present invention includes the organic electroluminescence element which is one embodiment of the present invention.
- the organic electroluminescent element which is one embodiment of the present invention can be used for various electronic devices.
- the organic electroluminescence element which is one embodiment of the present invention can be used for a planar light emitter, a backlight, a light source such as an instrument, a display board, a marker lamp, and the like.
- the flat light emitter include a flat panel display of a wall-mounted television.
- the backlight include backlights such as copying machines, printers, and liquid crystal displays.
- the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.
- the mode in which the composition is included in the light emitting layer is described as an example.
- the organic EL element of the aspect by which the composition is contained in one layer of organic layers other than a light emitting layer is mentioned, for example.
- an anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport zone included between the light-emitting layer and the cathode is illustrated.
- the light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked.
- the organic EL element has a plurality of light emitting layers, it is sufficient that at least one light emitting layer satisfies the conditions described in the above embodiment.
- the other light-emitting layer may be a fluorescent light-emitting layer or a phosphorescent light-emitting layer that utilizes light emission by electron transition from a triplet excited state to a direct ground state.
- these light emitting layers may be provided adjacent to each other, or a so-called tandem organic material in which a plurality of light emitting units are stacked via an intermediate layer. It may be an EL element.
- a barrier layer may be provided adjacent to at least one of the anode side and the cathode side of the light emitting layer.
- the barrier layer is preferably disposed in contact with the light emitting layer and blocks at least one of holes, electrons, and excitons.
- the barrier layer transports electrons, and holes reach a layer on the cathode side of the barrier layer (for example, an electron transport layer).
- an organic EL element contains an electron carrying layer, it is preferable to contain the said barrier layer between a light emitting layer and an electron carrying layer.
- the barrier layer transports holes, and the electrons are directed to a layer on the anode side of the barrier layer (for example, a hole transport layer). Stop reaching.
- the organic EL element includes a hole transport layer
- a barrier layer may be provided adjacent to the light emitting layer so that excitation energy does not leak from the light emitting layer to the peripheral layer. The excitons generated in the light emitting layer are prevented from moving to a layer (for example, an electron transport layer or a hole transport layer) closer to the electrode than the barrier layer.
- the light emitting layer and the barrier layer are preferably joined.
- the crucible, the crucible filled with compound ET-1, and the crucible filled with 8-quinolinolatolithium (Liq) were set in a vacuum deposition apparatus.
- a glass substrate manufactured by Geomat Co.
- an ITO transparent electrode anode
- the film thickness of ITO was 130 nm.
- Compound HAT was vapor-deposited to form a HAT film having a thickness of 10 nm to form a hole injection layer.
- a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
- a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
- a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm.
- the concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
- the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. . Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm. Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm. The organic EL device produced in this way was used as an organic EL device in the initial stage of vapor deposition.
- the ITO substrate is retracted out of the chamber, and the mixture of the compound PGH-P1 and the compound PGH-N1 is evaporated to a mass of 0.4 g (the remaining amount is 20% by mass). ) Continued until. Thereafter, the ITO substrate is returned to the chamber, and the already prepared organic EL element part is protected with a mask, and then the compound HAT is vapor deposited so as to cover the transparent electrode on the surface on which the transparent electrode line is formed. A HAT film having a thickness of 10 nm was formed to form a hole injection layer.
- a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
- a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
- a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm.
- the concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
- the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. . Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm. Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm. The organic EL device produced in this way was used as the organic EL device at the end of vapor deposition.
- the crucible residue was taken out from the vapor deposition apparatus, the crucible residue was dissolved in tetrahydrofuran, and the ratio (residue ratio) between compound PGH-P1 and compound PGH-N1 was determined from the peak area values of each component detected by HPLC.
- Table 1 shows the ratio (initial ratio) of the compound PGH-P1 and the compound PGH-N1 in the crucible in the initial stage (before deposition), and the ratio of the compound PGH-P1 and the compound PGH-N1 in the crucible after deposition ( Residue ratio).
- Example 2 Example 2 was carried out in the same manner as Example 1 except that compound PGH-N2 was used instead of compound PGH-N1 in the light emitting layer of Example 1.
- Table 1 shows the ratio (initial ratio) of compound PGH-P1 and compound PGH-N2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-P1 and compound PGH-N2 in the crucible after vapor deposition ( Residue ratio).
- Comparative Example 1 was the same as Example 1 except that compound PGH-C1 was used instead of compound PGH-P1 in the light emitting layer of Example 1, and compound PGH-C2 was used instead of compound PGH-N1.
- Table 1 shows the ratio (initial ratio) of compound PGH-C1 and compound PGH-C2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-C1 and compound PGH-C2 in the crucible after vapor deposition ( Residue ratio).
- the mass ratio (film ratio) of the compound PGH-P1 and the compound PGH-N1 in the light emitting layer was analyzed by HPLC.
- the compound PGH-P1: the compound PGH- N1 5: 5.
- the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N2 in the light emitting layer was analyzed by HPLC.
- the compound PGH-P1: the compound PGH- N2 5: 5.
- the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N1 in the light emitting layer was the same as that of the compound PGH-P1 in the initial crucible (before vapor deposition). The ratio was the same as the mass ratio (initial ratio) with compound PGH-N1. Further, regarding the organic EL device of Example 2 (initial stage of vapor deposition), the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N2 in the light emitting layer was the compound PGH- in the initial crucible (before vapor deposition).
- the ratio was the same as the mass ratio (initial ratio) between P1 and compound PGH-N2.
- the mass ratio (film ratio) of the compound PGH-C1 and the compound PGH-C2 in the light emitting layer was the compound PGH in the crucible at the initial stage (before vapor deposition).
- the mass ratio (initial ratio) of -C1 and compound PGH-C2 was significantly different.
- V The voltage (unit: V) when energized between the ITO transparent electrode and the metal Al cathode was measured so that the current density was 10 mA / cm 2 .
- External quantum efficiency EQE A spectral radiance spectrum when a voltage was applied to the device so that the current density was 10 mA / cm 2 was measured with a spectral radiance meter CS-1000 (manufactured by Konica Minolta). The external quantum efficiency EQE (unit:%) was calculated from the obtained spectral radiance spectrum, assuming that Lambtian radiation was performed.
- Example 1 and Example 2 it was found that there was less variation in device performance as compared to Comparative Example 1 with respect to the organic EL element at the initial stage of vapor deposition and the organic EL element at the end of the vapor deposition. While maintaining the performance of the organic electroluminescence device by using the composition containing the first compound represented by the general formula (1) and the second compound represented by the general formula (2), It has been found that it is possible to stably deposit the ratio of materials from one deposition source.
- SYMBOLS 1 Organic EL element, 3 ... Anode, 4 ... Cathode, 5 ... Light emitting layer, 7 ... Hole transport layer, 8 ... Electron transport layer.
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Abstract
Description
本発明は、組成物、有機エレクトロルミネッセンス素子用材料、組成物膜、有機エレクトロルミネッセンス素子、及び電子機器に関する。 The present invention relates to a composition, a material for an organic electroluminescence element, a composition film, an organic electroluminescence element, and an electronic apparatus.
特許文献1には、第一ホストとしてカルバゾリル基誘導体構造及び窒素含有へテロ芳香族環の両方を有する化合物を用い、第二ホストとして縮合アリール基、ジベンゾフラニル基、又はジベンゾチエニル基を有する特定構造のビスカルバゾール誘導体を用いた有機エレクトロルミネッセンス素子が記載されている。この有機エレクトロルミネッセンス素子によれば、高い効率を維持しながら、長寿命であることが特許文献1に記載されている。
従来、2つの材料(例えば、第一ホスト及び第二ホスト)を、互いに異なる蒸着源から蒸着させる場合、有機エレクトロルミネッセンス素子の製造プロセスが複雑化する課題がある。一方で、1つの材料(例えば、第一ホストまたは第二ホストのいずれかのみ)を用いた有機エレクトロルミネッセンス素子では寿命が短くなる。そのため、1つの蒸着源から2つ(又は複数)の材料を安定的に蒸着させる技術が要望されている。
特許文献1に記載された第一ホスト及び第二ホストの組み合わせでは、2種のホスト材料を1つの蒸着源から蒸着した場合、蒸着初期に形成された層を用いた有機エレクトロルミネッセンス素子は良好な特性を示す。しかし、同じ蒸着源からの蒸着を長時間、続けた場合、蒸着時間の経過に伴い、形成された層に含まれる第一ホスト及び第二ホストの比率が安定しなくなるため、有機エレクトロルミネッセンス素子の性能が安定しないという課題がある。
Conventionally, when two materials (for example, a first host and a second host) are vapor-deposited from different vapor deposition sources, there is a problem that the manufacturing process of the organic electroluminescence element becomes complicated. On the other hand, the lifetime of an organic electroluminescent element using one material (for example, only one of the first host and the second host) is shortened. Therefore, a technique for stably depositing two (or a plurality of) materials from one deposition source is desired.
In the combination of the first host and the second host described in
本発明の目的は、有機エレクトロルミネッセンス素子の性能を維持しながら、1つの蒸着源から材料の比率を安定的に蒸着させることのできる組成物を提供すること、当該組成物を含む有機エレクトロルミネッセンス素子用材料を提供すること、当該組成物を含む組成物膜を提供すること、当該組成物を含む有機エレクトロルミネッセンス素子を提供すること、並びに当該有機エレクトロルミネッセンス素子を備える電子機器を提供することである。 An object of the present invention is to provide a composition capable of stably depositing a ratio of materials from one vapor deposition source while maintaining the performance of the organic electroluminescence element, and an organic electroluminescence element including the composition Providing a material for use, providing a composition film containing the composition, providing an organic electroluminescence device containing the composition, and providing an electronic device including the organic electroluminescence device. .
本発明の一態様によれば、2種以上の化合物が混合された組成物であって、少なくとも下記一般式(1)で表される第一の化合物及び下記一般式(2)で表される第二の化合物が含有される組成物が提供される。 According to one embodiment of the present invention, a composition in which two or more kinds of compounds are mixed, at least the first compound represented by the following general formula (1) and the following general formula (2) is represented. Compositions containing a second compound are provided.
(前記一般式(1)中、
R1、R2、R3及びR4は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
A1及びA2のうち、一方が、下記一般式(1a)で表される置換基であり、他方が、下記一般式(1b)で表される部分構造を含む置換基である。)
(In the general formula (1),
R 1 , R 2 , R 3 and R 4 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
One of A 1 and A 2 is a substituent represented by the following general formula (1a), and the other is a substituent including a partial structure represented by the following general formula (1b). )
(前記一般式(1a)中、X1、X2、X3、X4及びX5は、それぞれ独立して、CRX又は窒素原子を示す。RXは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRXは、互いに同一であるか、又は異なる。)
(In the
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R X are the same as or different from each other. )
(前記一般式(1b)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
X9、X10、X11、X12、X13、X14、X15、X16、X17及びX18は、それぞれ独立して、CRZ又は窒素原子を示す。RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。)
(In the
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 each independently represent CR Z or a nitrogen atom. R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other. )
(前記一般式(2)中、R5、R6、R7及びR8は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
eは、0、1、2、3又は4である。
fは、0、1、2又は3である。
gは、0、1、2又は3である。
hは、0、1、2、3又は4である。
eが2以上の場合、複数のR5は、互いに同一であるか、又は異なる。
fが2以上の場合、複数のR6は、互いに同一であるか、又は異なる。
gが2以上の場合、複数のR7は、互いに同一であるか、又は異なる。
hが2以上の場合、複数のR8は、互いに同一であるか、又は異なる。
A3及びA4のうち、一方が、下記一般式(2a)で表される置換基であり、他方が、下記一般式(2b)で表される置換基である。)
(In the general formula (2), R 5 , R 6 , R 7 and R 8 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3 or 4;
f is 0, 1, 2 or 3.
g is 0, 1, 2 or 3.
h is 0, 1, 2, 3 or 4.
When e is 2 or more, the plurality of R 5 are the same as or different from each other.
When f is 2 or more, the plurality of R 6 are the same as or different from each other.
When g is 2 or more, the plurality of R 7 are the same as or different from each other.
When h is 2 or more, the plurality of R 8 are the same as or different from each other.
One of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b). )
(前記一般式(2a)中、R9は、ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
iは0、1、2、3、4又は5である。)
(In the general formula (2a), R 9 represents a halogen atom,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
i is 0, 1, 2, 3, 4 or 5. )
(前記一般式(2b)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。)
(In the general formula (2b), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
本発明の一態様によれば、前述の本発明の一態様に係る組成物を含む、有機エレクトロルミネッセンス素子用材料が提供される。 According to one aspect of the present invention, there is provided a material for an organic electroluminescence device comprising the composition according to one aspect of the present invention.
本発明の一態様によれば、前述の本発明の一態様に係る組成物を含む組成物膜が提供される。 According to an aspect of the present invention, there is provided a composition film including the composition according to the above-described aspect of the present invention.
本発明の一態様によれば、陽極と、陰極と、前記陽極と前記陰極との間に含まれた有機層と、を備え、前記有機層は、前述の本発明の一態様に係る組成物を含む有機エレクトロルミネッセンス素子が提供される。 According to one aspect of the present invention, an anode, a cathode, and an organic layer included between the anode and the cathode, wherein the organic layer is a composition according to one aspect of the present invention described above. An organic electroluminescent device comprising:
本発明の一態様によれば、陽極と、陰極と、前記陽極と前記陰極との間に含まれた発光層と、前記発光層と前記陰極との間に含まれた電子輸送帯域を備え、前記電子輸送帯域は、前述の本発明の一態様に係る組成物を含む有機エレクトロルミネッセンス素子が提供される。 According to one aspect of the present invention, an anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport zone included between the light-emitting layer and the cathode, The electron transport zone is provided with an organic electroluminescence device including the composition according to one embodiment of the present invention.
本発明の一態様によれば、前述の本発明の一態様に係る有機エレクトロルミネッセンス素子を搭載した、電子機器が提供される。 According to one aspect of the present invention, there is provided an electronic device equipped with the organic electroluminescence element according to one aspect of the present invention described above.
本発明の一態様によれば、有機エレクトロルミネッセンス素子の性能を維持しながら、1つの蒸着源から材料の比率を安定的に蒸着させることのできる組成物を提供すること、当該組成物を含む有機エレクトロルミネッセンス素子用材料を提供すること、当該組成物を含む組成物膜を提供すること、当該組成物を含む有機エレクトロルミネッセンス素子を提供すること、並びに当該有機エレクトロルミネッセンス素子を備える電子機器を提供することができる。 According to one embodiment of the present invention, it is possible to provide a composition capable of stably depositing a ratio of materials from one deposition source while maintaining the performance of the organic electroluminescence device, and to provide an organic including the composition. Providing a material for an electroluminescent element, providing a composition film including the composition, providing an organic electroluminescent element including the composition, and providing an electronic device including the organic electroluminescent element be able to.
〔第一実施形態〕
(組成物)
本実施形態に係る組成物は、2種以上の化合物が混合された組成物である。
本実施形態に係る組成物は、少なくとも下記一般式(1)で表される第一の化合物及び下記一般式(2)で表される第二の化合物を含有する。
[First embodiment]
(Composition)
The composition according to this embodiment is a composition in which two or more compounds are mixed.
The composition according to this embodiment contains at least a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2).
本実施形態に係る組成物の形態は特に限定されない。本実施形態に係る組成物の形態としては、例えば、固体、粉末、溶液、及び膜などが挙げられる。本実施形態に係る組成物が固体である場合、ペレット状に成形されていてもよい。 The form of the composition according to the present embodiment is not particularly limited. Examples of the form of the composition according to this embodiment include solids, powders, solutions, and films. When the composition according to this embodiment is a solid, it may be formed into a pellet.
(第一の化合物)
第一の化合物は、下記一般式(1)で表される。
(First compound)
The first compound is represented by the following general formula (1).
(前記一般式(1)中、
R1、R2、R3及びR4は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
A1及びA2のうち、一方が、下記一般式(1a)で表される置換基であり、他方が、下記一般式(1b)で表される部分構造を含む置換基である。)
(In the general formula (1),
R 1 , R 2 , R 3 and R 4 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
One of A 1 and A 2 is a substituent represented by the following general formula (1a), and the other is a substituent including a partial structure represented by the following general formula (1b). )
(前記一般式(1a)中、X1、X2、X3、X4及びX5は、それぞれ独立して、CRX又は窒素原子を示す。RXは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRXは、互いに同一であるか、又は異なる。)
(In the
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R X are the same as or different from each other. )
(前記一般式(1b)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
X9、X10、X11、X12、X13、X14、X15、X16、X17及びX18は、それぞれ独立して、CRZ又は窒素原子を示す。RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。)
(In the
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 each independently represent CR Z or a nitrogen atom. R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other. )
第一の化合物において、X1、X2、X3、X4及びX5は、CRXであることが好ましい。この場合、RXは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示し、
複数のRXは、互いに同一であるか、又は異なる。
In the first compound, X 1 , X 2 , X 3 , X 4 and X 5 are preferably CR X. In this case, R X is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group;
The plurality of R X are the same as or different from each other.
第一の化合物において、a、b、c、及びdが0であることが好ましい。 In the first compound, a, b, c, and d are preferably 0.
前記一般式(1)におけるa、b、c、及びdが0であるとき、第一の化合物は、下記一般式(1A)で表される。 When a, b, c, and d in the general formula (1) are 0, the first compound is represented by the following general formula (1A).
(前記一般式(1A)中、
A1及びA2のうち、一方が、前記一般式(1a)で表される置換基であり、他方が、前記一般式(1b)で表される部分構造を含む置換基である。)
(In the general formula (1A),
One of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is a substituent including a partial structure represented by the general formula (1b). )
第一の化合物において、A1及びA2のうち、一方が、前記一般式(1a)で表される置換基であり、他方が、下記一般式(1c)で表される置換基であることが好ましい。 In the first compound, one of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is a substituent represented by the following general formula (1c). Is preferred.
(前記一般式(1c)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19、X20、X21、X22及びX23は、それぞれ独立して、CRZ又は窒素原子を示す。RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。
X19、X20、X21、X22及びX23の少なくとも1つはCRZであり、少なくとも1つのRZは、*と結合する単結合である。)
(In the
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 21 , X 22 and X 23 are each independently shows a CR Z or a nitrogen atom. R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other.
At least one of X 19 , X 20 , X 21 , X 22 and X 23 is CR Z , and at least one R Z is a single bond bonded to *. )
例えば、X21がCRZで、RZが*と結合する単結合である場合は、前記一般式(1c)は下記一般式(1d)で表される。 For example, when X 21 is CR Z and R Z is a single bond bonded to *, the general formula (1c) is represented by the following general formula (1d).
X19がCRZで、RZが*と結合する単結合である場合は、前記一般式(1c)は下記一般式(1d-1)で表される。 When X 19 is CR Z and R Z is a single bond bonded to *, the general formula (1c) is represented by the following general formula (1d-1).
X20がCRZで、RZが*と結合する単結合である場合は、前記一般式(1c)は下記一般式(1d-2)で表される。 When X 20 is CR Z and R Z is a single bond bonded to *, the general formula (1c) is represented by the following general formula (1d-2).
(前記一般式(1d)、(1d-1)、及び(1d-2)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
前記一般式(1d)中、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19、X20、X22及びX23は、それぞれ独立して、CRZ又は窒素原子を示す。
前記一般式(1d-1)中、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X20、X21、X22及びX23は、それぞれ独立して、CRZ又は窒素原子を示す。
前記一般式(1d-2)中、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19、X21、X22及びX23は、それぞれ独立して、CRZ又は窒素原子を示す。
前記一般式(1d)、(1d-1)、及び(1d-2)中、RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。)
(Formula (1d), (1d-1 ), and in (1d-2), X 6 ,
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
In the general formula (1d), X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 22 and X 23 are Each independently represents
In the general formula (1d-1), X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 20 , X 21 , X 22 and X 23 each independently represents CRZ or a nitrogen atom.
In the general formula (1d-2), X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 21 , X 22 and X 23 each independently represents CRZ or a nitrogen atom.
In the general formulas (1d), (1d-1), and (1d-2), R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other. )
第一の化合物が、下記一般式(3)で表される化合物であることが好ましい。 It is preferable that the first compound is a compound represented by the following general formula (3).
(前記一般式(3)中、
R1、R2、R3、R4、R14及びR15は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
pは、0、1、2、3、4又は5である。
qは、0、1、2、3、4又は5である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
pが2以上の場合、複数のR14は、互いに同一であるか、又は異なる。
qが2以上の場合、複数のR15は、互いに同一であるか、又は異なる。
B1及びB2は、下記一般式(4)で表される置換基を示す。
rは、0又は1である。
sは、0又は1である。
ただし、r+s=1である。)
(In the general formula (3),
R 1 , R 2 , R 3 , R 4 , R 14 and R 15 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
p is 0, 1, 2, 3, 4 or 5.
q is 0, 1, 2, 3, 4 or 5.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
When p is 2 or more, the plurality of R 14 are the same as or different from each other.
When q is 2 or more, the plurality of R 15 are the same as or different from each other.
B 1 and B 2 represent a substituent represented by the following general formula (4).
r is 0 or 1.
s is 0 or 1.
However, r + s = 1. )
(前記一般式(4)中、
X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
R16及びR17は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、又は
シアノ基を示す。
tは、0、1、2、3、4又は5である。
uは、0、1、2、3、4又は5である。
tが2以上の場合、複数のR16は、互いに同一であるか、又は異なる。
uが2以上の場合、複数のR17は、互いに同一であるか、又は異なる。)
(In the general formula (4),
X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom. R Y is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
R 16 and R 17 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
t is 0, 1, 2, 3, 4 or 5.
u is 0, 1, 2, 3, 4 or 5.
When t is 2 or more, the plurality of R 16 are the same as or different from each other.
When u is 2 or more, the plurality of R 17 are the same as or different from each other. )
前記一般式(3)におけるa、b、c及びdが0であるとき、第一の化合物は、下記一般式(3A)で表される。 When a, b, c and d in the general formula (3) are 0, the first compound is represented by the following general formula (3A).
(前記一般式(3A)中、
R14及びR15は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
pは、0、1、2、3、4又は5である。
qは、0、1、2、3、4又は5である。
pが2以上の場合、複数のR14は、互いに同一であるか、又は異なる。
qが2以上の場合、複数のR15は、互いに同一であるか、又は異なる。
B1及びB2は、前記一般式(4)で表される置換基を示す。
rは、0又は1である。
sは、0又は1である。
ただし、r+s=1である。)
(In the general formula (3A),
R 14 and R 15 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
p is 0, 1, 2, 3, 4 or 5.
q is 0, 1, 2, 3, 4 or 5.
When p is 2 or more, the plurality of R 14 are the same as or different from each other.
When q is 2 or more, the plurality of R 15 are the same as or different from each other.
B 1 and B 2 represent a substituent represented by the general formula (4).
r is 0 or 1.
s is 0 or 1.
However, r + s = 1. )
第一の化合物において、a、b、c、d、p、及びqが0であることが好ましい。 In the first compound, a, b, c, d, p, and q are preferably 0.
前記一般式(3)におけるa、b、c、d、p、及びqが0であるとき、第一の化合物は、下記一般式(3B)で表される。 When a, b, c, d, p, and q in the general formula (3) are 0, the first compound is represented by the following general formula (3B).
(前記一般式(3B)中、
B1及びB2は、前記一般式(4)で表される置換基を示す。
rは、0又は1である。
sは、0又は1である。
ただし、r+s=1である。)
(In the general formula (3B),
B 1 and B 2 represent a substituent represented by the general formula (4).
r is 0 or 1.
s is 0 or 1.
However, r + s = 1. )
第一の化合物において、X6、X7及びX8が、窒素原子を示すことが好ましい。 In the first compound, X 6 , X 7 and X 8 preferably represent a nitrogen atom.
第一の化合物において、rが1であり、sが0であることが好ましい。 In the first compound, it is preferable that r is 1 and s is 0.
例えば、前記一般式(3)におけるrが1であり、sが0である場合、第一の化合物は、下記一般式(3C)で表される。 For example, when r in the general formula (3) is 1 and s is 0, the first compound is represented by the following general formula (3C).
(前記一般式(3C)中、
R1、R2、R3、R4、R14及びR15は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
pは、0、1、2、3又は4である。
qは、0、1、2、3、4又は5である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
pが2以上の場合、複数のR14は、互いに同一であるか、又は異なる。
qが2以上の場合、複数のR15は、互いに同一であるか、又は異なる。
X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
R16及びR17は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、又は
シアノ基を示す。
tは、0、1、2、3、4又は5である。
uは、0、1、2、3、4又は5である。
tが2以上の場合、複数のR16は、互いに同一であるか、又は異なる。
uが2以上の場合、複数のR17は、互いに同一であるか、又は異なる。)
(In the general formula (3C),
R 1 , R 2 , R 3 , R 4 , R 14 and R 15 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
p is 0, 1, 2, 3 or 4.
q is 0, 1, 2, 3, 4 or 5.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
When p is 2 or more, the plurality of R 14 are the same as or different from each other.
When q is 2 or more, the plurality of R 15 are the same as or different from each other.
X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom. R Y is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
R 16 and R 17 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
t is 0, 1, 2, 3, 4 or 5.
u is 0, 1, 2, 3, 4 or 5.
When t is 2 or more, the plurality of R 16 are the same as or different from each other.
When u is 2 or more, the plurality of R 17 are the same as or different from each other. )
第一の化合物において、A1及びA2のうち、一方が、前記一般式(1a)で表される置換基であり、他方が、下記一般式(1e)で表されることも好ましい。 In the first compound, it is also preferable that one of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is represented by the following general formula (1e).
(前記一般式(1e)中、
X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
R16、R17及びR18は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、又は
シアノ基を示す。
tは、1、2、3、4又は5である。
uは、0、1、2、3、4又は5である。
vは、0、1、2、3、4又は5である。
tが3以上の場合(t-1=2以上の場合)、複数のR16は、互いに同一であるか、又は異なる。
uが2以上の場合、複数のR17は、互いに同一であるか、又は異なる。
vが2以上の場合、複数のR18は、互いに同一であるか、又は異なる。)
(In the general formula (1e),
X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom. R Y is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
R 16 , R 17 and R 18 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
t is 1, 2, 3, 4 or 5.
u is 0, 1, 2, 3, 4 or 5.
v is 0, 1, 2, 3, 4 or 5.
When t is 3 or more (when t−1 = 2 or more), the plurality of R 16 are the same as or different from each other.
When u is 2 or more, the plurality of R 17 are the same as or different from each other.
When v is 2 or more, the plurality of R 18 are the same as or different from each other. )
第一の化合物におけるアルキル基の例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、ペンチル基(異性体基を含む)、ヘキシル基(異性体基を含む)、ヘプチル基(異性体基を含む)、オクチル基(異性体基を含む)、ノニル基(異性体基を含む)、デシル基(異性体基を含む)、ウンデシル基(異性体基を含む)、及びドデシル基(異性体基を含む)などが挙げられる。これらの中でも、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、及びペンチル基(いずれも異性体基を含む)が好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、及びt-ブチル基がより好ましく、メチル基、エチル基、イソプロピル基、及びt-ブチル基がさらに好ましい。 Examples of the alkyl group in the first compound include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (isomer group) ), Hexyl group (including isomer group), heptyl group (including isomer group), octyl group (including isomer group), nonyl group (including isomer group), decyl group (isomer group) ), Undecyl group (including isomer group), dodecyl group (including isomer group), and the like. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a pentyl group (all including an isomer group) are preferable. , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group are more preferable, and methyl group, ethyl group, isopropyl group, and t-butyl group are more preferable. More preferred are groups.
第一の化合物におけるアルキル基の炭素数は、1~25であり、好ましくは1~10である。 The carbon number of the alkyl group in the first compound is 1 to 25, preferably 1 to 10.
第一の化合物におけるシクロアルキル基の例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、アダマンチル基などが挙げられる。これらの中でも、シクロペンチル基、シクロヘキシル基が好ましい。 Examples of the cycloalkyl group in the first compound include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
第一の化合物におけるシクロアルキル基の環形成炭素数は、3~25であり、好ましくは3~10であり、より好ましくは3~8であり、さらに好ましくは3~6である。 The number of carbon atoms of the cycloalkyl group in the first compound is 3 to 25, preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.
第一の化合物におけるハロゲン原子としては、フッ素、塩素、臭素、及びヨウ素等が挙げられ、好ましくはフッ素原子である。 Examples of the halogen atom in the first compound include fluorine, chlorine, bromine and iodine, and a fluorine atom is preferable.
第一の化合物におけるアリール基の例としては、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アセナフチレニル基、アントリル基、ベンゾアントリル基、アセアントリル基、フェナントリル基、ベンゾ[c]フェナントリル基、フェナレニル基、フルオレニル基、ピセニル基、ペンタフェニル基、ピレニル基、クリセニル基、ベンゾ[g]クリセニル基、s-インダセニル基、as-インダセニル基、フルオランテニル基、ベンゾ[k]フルオランテニル基、トリフェニレニル基、ベンゾ[b]トリフェニレニル基、及びペリレニル基などが挙げられる。これらの中でも、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、フェナントリル基、トリフェニレニル基、フルオランテニル基、及びフルオレニル基が好ましく、フェニル基、ビフェニリル基、及びターフェニリル基がより好ましく、フェニル基がさらに好ましい。 Examples of aryl groups in the first compound include phenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c] phenanthryl, phenalenyl Group, fluorenyl group, picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl Group, benzo [b] triphenylenyl group, perylenyl group and the like. Among these, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluoranthenyl group, and a fluorenyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is further preferable.
第一の化合物におけるアリール基の環形成炭素数は、6~24であり、好ましくは6~20であり、より好ましくは6~18である。 The number of ring-forming carbon atoms of the aryl group in the first compound is 6 to 24, preferably 6 to 20, and more preferably 6 to 18.
第一の化合物における複素環基は、芳香族性を有しない複素環基と、芳香族性を有する芳香族複素環基(1価であればヘテロアリール基、2価であればヘテロアリーレン基という)とを含む。 The heterocyclic group in the first compound includes a heterocyclic group having no aromaticity and an aromatic heterocyclic group having aromaticity (a heteroaryl group if monovalent, a heteroarylene group if bivalent). ).
第一の化合物における芳香族性を有しない複素環基としては、窒素原子、酸素原子もしくは硫黄原子を含む、環形成原子数3~30、好ましくは3~20の複素環基が挙げられる。芳香族性を有しない複素環の具体例としては、アジリジン、オキシラン、チイラン、アゼチジン、オキセタン、トリメチレンスルフィド、ピロリジン、テトラヒドロフラン、テトラヒドロチオフェン、ピペリジン、テトラヒドロピラン、及びテトラヒドロチオピラン等が挙げられる。 Examples of the heterocyclic group having no aromaticity in the first compound include heterocyclic groups containing 3 to 30 ring-forming atoms, preferably 3 to 20 containing a nitrogen atom, oxygen atom or sulfur atom. Specific examples of the heterocyclic ring having no aromaticity include aziridine, oxirane, thiirane, azetidine, oxetane, trimethylene sulfide, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, and tetrahydrothiopyran.
第一の化合物における複素環基としては、窒素原子、酸素原子、硫黄原子、及びリン原子等のヘテロ原子を含む環状基が挙げられ、環形成原子として、窒素原子、酸素原子又は硫黄原子からなる群から選ばれる原子を含有することが好ましい。複素環基としては、芳香族性を有するヘテロアリール基が好ましい。ヘテロアリール基の例としては、ピロリル基、フリル基、チエニル基、ピリジル基、イミダゾピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、オキサゾリル基、チアゾリル基、ピラゾリル基、イソオキサゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、インドリル基、イソインドリル基、ベンゾフラニル基、イソベンゾフラニル基、ベンゾチエニル基、イソベンゾチエニル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、シンノリル基、フタラジニル基、キナゾリニル基、キノキサリニル基、ベンズイミダゾリル基、ベンズオキサゾリル基、ベンズチアゾリル基、インダゾリル基、ベンズイソキサゾリル基、ベンズイソチアゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルバゾリル基、9-フェニルカルバゾリル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、フェナジニル基、フェノチアジニル基、フェノキサジニル基、及びキサンテニル基などが挙げられる。これらの中でも、ピリジル基、イミダゾピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、ベンズイミダゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルバゾリル基、9位にアリール基又は複素環基が置換したカルバゾリル基、フェナントロリニル基、及びキナゾリニル基が好ましい。 Examples of the heterocyclic group in the first compound include a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and the ring-forming atom includes a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable to contain an atom selected from the group. As the heterocyclic group, a heteroaryl group having aromaticity is preferable. Examples of heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, imidazopyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl , Isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothienyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl Group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimidazolyl group, benzoxazolyl group, benzthiazolyl group, indazolyl group, benzisoxazolyl group Benzisothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenylcarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl And xanthenyl group. Among these, pyridyl group, imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, substituted with aryl group or heterocyclic group at 9-position Preferred are carbazolyl group, phenanthrolinyl group, and quinazolinyl group.
第一の化合物における複素環基の環形成原子数は、3~30であり、好ましくは5~24であり、より好ましくは5~18である。
第一の化合物におけるヘテロアリール基の環形成原子数は、5~30であり、好ましくは5~24であり、より好ましくは5~18である。
第一の化合物におけるヘテロアリール基の炭素原子以外の環形成原子としては、窒素原子、酸素原子又は硫黄原子が好ましい。
The number of ring-forming atoms of the heterocyclic group in the first compound is 3 to 30, preferably 5 to 24, and more preferably 5 to 18.
The number of ring-forming atoms of the heteroaryl group in the first compound is 5 to 30, preferably 5 to 24, and more preferably 5 to 18.
The ring-forming atom other than the carbon atom of the heteroaryl group in the first compound is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
第一の化合物におけるヘテロアリーレン基は、前記ヘテロアリール基からさらに1つの水素原子又は置換基が除去された2価の基である。 The heteroarylene group in the first compound is a divalent group obtained by further removing one hydrogen atom or substituent from the heteroaryl group.
第一の化合物における炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基の例としては、モノ置換シリル基、ジ置換シリル基、及びトリ置換シリル基が挙げられる。 Examples of silyl groups substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 25 carbon atoms and aryl groups having 6 to 24 ring carbon atoms in the first compound include mono-substituted silyl groups , Disubstituted silyl groups, and trisubstituted silyl groups.
第一の化合物におけるモノ置換シリル基は、-SiH2(Y10)、又は-SiH2(Y20)で表される。
第一の化合物におけるジ置換シリル基は、-SiH(Y10)2、-SiH(Y20)2、又は-SiH(Y10)(Y20)で表される。
第一の化合物におけるトリ置換シリル基は、-Si(Y10)3、-Si(Y20)3、-Si(Y10)2(Y20)、又は-Si(Y10)(Y20)2で表される。
上記において、Y10は炭素数1~25のアルキル基を表し、Y20は環形成炭素数6~24のアリール基を表す。
Y10が複数存在する場合、複数のY10は、互いに同一であっても、異なっていてもよい。
Y20が複数存在する場合、複数のY20は、互いに同一であっても、異なっていてもよい。
The mono-substituted silyl group in the first compound is represented by —SiH 2 (Y 10 ) or —SiH 2 (Y 20 ).
The disubstituted silyl group in the first compound is represented by —SiH (Y 10 ) 2 , —SiH (Y 20 ) 2 , or —SiH (Y 10 ) (Y 20 ).
The tri-substituted silyl group in the first compound is —Si (Y 10 ) 3 , —Si (Y 20 ) 3 , —Si (Y 10 ) 2 (Y 20 ), or —Si (Y 10 ) (Y 20 ). It is represented by 2 .
In the above, Y 10 represents an alkyl group having 1 to 25 carbon atoms, and Y 20 represents an aryl group having 6 to 24 ring carbon atoms.
If Y 10 there are a plurality, the plurality of Y 10 can be the same as each other or may be different.
If Y 20 there are a plurality, the plurality of Y 20 can be the same as each other or may be different.
第一の化合物において、R1、R2、R3及びR4は、それぞれ独立して、ハロゲン原子、置換もしくは無置換の炭素数1~25のアルキル基、置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、炭素数1~25のアルキル基で置換されたシリル基、又はシアノ基を示すことが好ましい。 In the first compound, R 1 , R 2 , R 3 and R 4 each independently represent a halogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, or a substituted or unsubstituted ring forming carbon number. It preferably represents a cycloalkyl group having 3 to 25, a silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
第一の化合物は、従来公知の合成方法(例えば、国際公開第2011/132684号に記載の方法など)を組み合わせて製造することができる。
本実施形態に係る第一の化合物の例を以下に示す。本発明における第一の化合物は、これらの具体例に限定されない。
A 1st compound can be manufactured combining a conventionally well-known synthesis method (For example, the method of the international publication 2011/132684 etc.).
Examples of the first compound according to this embodiment are shown below. The first compound in the present invention is not limited to these specific examples.
(第二の化合物)
第二の化合物は、下記一般式(2)で表される。
(Second compound)
The second compound is represented by the following general formula (2).
(前記一般式(2)中、R5、R6、R7及びR8は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
eは、0、1、2、3又は4である。
fは、0、1、2又は3である。
gは、0、1、2又は3である。
hは、0、1、2、3又は4である。
eが2以上の場合、複数のR5は、互いに同一であるか、又は異なる。
fが2以上の場合、複数のR6は、互いに同一であるか、又は異なる。
gが2以上の場合、複数のR7は、互いに同一であるか、又は異なる。
hが2以上の場合、複数のR8は、互いに同一であるか、又は異なる。
A3及びA4のうち、一方が、下記一般式(2a)で表される置換基であり、他方が、下記一般式(2b)で表される置換基である。)
(In the general formula (2), R 5 , R 6 , R 7 and R 8 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3 or 4;
f is 0, 1, 2 or 3.
g is 0, 1, 2 or 3.
h is 0, 1, 2, 3 or 4.
When e is 2 or more, the plurality of R 5 are the same as or different from each other.
When f is 2 or more, the plurality of R 6 are the same as or different from each other.
When g is 2 or more, the plurality of R 7 are the same as or different from each other.
When h is 2 or more, the plurality of R 8 are the same as or different from each other.
One of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b). )
(前記一般式(2a)中、R9は、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
iは0、1、2、3、4又は5である。)
(In the general formula (2a), R 9 is
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
i is 0, 1, 2, 3, 4 or 5. )
(前記一般式(2b)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。)
(In the general formula (2b), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
第二の化合物において、R9は、
置換もしくは無置換の炭素数1~25のアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示すことが好ましい。
In the second compound, R 9 is
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
It is preferably a silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、下記一般式(5)で表される置換基であることが好ましい。 In the second compound, one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the following general formula (5). Is preferred.
(前記一般式(5)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。)
(In the general formula (5), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、下記一般式(2c)、下記一般式(2d)、又は下記一般式(2e)で表される置換基であることも好ましい。 In the second compound, one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the following general formula (2c), the following general formula (2d), or It is also preferable that it is a substituent represented by the following general formula (2e).
(前記一般式(2c)、前記一般式(2d)、及び前記一般式(2e)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。)
(In the general formula (2c), the general formula (2d), and the general formula (2e), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、下記一般式(5a)で表される置換基であることが好ましい。 In the second compound, one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the following general formula (5a). Is preferred.
(前記一般式(5a)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。)
(In the general formula (5a), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、前記一般式(5)、一般式(2c)、一般式(2d)、又は一般式(2e)で表される置換基であることが好ましい。
第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、前記一般式(5a)であることがより好ましい。
In the second compound, one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the general formula (5), the general formula (2c), or the general formula. It is preferable that it is a substituent represented by (2d) or general formula (2e).
In the second compound, it is more preferable that one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is the general formula (5a).
第二の化合物において、e、f、g及びhが0であることが好ましい。 In the second compound, e, f, g and h are preferably 0.
前記一般式(2)におけるe、f、g及びhが0であるとき、第二の化合物は、下記一般式(2A)で表される。 When e, f, g, and h in the general formula (2) are 0, the second compound is represented by the following general formula (2A).
(前記一般式(2A)中、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、前記一般式(2b)で表される置換基である。) (In the general formula (2A), one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the general formula (2b). .)
第二の化合物において、j、k、l及びmが0であることが好ましい。
第二の化合物において、i、j、k、l及びmが0であることがより好ましい。
第二の化合物において、e、f、g、h、i、j、k、l及びmが0であることがさらに好ましい。
In the second compound, j, k, l and m are preferably 0.
In the second compound, i, j, k, l and m are more preferably 0.
In the second compound, it is more preferable that e, f, g, h, i, j, k, l and m are 0.
第二の化合物において、e、f、g、h、i、j、k、l及びmが0であるとき、第二の化合物は、下記一般式(2B)で表される。 In the second compound, when e, f, g, h, i, j, k, l and m are 0, the second compound is represented by the following general formula (2B).
第二の化合物における炭素数1~25のアルキル基、環形成炭素数3~25のシクロアルキル基、環形成炭素数6~24のアリール基、環形成原子数3~30の複素環基、及び炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基の具体例は、それぞれ、第一の化合物において説明した置換基の具体例と同様である。 An alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 3 to 25 ring carbon atoms, an aryl group having 6 to 24 ring carbon atoms, a heterocyclic group having 3 to 30 ring atoms, and Specific examples of the silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms have been described in the first compound. The same as the specific examples of the substituent.
第二の化合物は、従来公知の合成方法(例えば、国際公開第2013/084885号に記載の方法など)を組み合わせて製造することができる。
本実施形態に係る第二の化合物の例を以下に示す。本発明における第二の化合物は、これらの具体例に限定されない。
A 2nd compound can be manufactured combining a conventionally well-known synthetic | combination method (For example, the method of the international publication 2013/084885 etc.).
Examples of the second compound according to this embodiment are shown below. The second compound in the present invention is not limited to these specific examples.
本実施形態の組成物は、前記第一の化合物及び前記第二の化合物を組み合わせて含有しているため、本実施形態の組成物は、有機エレクトロルミネッセンス素子の性能を維持しながら、1つの蒸着源から材料の比率を安定的に蒸着させることができる。 Since the composition of the present embodiment contains a combination of the first compound and the second compound, the composition of the present embodiment is a single vapor deposition while maintaining the performance of the organic electroluminescence device. The ratio of materials from the source can be stably deposited.
(組成物の配合比)
本発明の一実施形態では、前記第一の化合物と前記第二の化合物との配合比は特に限定されない。組成物に求める効果に応じて、前記第一の化合物と前記第二の化合物との配合比を適宜決定すればよい。「第一の化合物:第二の化合物」で表される化合物の配合比(質量比)は、通常、1:99~99:1の範囲内であり、10:90~90:10の範囲内が好ましく、40:60~60:40の範囲内がより好ましい。
(Composition ratio of the composition)
In one embodiment of the present invention, the compounding ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine the compounding ratio of said 1st compound and said 2nd compound suitably according to the effect calculated | required by the composition. The compounding ratio (mass ratio) of the compound represented by “first compound: second compound” is usually in the range of 1:99 to 99: 1, and in the range of 10:90 to 90:10. In the range of 40:60 to 60:40 is more preferable.
(有機エレクトロルミネッセンス素子用材料)
本実施形態に係る有機エレクトロルミネッセンス素子用材料は、本実施形態に係る組成物を含む。すなわち、本実施形態に係る有機エレクトロルミネッセンス素子用材料は、前記第一の化合物、及び前記第二の化合物を含有する。
本実施形態に係る有機エレクトロルミネッセンス素子用材料は、さらにその他の化合物を含有していてもよい。本実施形態に係る有機エレクトロルミネッセンス素子用材料が、さらにその他の化合物を含んでいる場合、該その他の化合物は、固体であっても液体であってもよい。
(Materials for organic electroluminescence elements)
The material for an organic electroluminescence element according to this embodiment includes the composition according to this embodiment. That is, the organic electroluminescent element material according to the present embodiment contains the first compound and the second compound.
The material for an organic electroluminescence element according to this embodiment may further contain other compounds. When the organic electroluminescent element material according to the present embodiment further includes other compounds, the other compounds may be solid or liquid.
(組成物膜)
本実施形態に係る組成物膜は、本実施形態に係る組成物を含む。すなわち、本実施形態に係る組成物を含む膜(組成物膜)は、前記第一の化合物、及び前記第二の化合物を含有する膜を意味する。
本実施形態に係る組成物膜は、さらにその他の化合物を含有していてもよい。
本実施形態に係る組成物膜の形成方法は、本明細書において特に限定される旨を言及した場合を除いて、形成方法は特に制限されない。組成物膜の形成方法としては、乾式成膜法、及び湿式成膜法等の公知の方法を採用できる。乾式成膜法としては、真空蒸着法、スパッタリング法、プラズマ法、及びイオンプレーティング法等が挙げられる。湿式成膜法としては、スピンコーティング法、ディッピング法、フローコーティング法、及びインクジェット法等が挙げられる。
(Composition film)
The composition film according to the present embodiment includes the composition according to the present embodiment. That is, the film (composition film) containing the composition according to the present embodiment means a film containing the first compound and the second compound.
The composition film according to the present embodiment may further contain other compounds.
The method for forming the composition film according to the present embodiment is not particularly limited unless otherwise specified in the present specification. As a method for forming the composition film, known methods such as a dry film forming method and a wet film forming method can be employed. Examples of the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method. Examples of the wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.
(有機EL素子の素子構成)
本実施形態に係る有機EL素子は、陽極と、陰極と、前記陽極と前記陰極との間に有機層を備える。前記有機層は、有機化合物で構成される層を少なくとも一つ含む。あるいは、前記有機層は、有機化合物で構成される複数の層が積層されてなる。前記有機層は、無機化合物をさらに含んでいてもよい。本実施形態の有機EL素子において、前記有機層のうち少なくとも一層は、発光層である。ゆえに、前記有機層は、例えば、一つの発光層で構成されていてもよいし、有機EL素子に採用され得る層を含んでいてもよい。有機EL素子に採用され得る層としては、特に限定されないが、例えば、正孔注入層、正孔輸送層、電子注入層、電子輸送層、及び障壁層からなる群から選択される少なくともいずれかの層が挙げられる。
(Element structure of organic EL element)
The organic EL device according to this embodiment includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer includes at least one layer composed of an organic compound. Alternatively, the organic layer is formed by laminating a plurality of layers composed of organic compounds. The organic layer may further contain an inorganic compound. In the organic EL device of the present embodiment, at least one of the organic layers is a light emitting layer. Therefore, the organic layer may be composed of, for example, a single light emitting layer, or may include a layer that can be employed in an organic EL element. The layer that can be employed in the organic EL element is not particularly limited. For example, at least one selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a barrier layer. Layer.
本実施形態において、前記有機層は、複数の層で構成され、本実施形態に係る組成物は、前記複数の層のうちの1層以上に含まれていることが好ましい。 In the present embodiment, the organic layer is preferably composed of a plurality of layers, and the composition according to the embodiment is preferably contained in one or more of the plurality of layers.
本実施形態に係る有機EL素子のいずれか1層以上に本実施形態に係る組成物を使用することにより、高い有機EL性能(例えば、駆動電圧、発光効率、及び寿命の少なくともいずれかの発光性能)を得ることができる。さらに、本実施形態に係る組成物が本実施形態に係る方法(例えば真空蒸着法)を用いて成膜されている場合、蒸着初期から蒸着終期まで、発光層中の第一の化合物と第二の化合物との材料比が安定する。その結果、有機EL素子も、蒸着時間によらず、安定して高い発光性能を維持することができる。
本実施形態に係る有機EL素子において、発光層が本実施形態に係る組成物を含有することが好ましい。
By using the composition according to this embodiment in any one or more layers of the organic EL element according to this embodiment, high organic EL performance (for example, light emission performance of at least one of driving voltage, light emission efficiency, and lifetime) ) Can be obtained. Further, when the composition according to the present embodiment is formed using the method according to the present embodiment (for example, vacuum deposition method), the first compound and the second compound in the light emitting layer from the initial deposition stage to the final deposition stage. The material ratio with the compound is stable. As a result, the organic EL element can stably maintain high light emission performance regardless of the deposition time.
In the organic EL device according to this embodiment, the light emitting layer preferably contains the composition according to this embodiment.
本実施形態において、前記陽極と前記発光層との間に、さらに正孔輸送層を有することが好ましい。
本実施形態において、前記陰極と前記発光層との間に、さらに電子輸送層を有することが好ましい。
別の実施形態として、本発明の一実施形態に係る組成物が電子輸送帯域に使用されることも好ましい。
In this embodiment, it is preferable that a hole transport layer is further provided between the anode and the light emitting layer.
In this embodiment, it is preferable to further have an electron transport layer between the cathode and the light emitting layer.
As another embodiment, it is also preferable that the composition according to an embodiment of the present invention is used in the electron transport zone.
有機EL素子の代表的な素子構成としては、例えば、次の(a)~(f)等の構成を挙げることができる。
(a)陽極/発光層/陰極
(b)陽極/正孔注入・輸送層/発光層/陰極
(c)陽極/発光層/電子注入・輸送層/陰極
(d)陽極/正孔注入・輸送層/発光層/電子注入・輸送層/陰極
(e)陽極/正孔注入・輸送層/発光層/障壁層/電子注入・輸送層/陰極
(f)陽極/正孔注入・輸送層/障壁層/発光層/障壁層/電子注入・輸送層/陰極
上記の中で(d)の構成が好ましく用いられる。ただし、本発明は、これらの構成に限定されない。なお、上記「発光層」とは、発光機能を有する有機層である。前記「正孔注入・輸送層」は「正孔注入層、及び正孔輸送層のうちの少なくともいずれか1つ」を意味する。前記「電子注入・輸送層」は「電子注入層、及び電子輸送層のうちの少なくともいずれか1つ」を意味する。有機EL素子が、正孔注入層、及び正孔輸送層を有する場合には、正孔輸送層と陽極との間に正孔注入層が設けられていることが好ましい。また、有機EL素子が電子注入層、及び電子輸送層を有する場合には、電子輸送層と陰極との間に電子注入層が設けられていることが好ましい。また、正孔注入層、正孔輸送層、電子輸送層、及び電子注入層のそれぞれは、一層で構成されていてもよいし、複数の層で構成されていてもよい。
As typical element configurations of the organic EL element, for example, the following configurations (a) to (f) can be given.
(A) Anode / light emitting layer / cathode (b) Anode / hole injection / transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron injection / transport layer / cathode (d) Anode / hole injection / transport Layer / light emitting layer / electron injection / transport layer / cathode (e) anode / hole injection / transport layer / light emitting layer / barrier layer / electron injection / transport layer / cathode (f) anode / hole injection / transport layer / barrier Layer / light emitting layer / barrier layer / electron injection / transport layer / cathode Among the above, the structure of (d) is preferably used. However, the present invention is not limited to these configurations. The “light emitting layer” is an organic layer having a light emitting function. The “hole injection / transport layer” means “at least one of a hole injection layer and a hole transport layer”. The “electron injection / transport layer” means “at least one of an electron injection layer and an electron transport layer”. When the organic EL element has a hole injection layer and a hole transport layer, it is preferable that a hole injection layer is provided between the hole transport layer and the anode. Moreover, when an organic EL element has an electron injection layer and an electron carrying layer, it is preferable that the electron injection layer is provided between the electron carrying layer and the cathode. In addition, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be composed of a single layer or a plurality of layers.
図1に、本実施形態に係る有機EL素子の一例の概略構成を示す。
有機EL素子1は、透光性の基板2と、陽極3と、陰極4と、陽極3と陰極4との間に配置された有機層10と、を有する。有機層10は、正孔注入層6、正孔輸送層7、発光層5、電子輸送層8、及び電子注入層9を含む。有機層10は、陽極3側から順に、正孔注入層6、正孔輸送層7、発光層5、電子輸送層8、及び電子注入層9が、この順番で積層されている。
FIG. 1 shows a schematic configuration of an example of the organic EL element according to this embodiment.
The
有機EL素子1の発光層5は、本実施形態に係る組成物を含有する。すなわち、発光層5は、前記第一の化合物、及び前記第二の化合物を含む。
The
本実施形態の有機EL素子によれば、前記第一の化合物、及び前記第二の化合物を組み合わせて有機層に用いたことにより、有機EL素子が低電圧で駆動する。有機EL素子を低電圧で駆動させるという観点から、前記第一の化合物、及び前記第二の化合物が1つの発光層に含まれている態様が好ましい。 According to the organic EL device of the present embodiment, the organic EL device is driven at a low voltage by using the first compound and the second compound in combination in the organic layer. From the viewpoint of driving the organic EL element at a low voltage, an embodiment in which the first compound and the second compound are contained in one light emitting layer is preferable.
(有機EL素子における配合比)
本発明の一実施形態では、第一の化合物と第二の化合物との配合比は特に限定されない。有機EL素子に求める効果に応じて、第一の化合物と第二の化合物との配合比を適宜決定すればよい。「第一の化合物:第二の化合物」で表される化合物の配合比(質量比)は、通常、1:99~99:1の範囲内であり、10:90~90:10の範囲内が好ましく、40:60~60:40の範囲内がより好ましい。
(Compounding ratio in organic EL device)
In one embodiment of the present invention, the blending ratio of the first compound and the second compound is not particularly limited. What is necessary is just to determine suitably the compounding ratio of a 1st compound and a 2nd compound according to the effect calculated | required from an organic EL element. The compounding ratio (mass ratio) of the compound represented by “first compound: second compound” is usually in the range of 1:99 to 99: 1, and in the range of 10:90 to 90:10. In the range of 40:60 to 60:40 is more preferable.
(発光材料)
本発明の一態様である有機EL素子は、前記発光層が、さらに発光材料を含有することが好ましい。
本発明の一実施形態では、前記発光層が発光材料として燐光発光材料を含有することが好ましい。前記燐光発光材料がイリジウム(Ir)、オスミウム(Os)、及び白金(Pt)からなる群から選択されるいずれかの金属原子のオルトメタル化錯体であることが好ましい。好適な燐光発光材料については後述する。
(Luminescent material)
In the organic EL element which is one embodiment of the present invention, the light emitting layer preferably further contains a light emitting material.
In one embodiment of the present invention, it is preferable that the light emitting layer contains a phosphorescent material as a light emitting material. The phosphorescent material is preferably an orthometalated complex of any metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt). Suitable phosphorescent materials will be described later.
前記発光層が、第一の化合物と第二の化合物と発光材料とを含む場合、発光層における発光材料の含有率は、0.1質量%以上50質量%以下であることが好ましく、1質量%以上20質量%以下であることがより好ましい。 When the light emitting layer includes the first compound, the second compound, and the light emitting material, the content of the light emitting material in the light emitting layer is preferably 0.1% by mass or more and 50% by mass or less. % To 20% by mass is more preferable.
(層形成方法)
本発明の一態様である有機EL素子の各層の形成方法は、本明細書において特に限定される旨を言及した場合を除いて、形成方法は特に制限されない。各層の形成方法としては、乾式成膜法、及び湿式成膜法等の公知の方法を採用できる。乾式成膜法としては、真空蒸着法、スパッタリング法、プラズマ法、及びイオンプレーティング法等が挙げられる。湿式成膜法としては、スピンコーティング法、ディッピング法、フローコーティング法、及びインクジェット法等が挙げられる。
(Layer formation method)
The formation method of each layer of the organic EL element which is one embodiment of the present invention is not particularly limited unless otherwise specified in the present specification. As a method for forming each layer, known methods such as a dry film forming method and a wet film forming method can be employed. Examples of the dry film forming method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method. Examples of the wet film forming method include a spin coating method, a dipping method, a flow coating method, and an ink jet method.
(膜厚)
本発明の一態様である有機EL素子の各層の膜厚は、本明細書において特に言及した以外には制限されない。各層の膜厚は、適切な膜厚に設定することが好ましい。膜が厚すぎると、一定の光出力を得るために大きな印加電圧が必要になり効率が悪くなるおそれがある。膜が薄すぎるとピンホール等が発生して、電界を印加しても充分な発光輝度が得られないおそれがある。通常、膜厚は、5nm~10μmの範囲が適しており、10nm~0.2μmの範囲がさらに好ましい。
(Film thickness)
The film thickness of each layer of the organic EL element which is one embodiment of the present invention is not limited except as specifically mentioned in the present specification. The film thickness of each layer is preferably set to an appropriate film thickness. If the film is too thick, a large applied voltage is required to obtain a constant light output, and the efficiency may deteriorate. If the film is too thin, pinholes and the like are generated, and there is a possibility that sufficient light emission luminance cannot be obtained even when an electric field is applied. Usually, the film thickness is suitably in the range of 5 nm to 10 μm, more preferably in the range of 10 nm to 0.2 μm.
以下、有機EL素子の構成要素の材料等について説明する。
(基板)
基板は、発光素子の支持体として用いられる。基板としては、例えば、ガラス、石英、又はプラスチック等を用いることができる。また、基板としては、可撓性基板を用いてもよい。可撓性基板とは、折り曲げることができる(フレキシブル)基板のことであり、例えば、ポリカーボネート、及びポリ塩化ビニルからなるプラスチック基板等が挙げられる。
Hereinafter, materials of constituent elements of the organic EL element will be described.
(substrate)
The substrate is used as a support for the light emitting element. For example, glass, quartz, plastic, or the like can be used as the substrate. Further, a flexible substrate may be used as the substrate. The flexible substrate is a substrate that can be bent (flexible), and examples thereof include a plastic substrate made of polycarbonate and polyvinyl chloride.
(陽極)
基板上に形成される陽極には、仕事関数の大きい(具体的には4.0eV以上)金属、合金、電気伝導性化合物、及びこれらの混合物等を用いることが好ましい。具体的には、例えば、酸化インジウム-酸化スズ(ITO:Indium Tin Oxide)、珪素若しくは酸化珪素を含有した酸化インジウム-酸化スズ、酸化インジウム-酸化亜鉛、酸化タングステン、及び酸化亜鉛を含有した酸化インジウム、並びにグラフェン等が挙げられる。この他、金(Au)、白金(Pt)、又は金属材料の窒化物(例えば、窒化チタン)等が挙げられる。
(anode)
For the anode formed on the substrate, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more). Specifically, for example, indium tin oxide (ITO), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, and indium oxide containing zinc oxide. And graphene. In addition, gold (Au), platinum (Pt), a nitride of a metal material (for example, titanium nitride), or the like can be given.
(正孔注入層)
正孔注入層は、陽極から有機層に効率よく正孔を注入するために設けられる層である。正孔注入層に使用される物質としては、モリブデン酸化物、チタン酸化物、バナジウム酸化物、レニウム酸化物、ルテニウム酸化物、クロム酸化物、ジルコニウム酸化物、ハフニウム酸化物、タンタル酸化物、銀酸化物、タングステン酸化物、マンガン酸化物、芳香族アミン化合物、アクセプター性の化合物、又は高分子化合物(オリゴマー、デンドリマー、ポリマー等)等も使用できる。
正孔注入層に使用される物質としては、中でも、芳香族アミン誘導体、又はアクセプター性の化合物であることが好ましく、アクセプター性の化合物であることが更に好ましい。アクセプター性の化合物として、電子吸引基により置換された複素環誘導体、電子吸引基により置換されたキノン誘導体、アリールボラン誘導体、またはヘテロアリールボラン誘導体等が好適に用いられ、中でも、ヘキサシアノヘキサアザトリフェニレン、F4TCNQ(2,3,5,6-テトラフルオロ-7,7,8,8-テトラシアノキノジメタン)、又は1,2,3-トリス[(シアノ)(4-シアノ-2,3,5,6-テトラフルオロフェニル)メチレン]シクロプロパン等が好ましく用いられる。
アクセプター性の化合物を含む層は、更にマトリクス材料を含有する形態であっても好ましい。マトリクス材料としては、有機EL用の材料を幅広く使用することができる。アクセプター性の化合物と共に使用するマトリクス材料として、ドナー性化合物を用いることが好ましく、芳香族アミン化合物を用いることが更に好ましい。
(Hole injection layer)
The hole injection layer is a layer provided for efficiently injecting holes from the anode into the organic layer. Substances used for the hole injection layer include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide An oxide, a tungsten oxide, a manganese oxide, an aromatic amine compound, an acceptor compound, a polymer compound (oligomer, dendrimer, polymer, etc.), or the like can also be used.
Among them, the substance used for the hole injection layer is preferably an aromatic amine derivative or an acceptor compound, and more preferably an acceptor compound. As the acceptor compound, a heterocyclic derivative substituted with an electron withdrawing group, a quinone derivative substituted with an electron withdrawing group, an arylborane derivative, a heteroarylborane derivative, or the like is preferably used. Among them, hexacyanohexaazatriphenylene, F 4 TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or 1,2,3-tris [(cyano) (4-cyano-2,3 , 5,6-tetrafluorophenyl) methylene] cyclopropane or the like is preferably used.
The layer containing an acceptor compound is preferably in a form further containing a matrix material. A wide variety of materials for organic EL can be used as the matrix material. As the matrix material used together with the acceptor compound, a donor compound is preferably used, and an aromatic amine compound is more preferably used.
(正孔輸送層)
正孔輸送層は、正孔輸送性の高い物質を含む層である。正孔輸送層には、芳香族アミン化合物、カルバゾール誘導体、又はアントラセン誘導体等を使用する事ができる。ポリ(N-ビニルカルバゾール)(略称:PVK)やポリ(4-ビニルトリフェニルアミン)(略称:PVTPA)等の高分子化合物を用いることもできる。但し、電子よりも正孔の輸送性の高い物質であれば、これら以外の物質を用いてもよい。尚、正孔輸送性の高い物質を含む層は、単層でもよく、又は上記物質からなる層が二層以上積層されていてもよい。正孔輸送材料は、好ましくは、下記一般式(H)で表される化合物である。
(Hole transport layer)
The hole transport layer is a layer containing a substance having a high hole transport property. An aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used for the hole transport layer. A high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used. However, any substance other than these may be used as long as it has a property of transporting more holes than electrons. Note that the layer containing a substance having a high hole-transport property may be a single layer, or two or more layers containing the above substances may be stacked. The hole transport material is preferably a compound represented by the following general formula (H).
前記一般式(H)中、Ar1~Ar3は、それぞれ独立に、置換もしくは無置換の環形成炭素数6~50のアリール基、置換もしくは無置換の環形成原子数5~50の複素環基または、置換もしくは無置換のアリール基と置換もしくは無置換の複素環基との組合せで構成される基を示す。アリール基としては、フェニル基、ビフェニル基、ターフェニル基、フルオレニル基、スピロビフルオレニル基、インデノフルオレニル基、ナフチル基、フェナントリル基、アントリル基、又はトリフェニレニル基等の置換基が好ましい。複素環基としては、ジベンゾフラニル基、ジベンゾチエニル基、又はカルバゾリル基等が好ましい。アリール基と複素環基との組合せで構成される基としては、ジベンゾフラン置換のアリール基、ジベンゾチオフェン置換のアリール基、又はカルバゾール置換のアリール基等が好ましい。これら置換基はさらに置換基を有していてもよく、好ましい置換基は後述の通りである。
好ましい1つの態様として、前記一般式(H)のAr1~Ar3の少なくとも1つが、アリールアミノ基によって更に置換されている化合物であることが好ましく、ジアミン誘導体、トリアミン誘導体、又はテトラアミン誘導体であることも好ましい。ジアミン誘導体として、テトラアリール置換ベンジジン誘導体、及びTPTE(4,4’-ビス[N-フェニル-N-[4’-ジフェニルアミノ-1,1’-ビフェニル-4-イル]アミノ]-1,1’-ビフェニル)等が好ましく用いられる。
燐光発光層に接する層に使用する正孔輸送材料は、三重項準位が高いことが好ましく、前記一般式(H)におけるAr1~Ar3は、それぞれ独立に、フルオレニル基、スピロフルオレニル基、フェニル基、ビフェニル基、フェナントリル基、トリフェニレニル基、ジベンゾフラニル基、及びジベンゾチエニル基等の置換基、並びにそれらの基の組合せで形成される基からなる群から選択される少なくともいずれかの基であることが好ましい。
In the general formula (H), Ar 1 to Ar 3 are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 50 ring atoms. Or a group composed of a combination of a substituted or unsubstituted aryl group and a substituted or unsubstituted heterocyclic group. As the aryl group, a substituent such as a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a triphenylenyl group is preferable. . As the heterocyclic group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, or the like is preferable. The group composed of a combination of an aryl group and a heterocyclic group is preferably a dibenzofuran-substituted aryl group, a dibenzothiophene-substituted aryl group, a carbazole-substituted aryl group, or the like. These substituents may further have a substituent, and preferred substituents are as described below.
As a preferred embodiment, at least one of Ar 1 to Ar 3 in the general formula (H) is preferably a compound further substituted with an arylamino group, and is a diamine derivative, a triamine derivative, or a tetraamine derivative. It is also preferable. As diamine derivatives, tetraaryl-substituted benzidine derivatives and TPTE (4,4′-bis [N-phenyl-N- [4′-diphenylamino-1,1′-biphenyl-4-yl] amino] -1,1 '-Biphenyl) and the like are preferably used.
The hole transport material used for the layer in contact with the phosphorescent light emitting layer preferably has a high triplet level, and Ar 1 to Ar 3 in the general formula (H) are each independently a fluorenyl group or spirofluorenyl. At least one selected from the group consisting of substituents such as a group, phenyl group, biphenyl group, phenanthryl group, triphenylenyl group, dibenzofuranyl group, and dibenzothienyl group, and a group formed by a combination of these groups It is preferably a group.
(発光層)
発光層は、発光性の高い物質を含む層である。発光層には、種々の材料を用いることができる。発光層は、通常、発光性の高い発光材料(ドーパント材料)と、発光材料を効率よく発光させるためのホスト材料とが含有されている。例えば、発光性の高い物質としては、蛍光を発光する蛍光性化合物又は燐光を発光する燐光性化合物を用いることができる。蛍光性化合物は、一重項励起状態から発光可能な化合物である。燐光性化合物は、三重項励起状態から発光可能な化合物である。蛍光性化合物を含む発光層は、蛍光発光層と呼ばれる。燐光性化合物を含む発光層は、燐光発光層と呼ばれている。
(Light emitting layer)
The light emitting layer is a layer containing a substance having high light emitting property. Various materials can be used for the light emitting layer. The light emitting layer usually contains a light emitting material (dopant material) having high light emitting property and a host material for causing the light emitting material to emit light efficiently. For example, as the substance having high light-emitting property, a fluorescent compound that emits fluorescence or a phosphorescent compound that emits phosphorescence can be used. A fluorescent compound is a compound that can emit light from a singlet excited state. A phosphorescent compound is a compound that can emit light from a triplet excited state. The light emitting layer containing a fluorescent compound is called a fluorescent light emitting layer. The light emitting layer containing a phosphorescent compound is called a phosphorescent light emitting layer.
蛍光発光層のドーパント材料として、蛍光発光性の化合物を幅広く用いることができる。蛍光発光層のドーパント材料としては、中でも、縮合多環芳香族誘導体、スチリルアミン誘導体、縮合環アミン誘導体、ホウ素含有化合物、ピロール誘導体、インドール誘導体、及びカルバゾール誘導体等が好ましい。蛍光発光層のドーパント材料としては、さらに好ましくは、縮合環アミン誘導体、及びホウ素含有化合物が挙げられる。縮合環アミン誘導体としては、例えば、ジアミノピレン誘導体、ジアミノクリセン誘導体、ジアミノアントラセン誘導体、ジアミノフルオレン誘導体、及びベンゾフロ骨格が1つ以上縮環したジアミノフルオレン誘導体などが挙げられる。ホウ素含有化合物としては、例えば、ピロメテン誘導体、及びトリフェニルボラン誘導体等が挙げられる。ここで誘導体とは、当該骨格を部分構造として含む化合物を示す言葉であり、当該骨格と更なる環を有し縮合環を形成する化合物、及び置換基同士で環を形成する当該骨格を有する化合物も含有する。例えば、縮合多環芳香族誘導体の場合は、縮合多環芳香族骨格を部分構造として含む化合物であり、当該縮合多環芳香族骨格にさらに縮合環を形成する化合物、及び当該縮合多環芳香族骨格の置換基同士で環を形成する化合物も含有する。 Fluorescent compounds can be widely used as dopant materials for the fluorescent layer. As the dopant material for the fluorescent light emitting layer, among them, condensed polycyclic aromatic derivatives, styrylamine derivatives, condensed ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like are preferable. More preferable examples of the dopant material for the fluorescent light emitting layer include condensed ring amine derivatives and boron-containing compounds. Examples of the condensed ring amine derivative include diaminopyrene derivatives, diaminochrysene derivatives, diaminoanthracene derivatives, diaminofluorene derivatives, and diaminofluorene derivatives in which one or more benzofuro skeletons are condensed. Examples of the boron-containing compound include a pyromethene derivative and a triphenylborane derivative. Here, the term “derivative” refers to a compound that includes the skeleton as a partial structure, a compound that has a further ring with the skeleton and forms a condensed ring, and a compound that has the skeleton that forms a ring with substituents. Also contains. For example, in the case of a condensed polycyclic aromatic derivative, it is a compound that contains a condensed polycyclic aromatic skeleton as a partial structure, a compound that further forms a condensed ring in the condensed polycyclic aromatic skeleton, and the condensed polycyclic aromatic Also included are compounds that form a ring with substituents of the skeleton.
蛍光発光層に用いるホスト材料としては、一般的な蛍光材料を使用することができる。蛍光発光層に用いるホスト材料としては、中でも、縮合多環芳香族誘導体を主骨格に持つ化合物であることが好ましく、より好ましくは、アントラセン誘導体、ピレン誘導体、クリセン誘導体、及びナフタセン誘導体等が挙げられる。青色ホスト材料(青色蛍光発光性のドーパント材料と共に用いられるホスト材料)、及び緑色ホスト材料(緑色蛍光発光性のドーパント材料と共に用いられるホスト材料)として好適なホストは、下記一般式(X)で表されるアントラセン誘導体である。 A general fluorescent material can be used as a host material used for the fluorescent light emitting layer. Among them, the host material used for the fluorescent light emitting layer is preferably a compound having a condensed polycyclic aromatic derivative as a main skeleton, and more preferably an anthracene derivative, a pyrene derivative, a chrysene derivative, a naphthacene derivative, or the like. . A host suitable as a blue host material (a host material used with a blue fluorescent material dopant material) and a green host material (a host material used with a green fluorescent material dopant material) is represented by the following general formula (X). Anthracene derivatives.
前記一般式(X)において、ArX1、及びArX2は、それぞれ独立に、置換もしくは無置換の環形成炭素数6~50のアリール基、又は置換もしくは無置換の環形成原子数3~50の複素環基を示す。ArX1、及びArX2は、それぞれ独立に、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示すことが好ましい。 In the general formula (X), Ar X1 and Ar X2 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring atom having 3 to 50 ring atoms. A heterocyclic group is shown. Ar X1 and Ar X2 each independently preferably represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. .
燐光発光層に用いることができる燐光発光材料(ドーパント材料)として、イリジウム錯体、オスミウム錯体、及び白金錯体等の金属錯体が使用される。
イリジウム(Ir)、オスミウム(Os)、及び白金(Pt)からなる群から選択される金属原子のオルトメタル化錯体である燐光発光材料は、下記式(α)で表される錯体であることが好ましい。
As a phosphorescent material (dopant material) that can be used for the phosphorescent layer, a metal complex such as an iridium complex, an osmium complex, or a platinum complex is used.
The phosphorescent material that is an orthometalated complex of a metal atom selected from the group consisting of iridium (Ir), osmium (Os), and platinum (Pt) is a complex represented by the following formula (α). preferable.
式(α)において、Mは、オスミウム、イリジウム及び白金からなる群から選ばれる少なくとも一つの金属を示し、nは、該金属の価数を示す。
環A1は、置換もしくは無置換の環形成炭素数6~24のアリール基又は置換もしくは無置換の環形成原子数5~30のヘテロアリール基を表し、環A2は、窒素をヘテロ環形成原子として含有する置換もしくは無置換の環形成原子数5~30のヘテロアリール基を表す。
In the formula (α), M represents at least one metal selected from the group consisting of osmium, iridium and platinum, and n represents the valence of the metal.
Ring A 1 represents a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, and Ring A 2 forms a nitrogen heterocycle A substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms contained as an atom is represented.
式(α)の環A1における環形成炭素数6~24のアリール基としては、前述した一般式(1)におけるアリール基が挙げられる。
式(α)の環A1及び環A2における環形成原子数5~30のヘテロアリール基としては、前述した一般式(1)におけるヘテロアリール基が挙げられる。
式(α)の環A1及び環A2が有し得る置換基は、前述した一般式(1)における置換基と同じである。
さらに、式(α)で表される錯体は、下記式(T)又は(U)で表される錯体であることが好ましい。
Examples of the aryl group having 6 to 24 ring carbon atoms in the ring A 1 of the formula (α) include the aryl groups in the general formula (1) described above.
Examples of the heteroaryl group having 5 to 30 ring atoms in the ring A 1 and the ring A 2 of the formula (α) include the heteroaryl groups in the general formula (1) described above.
The substituent that the ring A 1 and the ring A 2 of the formula (α) may have is the same as the substituent in the general formula (1) described above.
Furthermore, the complex represented by the formula (α) is preferably a complex represented by the following formula (T) or (U).
式(T)において、Mは、金属を表し、環B及び環Cは、各々独立に環形成原子数5若しくは6のアリール基又はヘテロアリール基を表す。
環A-環Bは、ヘテロアリール基と、アリール基又はヘテロアリール基との結合対を表す。環A-環Bは、環Aの窒素原子及び環Bのsp2混成原子を介して金属Mに配位する。
環A-環Cは、ヘテロアリール基と、アリール基又はヘテロアリール基との結合対を表す。
Ra、Rb及びRcは、各々独立に、水素原子、置換もしくは無置換の炭素数1~25のアルキル基、置換もしくは無置換の炭素数1~25のアルコキシ基、置換もしくは無置換のアミノ基、置換もしくは無置換の炭素数2~25のアルケニル基、置換もしくは無置換の炭素数2~25のアルキニル基、置換もしくは無置換の炭素数7~50のアラルキル基、置換もしくは無置換の環形成炭素数6~24のアリール基、及び置換もしくは無置換の環形成原子数5~30のヘテロアリール基からなる群より選択されるいずれかを表し、Raは、1つ以上4つ以下であり、Rbは、1つ以上4つ以下であり、Rcは、1つ以上4つ以下であり、Ra、Rb及びRcの数は、各々独立である。
X1~X9は、各々独立に、炭素原子又は窒素原子を表す。
Rd及びReは、各々独立に、水素原子、置換もしくは無置換の炭素数1~25のアルキル基、置換もしくは無置換の炭素数1~25のアルコキシ基、置換もしくは無置換のアミノ基、置換もしくは無置換の炭素数2~25のアルケニル基、置換もしくは無置換の炭素数2~25のアルキニル基、置換もしくは無置換の炭素数7~50のアラルキル基、置換もしくは無置換の環形成炭素数6~24のアリール基、及び置換もしくは無置換の環形成原子数5~30のヘテロアリール基からなる群より選択されるいずれかを表し、環Cに結合するRc、Rd及びReの少なくとも1つは、水素原子ではない。
mは、金属Mの酸化状態を表し、nは1以上である。L’は、モノアニオン性の二座配位子を表す。
In formula (T), M represents a metal, and ring B and ring C each independently represent an aryl group or heteroaryl group having 5 or 6 ring atoms.
Ring A-ring B represents a bond pair of a heteroaryl group and an aryl group or heteroaryl group. Ring A-ring B is coordinated to metal M via the nitrogen atom of ring A and the sp 2 hybrid atom of ring B.
Ring A to ring C represent a bond pair of a heteroaryl group and an aryl group or heteroaryl group.
R a , R b and R c are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted group; Amino group, substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted This represents any one selected from the group consisting of an aryl group having 6 to 24 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, and R a is 1 or more and 4 or less R b is 1 or more and 4 or less, R c is 1 or more and 4 or less, and the numbers of R a , R b and R c are independent of each other.
X 1 to X 9 each independently represents a carbon atom or a nitrogen atom.
R d and R e are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, a substituted or unsubstituted amino group, Substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, substituted or unsubstituted ring-forming carbon R c , R d and R e bonded to the ring C, each represented by any one selected from the group consisting of an aryl group having 6 to 24 and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms At least one of is not a hydrogen atom.
m represents an oxidation state of the metal M, and n is 1 or more. L ′ represents a monoanionic bidentate ligand.
式(T)において、Mは、オスミウム、イリジウム、及び白金等が挙げられ、中でもイリジウムが好ましい。
環B及び環Cで表される環形成炭素数6のアリール基としては、前述した一般式(1)におけるアリール基が挙げられる。
環B及び環Cで表される環形成原子数5若しくは6のヘテロアリール基としては、前述した一般式(1)におけるヘテロアリール基が挙げられる。
R1、R2、Ra、Rb及びRcで表される置換もしくは無置換の炭素数1~25のアルキル基、置換もしくは無置換の炭素数1~25のアルコキシ基、置換もしくは無置換の炭素数7~50のアラルキル基、置換もしくは無置換の環形成炭素数6~24のアリール基及び置換もしくは無置換の環形成原子数5~30のヘテロアリール基としては、それぞれ、前述した基と同様の基が挙げられる。
R1、R2、Ra、Rb及びRcで表される置換もしくは無置換の炭素数2~25のアルケニル基、及び置換もしくは無置換の炭素数2~25のアルキニル基としては、それぞれ、前述した基と同様の基が挙げられる。
L’で表されるモノアニオン性の二座配位子としては、下記式(L’)で表わされる配位子が挙げられる。
In the formula (T), examples of M include osmium, iridium, and platinum, and iridium is particularly preferable.
Examples of the aryl group having 6 ring-forming carbon atoms represented by ring B and ring C include the aryl group in the general formula (1) described above.
Examples of the heteroaryl group having 5 or 6 ring atoms represented by ring B and ring C include the heteroaryl group in the general formula (1) described above.
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms represented by R 1 , R 2 , R a , R b and R c , a substituted or unsubstituted alkoxy group having 1 to 25 carbon atoms, substituted or unsubstituted Examples of the aralkyl group having 7 to 50 carbon atoms, the substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms and the substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms are the groups described above. The same group is mentioned.
As the substituted or unsubstituted alkenyl group having 2 to 25 carbon atoms and the substituted or unsubstituted alkynyl group having 2 to 25 carbon atoms represented by R 1 , R 2 , R a , R b and R c , respectively, And the same groups as those described above.
Examples of the monoanionic bidentate ligand represented by L ′ include a ligand represented by the following formula (L ′).
式(L’)において、X4~X9、Ra、及びRbは、式(T)におけるX4~X9、Ra、及びRbと同義であり、好ましい態様も同様である。
X9から環Bより外側に伸びる実線と、環Aの窒素原子から環Aより外側に伸びる破線を介して、式(L’)で表わされる配位子は、式(T)で表される金属Mに配位する。
In the formula (L '), X 4 ~ X 9, R a, and R b are the same as X 4 ~ X 9, R a , and R b in Formula (T), preferable embodiments thereof are also the same.
The ligand represented by the formula (L ′) is represented by the formula (T) through a solid line extending from the ring X 9 to the outside of the ring B and a broken line extending from the nitrogen atom of the ring A to the outside of the ring A. Coordinates to metal M.
式(U)において、Xは、NR、酸素原子、硫黄原子、BR、及びセレン原子からなる群より選択されるいずれかを表し、Rは、水素原子又は置換もしくは無置換の炭素数1~25のアルキル基である。
R1、R2、R3及びR4は、各々独立に、水素原子、置換もしくは無置換の炭素数1~25のアルキル基、及び置換もしくは無置換の環形成炭素数6~24のアリール基からなる群より選択されるいずれかを表し、R1は、1つ以上4つ以下であり、R2は、1つ以上4つ以下であり、R3は、1つ以上4つ以下であり、R4は、1つ以上4つ以下であり、R1、R2、R3及びR4の数は、各々独立である。
In the formula (U), X represents any one selected from the group consisting of NR, oxygen atom, sulfur atom, BR, and selenium atom, and R represents a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 25 It is an alkyl group.
R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms. R 1 is 1 or more and 4 or less, R 2 is 1 or more and 4 or less, and R 3 is 1 or more and 4 or less , R 4 is 1 or more and 4 or less, and the numbers of R 1 , R 2 , R 3 and R 4 are independent of each other.
式(U)において、R、R1、R2、R3及びR4で表される炭素数1~25のアルキル基としては、前述した基が挙げられ、好ましい態様も同様である。
また、R1、R2、R3及びR4で表される環形成炭素数6~24のアリール基としては、前述した基が挙げられ、好ましい態様も同様である。
In the formula (U), examples of the alkyl group having 1 to 25 carbon atoms represented by R, R 1 , R 2 , R 3 and R 4 include the groups described above, and preferred embodiments thereof are also the same.
In addition, examples of the aryl group having 6 to 24 ring carbon atoms represented by R 1 , R 2 , R 3, and R 4 include the groups described above, and preferred embodiments thereof are also the same.
式(T)又は(U)で表される錯体としては、以下の化合物が好適であるが、特にこれらに限定されない。 As the complex represented by the formula (T) or (U), the following compounds are suitable, but are not particularly limited thereto.
また、燐光発光材料として、下記式(β)で表されるイリジウム錯体も好ましい。 Further, as the phosphorescent material, an iridium complex represented by the following formula (β) is also preferable.
式(β)において、A1~A8は炭素原子又は窒素原子を含み、A1~A8の少なくとも1つは窒素原子であり、環BはC-C結合により環Aに結合し、イリジウム(Ir)はIr-C結合により環Aに結合する。
式(β)において、A1~A8の内、1つのみが窒素原子であることが好ましく、A5~A8の内、1つのみが窒素原子であることがさらに好ましく、A5が窒素原子であることが好ましい。式(β)において、A1~A4の内、A3及びA4が炭素原子であることが好ましい。式(β)において、A5が窒素原子であり、A1~A4、並びにA6~A8が炭素原子であることが好ましい。
A6が、CR(Rが結合する炭素原子)であることが好ましく、Rは、置換もしくは無置換の炭素数1~25のアルキル、置換もしくは無置換の環形成炭素数3~25のシクロアルキル、及びこれらの組み合わせからなる群から選択される。Rは、好ましくは、置換もしくは無置換の炭素数1~25のアルキル又は置換もしくは無置換の環形成炭素数3~25のシクロアルキルである。
式(β)において、XはO,S又はSeであり、Oが好ましい。
式(β)において、R1~R4は、各々独立して、モノ-置換、ジ-置換、トリ-置換もしくはテトラ-置換、又は無置換であり、隣接するR1は互いに結合して環を形成してもよく、隣接するR2は互いに結合して環を形成してもよく、隣接するR3は互いに結合して環を形成してもよく、隣接するR4は互いに結合して環を形成してもよく、R1~R4は、各々独立して、
水素、
重水素、
ハロゲン、
置換もしくは無置換の炭素数1~25のアルキル、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル、
置換もしくは無置換の原子数2~25のヘテロアルキル、
置換もしくは無置換の炭素数7~50のアリールアルキル、
置換もしくは無置換の炭素数1~25のアルコキシ、
置換もしくは無置換の環形成炭素数6~24のアリールオキシ、
置換もしくは無置換のアミノ、
置換シリル、
置換もしくは無置換の炭素数2~25のアルケニル、
置換もしくは無置換の環形成炭素数3~25のシクロアルケニル、
置換もしくは無置換の原子数3~25のヘテロアルケニル、
置換もしくは無置換の炭素数2~25のアルキニル、
置換もしくは無置換の環形成炭素数6~24のアリール、
置換もしくは無置換の環形成原子数5~30のヘテロアリール、
アシル、
置換カルボニル、
カルボン酸、
エステル、
ニトリル、
イソニトリル、
スルファニル、
スルフィニル、
スルホニル、
ホスフィノ、及びこれらの組み合わせからなる群から選択され、置換シリルは、炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリルであり、置換カルボニルは、炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたカルボニルである。式(β)において、R1~R4は、各々独立して、水素、重水素、炭素数1~25のアルキル及びこれらの組み合わせからなる群から選択することが好ましい。R2及びR3の少なくともいずれかが炭素数1~25のアルキル基であることが好ましく、当該アルキル基が重水素化されているか、もしくは部分的に重水素化されていることがさらに好ましい。
式(β)において、nは1~3の整数であり、1であることが好ましい。
In the formula (β), A 1 to A 8 contain a carbon atom or a nitrogen atom, at least one of A 1 to A 8 is a nitrogen atom, ring B is bonded to ring A by a C—C bond, and iridium (Ir) is bonded to ring A through an Ir—C bond.
In the formula (β), it is preferred that only one of A 1 to A 8 is a nitrogen atom, more preferred that only one of A 5 to A 8 is a nitrogen atom, and A 5 is A nitrogen atom is preferred. In the formula (β), it is preferable that A 3 and A 4 are carbon atoms among A 1 to A 4 . In the formula (β), A 5 is preferably a nitrogen atom, and A 1 to A 4 and A 6 to A 8 are preferably carbon atoms.
A 6 is preferably CR (carbon atom to which R is bonded), and R is a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms. , And combinations thereof. R is preferably a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms or a substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms.
In the formula (β), X is O, S or Se, and O is preferable.
In the formula (β), R 1 to R 4 are each independently mono-substituted, di-substituted, tri-substituted or tetra-substituted, or unsubstituted, and adjacent R 1 are bonded to each other to form a ring Adjacent R 2 may be bonded to each other to form a ring, adjacent R 3 may be bonded to each other to form a ring, and adjacent R 4 may be bonded to each other. A ring may be formed, and R 1 to R 4 each independently represent:
hydrogen,
deuterium,
halogen,
Substituted or unsubstituted alkyl having 1 to 25 carbon atoms,
Substituted or unsubstituted cycloalkyl having 3 to 25 ring carbon atoms,
Substituted or unsubstituted heteroalkyl having 2 to 25 atoms,
Substituted or unsubstituted arylalkyl having 7 to 50 carbon atoms,
Substituted or unsubstituted alkoxy having 1 to 25 carbon atoms,
Substituted or unsubstituted aryloxy having 6 to 24 ring carbon atoms,
Substituted or unsubstituted amino,
Substituted silyl,
Substituted or unsubstituted alkenyl having 2 to 25 carbon atoms,
Substituted or unsubstituted cycloalkenyl having 3 to 25 ring carbon atoms,
Substituted or unsubstituted heteroalkenyl having 3 to 25 atoms,
Substituted or unsubstituted alkynyl having 2 to 25 carbon atoms,
Substituted or unsubstituted aryl having 6 to 24 ring carbon atoms,
Substituted or unsubstituted heteroaryl having 5 to 30 ring atoms,
Acyl,
Substituted carbonyls,
carboxylic acid,
ester,
Nitrile,
Isonitrile,
Sulfanyl,
Sulfinyl,
Sulfonyl,
Selected from the group consisting of phosphino and combinations thereof, the substituted silyl is substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 25 carbon atoms and aryl groups having 6 to 24 ring carbon atoms. The substituted carbonyl is a carbonyl substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms. In the formula (β), R 1 to R 4 are preferably each independently selected from the group consisting of hydrogen, deuterium, alkyl having 1 to 25 carbon atoms, and combinations thereof. At least one of R 2 and R 3 is preferably an alkyl group having 1 to 25 carbon atoms, more preferably the alkyl group is deuterated or partially deuterated.
In the formula (β), n is an integer of 1 to 3, and is preferably 1.
式(β)で表されるイリジウム錯体の具体例を以下に示すが、これらに限定されない。 Specific examples of the iridium complex represented by the formula (β) are shown below, but are not limited thereto.
式(α)で表される錯体として、式(T)又は(U)で表される錯体以外に、下記式(V)、(X)、(Y)又は(Z)で表される錯体を用いることもできる。 As the complex represented by the formula (α), in addition to the complex represented by the formula (T) or (U), the complex represented by the following formula (V), (X), (Y) or (Z) It can also be used.
式(V)、(X)、(Y)又は(Z)において、R50~R54は、各々独立に、水素原子又は置換基であり、kは1~4の整数であり、lは1~4の整数であり、mは1~2の整数である。Mは、Ir、Os、又はPtである。
R50~R54の示す置換基としては、前述した置換基と同様の置換基が挙げられる。
式(V)は下記式(V-1)で表されることが好ましく、式(X)は下記式(X-1)又は式(X-2)で表されることが好ましい。下記式(V-1)、(X-1)、及び(X-2)において、R50、k及びMは、上記の、R50、k及びMと同じである。
In the formula (V), (X), (Y) or (Z), R 50 to R 54 are each independently a hydrogen atom or a substituent, k is an integer of 1 to 4, and 1 is 1 Is an integer from 4 to 4, and m is an integer from 1 to 2. M is Ir, Os, or Pt.
Examples of the substituent represented by R 50 to R 54 include the same substituents as those described above.
Formula (V) is preferably represented by the following formula (V-1), and formula (X) is preferably represented by the following formula (X-1) or formula (X-2). In the following formulas (V-1), (X-1), and (X-2), R 50 , k, and M are the same as R 50 , k, and M described above.
式(V)、(X)、(Y)又は(Z)で表される錯体の具体例を、以下に示すが、特にこれらに限定されない。 Specific examples of the complex represented by the formula (V), (X), (Y) or (Z) are shown below, but are not particularly limited thereto.
(発光層のホスト材料)
燐光発光層に用いるホスト材料としては、燐光ドーパントよりも高い三重項準位を持つ材料であることが好ましく、一般的な芳香族誘導体、複素環誘導体、及び金属錯体等の燐光ホスト材料を使用することができる。燐光発光層に用いるホスト材料としては、中でも芳香族誘導体、及び複素環誘導体が好ましく、芳香族誘導体としては、例えば、ナフタレン誘導体、トリフェニレン誘導体、フェナントレン誘導体、及びフルオランテン誘導体等が挙げられ、複素環誘導体としては、例えば、インドール誘導体、カルバゾール誘導体、ピリジン誘導体、ピリミジン誘導体、トリアジン誘導体、キノリン誘導体、イソキノリン誘導体、キナゾリン誘導体、ジベンゾフラン誘導体、及びジベンゾチエニル誘導体等が挙げられる。ここで、誘導体とは前述した通りの定義である。
燐光発光層に用いるホスト材料の好ましい一つの形態として、本発明の一実施形態に係る組成物が挙げられる。
(Host material for light emitting layer)
The host material used for the phosphorescent light-emitting layer is preferably a material having a triplet level higher than that of the phosphorescent dopant, and a phosphorescent host material such as a general aromatic derivative, heterocyclic derivative, or metal complex is used. be able to. Among the host materials used for the phosphorescent light emitting layer, aromatic derivatives and heterocyclic derivatives are preferable, and examples of aromatic derivatives include naphthalene derivatives, triphenylene derivatives, phenanthrene derivatives, and fluoranthene derivatives. Examples include indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, and dibenzothienyl derivatives. Here, the derivative is defined as described above.
One preferred form of the host material used for the phosphorescent light emitting layer is a composition according to an embodiment of the present invention.
(電子輸送層)
電子輸送層は、電子輸送性の高い物質を含む層である。
有機EL素子の性能向上のために、電子輸送層と発光層との間に1つ以上の層を設けることもできる。この層は第2電子輸送層、正孔障壁層、又は三重項ブロック層などと呼ばれる。正孔障壁性を高めるためには、HOMO準位が深い材料を用いることが好ましい。三重項ブロック性を高めるためには、三重項準位が高い材料を用いることが好ましい。
電子輸送層には、アルミニウム錯体、ベリリウム錯体、及び亜鉛錯体等の金属錯体、イミダゾール誘導体、ベンゾイミダゾール誘導体、アジン誘導体、カルバゾール誘導体、及びフェナントロリン誘導体等の複素環化合物、縮合芳香族炭化水素誘導体、並びに高分子化合物を使用することができる。好ましくは、イミダゾール誘導体(例えばベンズイミダゾール誘導体、イミダゾピリジン誘導体、ベンズイミダゾフェナントリジン誘導体)、アジン誘導体(例えば、ピリミジン誘導体、トリアジン誘導体、キノリン誘導体、イソキノリン誘導体、フェナントロリン誘導体が挙げられ、これら複素環はホスフィンオキサイド系の置換基で置換されていてもよい。)、及び芳香族炭化水素誘導体(例えば、アントラセン誘導体、フルオランテン誘導体が挙げられる)である。
電子輸送層、正孔障壁層、又は三重項ブロック層に含まれる材料の好ましい一つの形態として、本発明の一実施形態に係る組成物を用いることができる。
好ましい一つの形態として、電子輸送層は、アルカリ金属(LiやCs等)、アルカリ土類金属(Mg等)、および、これらを含む合金等、アルカリ金属の誘導体(例えば、リチウムキノリネート錯体)、並びにアルカリ土類金属の誘導体からなる群から選択される少なくとも一種を含有していてもよい。電子輸送層がアルカリ金属、アルカリ土類金属およびそれら合金の少なくともいずれかを含有する場合、電子輸送層中の含有比率は、好ましくは0.1~50質量%、より好ましくは0.1~20質量%、更に好ましくは1~10質量%であり、電子輸送層がアルカリ金属の誘導体及びアルカリ土類金属の誘導体の少なくともいずれかを含有する場合、電子輸送層中の含有比率は、好ましくは、1~99質量%、より好ましくは10~90質量%である。
(Electron transport layer)
The electron transport layer is a layer containing a substance having a high electron transport property.
In order to improve the performance of the organic EL element, one or more layers may be provided between the electron transport layer and the light emitting layer. This layer is called a second electron transport layer, a hole blocking layer, a triplet block layer, or the like. In order to improve the hole barrier property, it is preferable to use a material having a deep HOMO level. In order to improve the triplet blocking property, it is preferable to use a material having a high triplet level.
The electron transport layer includes metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, heterocyclic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, condensed aromatic hydrocarbon derivatives, and Polymeric compounds can be used. Preferably, imidazole derivatives (for example, benzimidazole derivatives, imidazopyridine derivatives, benzimidazophenanthridine derivatives), azine derivatives (for example, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, phenanthroline derivatives, etc., and these heterocyclic rings Phosphine oxide-based substituents), and aromatic hydrocarbon derivatives (for example, anthracene derivatives and fluoranthene derivatives).
As one preferred form of the material contained in the electron transport layer, hole blocking layer, or triplet block layer, the composition according to one embodiment of the present invention can be used.
As one preferable mode, the electron transport layer is formed of an alkali metal derivative (for example, lithium quinolinate complex) such as an alkali metal (Li, Cs, etc.), an alkaline earth metal (Mg, etc.), and an alloy containing these. And at least one selected from the group consisting of alkaline earth metal derivatives. When the electron transport layer contains at least one of alkali metals, alkaline earth metals and alloys thereof, the content ratio in the electron transport layer is preferably 0.1 to 50% by mass, more preferably 0.1 to 20%. % By mass, more preferably 1 to 10% by mass, and when the electron transport layer contains at least one of an alkali metal derivative and an alkaline earth metal derivative, the content ratio in the electron transport layer is preferably It is 1 to 99% by mass, more preferably 10 to 90% by mass.
(電子注入層)
電子注入層は、電子注入性の高い物質を含む層である。電子注入層には、リチウム(Li)、フッ化リチウム(LiF)、フッ化セシウム(CsF)、フッ化カルシウム(CaF2)、リチウム酸化物(LiOx)等のようなアルカリ金属、アルカリ土類金属、又はこれらを含む合金等、アルカリ金属の誘導体(例えば、リチウムキノリネート錯体)、並びにアルカリ土類金属の誘導体を用いることができる。
(Electron injection layer)
The electron injection layer is a layer containing a substance having a high electron injection property. For the electron injection layer, alkali metals such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), lithium oxide (LiO x ), and the like are used. Alkali metal derivatives (for example, lithium quinolinate complexes) and alkaline earth metal derivatives such as metals or alloys containing them can be used.
(陰極)
陰極には、仕事関数の小さい(具体的には3.8eV以下)金属、合金、電気伝導性化合物、及びこれらの混合物等を用いることが好ましい。このような陰極材料の具体例としては、元素周期表の第1族又は第2族に属する元素、即ちリチウム(Li)やセシウム(Cs)等のアルカリ金属、及びマグネシウム(Mg)等のアルカリ土類金属、及びこれらを含む合金(例えば、MgAg、AlLi)等の希土類金属及びこれらを含む合金等が挙げられる。
(cathode)
For the cathode, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less). Specific examples of such cathode materials include elements belonging to
本明細書において、水素原子とは、中性子数が異なる同位体、即ち、軽水素(protium)、重水素(deuterium)、三重水素(tritium)、を包含する。 In this specification, the hydrogen atom includes isotopes having different neutron numbers, that is, light hydrogen (protium), deuterium (triuterium), and tritium.
本明細書において、環形成炭素数とは、原子が環状に結合した構造の化合物(例えば、単環化合物、縮合環化合物、架橋化合物、炭素環化合物、複素環化合物)の当該環自体を構成する原子のうちの炭素原子の数を表す。当該環が置換基によって置換される場合、置換基に含まれる炭素は環形成炭素数には含まない。以下で記載される「環形成炭素数」については、特筆しない限り同様とする。例えば、ベンゼン環は環形成炭素数が6であり、ナフタレン環は環形成炭素数が10であり、ピリジニル基は環形成炭素数が5であり、フラニル基は環形成炭素数が4である。また、ベンゼン環やナフタレン環に置換基として例えばアルキル基が置換している場合、当該アルキル基の炭素数は、環形成炭素数の数に含めない。また、フルオレン環に置換基として例えばフルオレン環が結合している場合(スピロフルオレン環を含む)、置換基としてのフルオレン環の炭素数は環形成炭素数の数に含めない。 In this specification, the number of ring-forming carbon atoms constitutes the ring itself of a compound having a structure in which atoms are bonded cyclically (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, or a heterocyclic compound). Represents the number of carbon atoms in the atom. When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons. The “ring-forming carbon number” described below is the same unless otherwise specified. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridinyl group has 5 ring carbon atoms, and a furanyl group has 4 ring carbon atoms. Further, when an alkyl group is substituted as a substituent on the benzene ring or naphthalene ring, the carbon number of the alkyl group is not included in the number of ring-forming carbons. In addition, for example, when a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the carbon number of the fluorene ring as a substituent is not included in the number of ring-forming carbons.
本明細書において、環形成原子数とは、原子が環状に結合した構造(例えば単環、縮合環、環集合)の化合物(例えば単環化合物、縮合環化合物、架橋化合物、炭素環化合物、複素環化合物)の当該環自体を構成する原子の数を表す。環を構成しない原子や、当該環が置換基によって置換される場合の置換基に含まれる原子は環形成原子数には含まない。以下で記載される「環形成原子数」については、特筆しない限り同様とする。例えば、ピリジン環は環形成原子数が6であり、キナゾリン環は環形成原子数が10であり、フラン環は環形成原子数が5である。ピリジン環やキナゾリン環の炭素原子にそれぞれ結合している水素原子や置換基を構成する原子については、環形成原子数の数に含めない。また、フルオレン環に置換基として例えばフルオレン環が結合している場合(スピロフルオレン環を含む)、置換基としてのフルオレン環の原子数は環形成原子数の数に含めない。 In the present specification, the number of ring-forming atoms means a compound (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocycle) having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic ring, a condensed ring, or a ring assembly). Of the ring compound) represents the number of atoms constituting the ring itself. Atoms that do not constitute a ring or atoms included in a substituent when the ring is substituted by a substituent are not included in the number of ring-forming atoms. The “number of ring-forming atoms” described below is the same unless otherwise specified. For example, the pyridine ring has 6 ring atoms, the quinazoline ring has 10 ring atoms, and the furan ring has 5 ring atoms. A hydrogen atom bonded to a carbon atom of a pyridine ring or a quinazoline ring or an atom constituting a substituent is not included in the number of ring-forming atoms. Further, when, for example, a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.
本明細書において、「置換もしくは無置換の炭素数XX~YYのZZ基」という表現における「炭素数XX~YY」は、ZZ基が無置換である場合の炭素数を表し、置換されている場合の置換基の炭素数は含めない。 In the present specification, “carbon number XX to YY” in the expression “substituted or unsubstituted ZZ group having XX to YY” represents the number of carbon atoms when the ZZ group is unsubstituted and substituted. The carbon number of the substituent in the case is not included.
本明細書において、「置換もしくは無置換の原子数XX~YYのZZ基」という表現における「原子数XX~YY」は、ZZ基が無置換である場合の原子数を表し、置換されている場合の置換基の原子数は含めない。 In this specification, “atom number XX to YY” in the expression “a ZZ group having a substituted or unsubstituted atom number XX to YY” represents the number of atoms when the ZZ group is unsubstituted and substituted. The number of atoms of the substituent in the case is not included.
本明細書において、「置換もしくは無置換の」という場合における「無置換」とは前記置換基で置換されておらず、水素原子が結合していることを意味する。 In this specification, “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the above substituent.
本明細書における式中の各基、及び前記「置換もしくは無置換の」という記載における置換基の具体例について説明する。 Specific examples of each group in the formulas in this specification and substituents in the above-mentioned description of “substituted or unsubstituted” will be described.
本明細書において、「置換または無置換の」という場合における置換基(第一置換基)としては、環形成炭素数6~30のアリール基、環形成原子数5~30のヘテロアリール基、炭素数1~25のアルキル基(直鎖または分岐鎖のアルキル基)、環形成炭素数3~25のシクロアルキル基、炭素数1~25のハロゲン化アルキル基、炭素数3~25のアルキルシリル基、環形成炭素数6~30のアリールシリル基、炭素数1~25のアルコキシ基、環形成炭素数6~30のアリールオキシ基、環形成原子数5~30のヘテロアリールオキシ基、置換アミノ基、炭素数1~25のアルキルチオ基、環形成炭素数6~30のアリールチオ基、環形成原子数5~30のヘテロアリールチオ基、炭素数7~30のアラルキル基、炭素数5~30のヘテロアリール基が置換されたアルキル基、炭素数2~30のアルケニル基、炭素数2~30のアルキニル基、炭素数6~30のアリール基または原子数5~30の複素環基が置換されたホスホリル基、炭素数6~30のアリール基または原子数5~30の複素環基が置換されたボリル基、ハロゲン原子、シアノ基、ヒドロキシル基、ニトロ基、及びカルボキシ基からなる群から選択される少なくとも一種の基が挙げられる。 In the present specification, the substituent (first substituent) in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, carbon An alkyl group having 1 to 25 carbon atoms (straight or branched alkyl group), a cycloalkyl group having 3 to 25 ring carbon atoms, an alkyl halide group having 1 to 25 carbon atoms, and an alkylsilyl group having 3 to 25 carbon atoms An arylsilyl group having 6 to 30 ring carbon atoms, an alkoxy group having 1 to 25 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, a heteroaryloxy group having 5 to 30 ring atoms, and a substituted amino group Alkylthio groups having 1 to 25 carbon atoms, arylthio groups having 6 to 30 ring carbon atoms, heteroarylthio groups having 5 to 30 ring atoms, aralkyl groups having 7 to 30 carbon atoms, and 5 to 30 carbon atoms Phosphoryl substituted with an alkyl group substituted with a teloaryl group, an alkenyl group with 2 to 30 carbon atoms, an alkynyl group with 2 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms or a heterocyclic group with 5 to 30 atoms At least selected from the group consisting of a group, an aryl group having 6 to 30 carbon atoms, or a boryl group substituted with a heterocyclic group having 5 to 30 atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, and a carboxy group A kind of group is mentioned.
本明細書において、「置換または無置換の」という場合における置換基(第一置換基)としては、環形成炭素数6~30のアリール基、環形成原子数5~30のヘテロアリール基、炭素数1~25のアルキル基(直鎖または分岐鎖のアルキル基)、炭素数3~25のアルキルシリル基、環形成炭素数6~30のアリールシリル基、及びシアノ基からなる群から選択される少なくとも一種の基が好ましく、さらには、各置換基の説明において好ましいとした具体的な置換基が好ましい。 In the present specification, the substituent (first substituent) in the case of “substituted or unsubstituted” includes an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, carbon Selected from the group consisting of an alkyl group having 1 to 25 (straight chain or branched alkyl group), an alkylsilyl group having 3 to 25 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, and a cyano group At least one kind of group is preferable, and specific substituents that are preferable in the description of each substituent are preferable.
本明細書において、「置換または無置換の」という場合における置換基(第一置換基)は、環形成炭素数6~30のアリール基、環形成原子数5~30のヘテロアリール基、炭素数1~25のアルキル基(直鎖または分岐鎖のアルキル基)、炭素数3~25のシクロアルキル基、炭素数3~25のアルキルシリル基、環形成炭素数6~30のアリールシリル基、炭素数1~25のアルコキシ基、環形成炭素数6~30のアリールオキシ基、置換アミノ基、炭素数1~25のアルキルチオ基、環形成炭素数6~30のアリールチオ基、炭素数7~30のアラルキル基、炭素数2~30のアルケニル基、炭素数2~30のアルキニル基、ハロゲン原子、シアノ基、ヒドロキシル基、ニトロ基、及びカルボキシ基からなる群から選択される少なくとも一種の基(第二置換基)によってさらに置換されてもよい。また、これらの置換基は複数が互いに結合して環を形成してもよい。 In the present specification, the substituent (first substituent) in the case of “substituted or unsubstituted” refers to an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 5 to 30 ring atoms, 1 to 25 alkyl groups (straight or branched chain alkyl groups), cycloalkyl groups having 3 to 25 carbon atoms, alkylsilyl groups having 3 to 25 carbon atoms, arylsilyl groups having 6 to 30 ring carbon atoms, carbon An alkoxy group having 1 to 25 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, a substituted amino group, an alkylthio group having 1 to 25 carbon atoms, an arylthio group having 6 to 30 ring carbon atoms, and 7 to 30 carbon atoms. At least selected from the group consisting of an aralkyl group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, a nitro group, and a carboxy group It may be further substituted with one group (secondary substituent) also. A plurality of these substituents may be bonded to each other to form a ring.
本明細書において、「置換または無置換の」という場合における置換基(第一置換基)に、さらに置換する置換基(第二置換基)としては、環形成炭素数6~30のアリール基、環形成原子数5~30のヘテロアリール基、炭素数1~25のアルキル基(直鎖または分岐鎖のアルキル基)、ハロゲン原子、及びシアノ基からなる群から選択される少なくとも一種の基であることが好ましく、各置換基の説明において好ましいとした具体的な置換基から選択される少なくとも一種の基であることがさらに好ましい。 In the present specification, the substituent (second substituent) further substituted with the substituent (first substituent) in the case of “substituted or unsubstituted” is an aryl group having 6 to 30 ring carbon atoms, It is at least one group selected from the group consisting of heteroaryl groups having 5 to 30 ring atoms, alkyl groups having 1 to 25 carbon atoms (straight chain or branched chain alkyl groups), halogen atoms, and cyano groups It is preferable that it is at least one group selected from the specific substituents preferred in the description of each substituent.
アルキル基の例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、ペンチル基(異性体基を含む)、ヘキシル基(異性体基を含む)、ヘプチル基(異性体基を含む)、オクチル基(異性体基を含む)、ノニル基(異性体基を含む)、デシル基(異性体基を含む)、ウンデシル基(異性体基を含む)、及びドデシル基(異性体基を含む)などが挙げられる。これらの中でも、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基及びペンチル基(いずれも異性体基を含む)が好ましく、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基及びt-ブチル基がより好ましく、メチル基、エチル基、イソプロピル基及びt-ブチル基がさらに好ましい。 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl (including isomeric groups), hexyl Groups (including isomer groups), heptyl groups (including isomer groups), octyl groups (including isomer groups), nonyl groups (including isomer groups), decyl groups (including isomer groups), undecyl Groups (including isomer groups), dodecyl groups (including isomer groups), and the like. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a pentyl group (all including an isomer group) are preferable. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group and t-butyl group are more preferable, and methyl group, ethyl group, isopropyl group and t-butyl group are further included. preferable.
アルキル基の炭素数は、1~25であり、好ましくは1~10である。 The carbon number of the alkyl group is 1 to 25, preferably 1 to 10.
アルキル基がハロゲン原子で置換されたハロゲン化アルキル基としては、例えば、前記炭素数1~25のアルキル基が1以上のハロゲン原子、好ましくはフッ素原子で置換された基が挙げられる。
本明細書における炭素数1~25のハロゲン化アルキル基としては、具体的には、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、フルオロエチル基、トリフルオロメチルメチル基、トリフルオロエチル基、及びペンタフルオロエチル基等が挙げられる。
Examples of the halogenated alkyl group in which the alkyl group is substituted with a halogen atom include a group in which the alkyl group having 1 to 25 carbon atoms is substituted with one or more halogen atoms, preferably a fluorine atom.
Specific examples of the halogenated alkyl group having 1 to 25 carbon atoms in the present specification include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a trifluoromethylmethyl group, a trifluoroethyl group, And a pentafluoroethyl group.
アルケニル基は、前記アルキル基中に二重結合を有する基であり、アルケニル基の炭素数は、2~25であり、好ましくは2~10である。より好ましくはビニル基である。 The alkenyl group is a group having a double bond in the alkyl group, and the alkenyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferably, it is a vinyl group.
アルキニル基は、前記アルキル基中に三重結合を有する基であり、アルキニル基の炭素数は、2~25であり、好ましくは2~10である。より好ましくはエチニル基である。 The alkynyl group is a group having a triple bond in the alkyl group, and the alkynyl group has 2 to 25 carbon atoms, preferably 2 to 10 carbon atoms. More preferred is an ethynyl group.
シクロアルキル基の例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、及びアダマンチル基などが挙げられる。これらの中でも、シクロペンチル基、及びシクロヘキシル基が好ましい。
シクロアルキル基の環形成炭素数は、3~25であり、好ましくは3~10であり、より好ましくは3~8であり、さらに好ましくは3~6である。
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group. Among these, a cyclopentyl group and a cyclohexyl group are preferable.
The number of carbon atoms forming the ring of the cycloalkyl group is 3 to 25, preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6.
アルコキシ基は、-OY10で表される基であり、Y10の例としては、前記アルキル基及び前記シクロアルキル基として挙げた基と同様の基が挙げられる。アルコキシ基の炭素数は、好ましくは1~25であり、より好ましくは1~10である。 The alkoxy group is a group represented by —OY 10 , and examples of Y 10 include the same groups as those described as the alkyl group and the cycloalkyl group. The number of carbon atoms of the alkoxy group is preferably 1 to 25, more preferably 1 to 10.
アルキルチオ基は、-SY10で表される基であり、Y10の例としては、前記アルキル基及び前記シクロアルキル基として挙げた基と同様の基が挙げられる。
アルキルチオ基の炭素数は、1~25であり、好ましくは1~10である。
The alkylthio group is a group represented by —SY 10 , and examples of Y 10 include the same groups as those described as the alkyl group and the cycloalkyl group.
The alkylthio group has 1 to 25 carbon atoms, preferably 1 to 10 carbon atoms.
ハロゲン原子としては、フッ素、塩素、臭素、及びヨウ素等が挙げられ、好ましくはフッ素原子である。 Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, preferably a fluorine atom.
アリール基の例としては、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アセナフチレニル基、アントリル基、ベンゾアントリル基、アセアントリル基、フェナントリル基、ベンゾ[c]フェナントリル基、フェナレニル基、フルオレニル基、ピセニル基、ペンタフェニル基、ピレニル基、クリセニル基、ベンゾ[g]クリセニル基、s-インダセニル基、as-インダセニル基、フルオランテニル基、ベンゾ[k]フルオランテニル基、トリフェニレニル基、ベンゾ[b]トリフェニレニル基及びペリレニル基などが挙げられる。これらの中でも、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、フェナントリル基、トリフェニレニル基、フルオランテニル基、及びフルオレニル基が好ましく、フェニル基、ビフェニリル基、及びターフェニリル基がより好ましく、フェニル基がさらに好ましい。
アリール基の環形成炭素数は、6~30であり、好ましくは6~24であり、より好ましくは6~20であり、さらに好ましくは6~18である。
Examples of aryl groups include phenyl, biphenylyl, terphenylyl, naphthyl, acenaphthylenyl, anthryl, benzoanthryl, aceanthryl, phenanthryl, benzo [c] phenanthryl, phenalenyl, fluorenyl, Picenyl group, pentaphenyl group, pyrenyl group, chrysenyl group, benzo [g] chrysenyl group, s-indacenyl group, as-indacenyl group, fluoranthenyl group, benzo [k] fluoranthenyl group, triphenylenyl group, benzo [b ] A triphenylenyl group, a perylenyl group, etc. are mentioned. Among these, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluoranthenyl group, and a fluorenyl group are preferable, a phenyl group, a biphenylyl group, and a terphenylyl group are more preferable, and a phenyl group is further preferable.
The aryl group has 6-30 ring-forming carbon atoms, preferably 6-24, more preferably 6-20, and even more preferably 6-18.
アリーレン基は、前記アリール基からさらに1つの水素原子又は置換基が除去された2価の基である。 The arylene group is a divalent group in which one hydrogen atom or substituent is further removed from the aryl group.
アラルキル基は、-Y11-Y20と表される。Y11の例としては、前記アルキル基及び前記シクロアルキル基として挙げた基からさらに1つの水素原子又は置換基が除去された2価の基(アルキレン基又はシクロアルキレン基)である。Y20の例としては、前記アリール基が挙げられる。 The aralkyl group is represented as —Y 11 —Y 20 . An example of Y 11 is a divalent group (an alkylene group or a cycloalkylene group) in which one hydrogen atom or substituent is further removed from the groups listed as the alkyl group and the cycloalkyl group. Examples of Y 20 include the aryl group.
アリールオキシ基は、-OY20と表され、Y20の例としては前記アリール基として挙げた基と同様の基が挙げられる。
ヘテロアリールオキシ基は、-OY30と表され、Y30の例としては前記ヘテロアリール基として挙げた基と同様の基が挙げられる。
The aryloxy group is represented by —OY 20 and examples of Y 20 include the same groups as those mentioned as the aryl group.
The heteroaryloxy group is represented as -OY 30. Examples of Y 30 include the same groups as those described above for the heteroaryl group.
アリールチオ基は、-SY20と表され、Y20の例としては前記アリール基として挙げた基と同様の基が挙げられる。
ヘテロアリールチオ基は、-SY30と表され、Y30の例としては前記ヘテロアリール基として挙げた基と同様の基が挙げられる。
The arylthio group is represented by —SY 20 and examples of Y 20 include the same groups as those mentioned as the aryl group.
The heteroarylthio group is represented by —SY 30 and examples of Y 30 include the same groups as those mentioned as the heteroaryl group.
アリールカルボニルオキシ基は、-O-(C=O)-Y20と表され、Y20の例としては前記アリール基として挙げた基と同様の基が挙げられる。 The arylcarbonyloxy group is represented by —O— (C═O) —Y 20, and examples of Y 20 include the same groups as those mentioned as the aryl group.
アルキル基及びアリール基から選ばれる置換基を有する置換カルボニル基は、-(C=O)-Y10又は-(C=O)-Y20と表され、Y10の例としては、前記アルキル基及び前記シクロアルキル基として挙げた基と同様の基が挙げられ、Y20の例としては前記アリール基として挙げた基と同様の基が挙げられる。 A substituted carbonyl group having a substituent selected from an alkyl group and an aryl group is represented by — (C═O) —Y 10 or — (C═O) —Y 20, and examples of Y 10 include the alkyl group And the same groups as those exemplified above as the cycloalkyl group, and examples of Y 20 include the same groups as those exemplified as the aryl group.
複素環基は、芳香族性を有しない複素環基と、芳香族性を有する芳香族複素環基(1価であればヘテロアリール基、2価であればヘテロアリーレン基という)とを含む。 The heterocyclic group includes a heterocyclic group having no aromaticity and an aromatic heterocyclic group having aromaticity (a monoaryl is a heteroaryl group, and a bivalent is a heteroarylene group).
芳香族性を有しない複素環基としては、窒素原子、酸素原子もしくは硫黄原子を含む、環形成原子数3~30、好ましくは3~20の複素環基が挙げられる。芳香族性を有しない複素環の具体例としては、アジリジン、オキシラン、チイラン、アゼチジン、オキセタン、トリメチレンスルフィド、ピロリジン、テトラヒドロフラン、テトラヒドロチオフェン、ピペリジン、テトラヒドロピラン、及びテトラヒドロチオピラン等が挙げられる。 Examples of the heterocyclic group having no aromaticity include heterocyclic groups containing 3 to 30, preferably 3 to 20 ring-forming atoms, including a nitrogen atom, an oxygen atom or a sulfur atom. Specific examples of the heterocyclic ring having no aromaticity include aziridine, oxirane, thiirane, azetidine, oxetane, trimethylene sulfide, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, and tetrahydrothiopyran.
複素環基としては、窒素原子、酸素原子、硫黄原子、及びリン原子等のヘテロ原子を含む環状基が挙げられ、環形成原子として、窒素原子、酸素原子又は硫黄原子からなる群から選ばれる原子を含有することが好ましい。複素環基としては、芳香族性を有するヘテロアリール基が好ましい。ヘテロアリール基の例としては、ピロリル基、フリル基、チエニル基、ピリジル基、イミダゾピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、イミダゾリル基、オキサゾリル基、チアゾリル基、ピラゾリル基、イソオキサゾリル基、イソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、インドリル基、イソインドリル基、ベンゾフラニル基、イソベンゾフラニル基、ベンゾチエニル基、イソベンゾチエニル基、インドリジニル基、キノリジニル基、キノリル基、イソキノリル基、シンノリル基、フタラジニル基、キナゾリニル基、キノキサリニル基、ベンズイミダゾリル基、ベンズオキサゾリル基、ベンズチアゾリル基、インダゾリル基、ベンズイソキサゾリル基、ベンズイソチアゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルバゾリル基、9-フェニルカルバゾリル基、フェナントリジニル基、アクリジニル基、フェナントロリニル基、フェナジニル基、フェノチアジニル基、フェノキサジニル基及びキサンテニル基などが挙げられる。これらの中でも、ピリジル基、イミダゾピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基、ベンズイミダゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルバゾリル基、9位にアリール基又は複素環基が置換したカルバゾリル基、フェナントロリニル基、及びキナゾリニル基が好ましい。 Examples of the heterocyclic group include a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, and the ring-forming atom is an atom selected from the group consisting of a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable to contain. As the heterocyclic group, a heteroaryl group having aromaticity is preferable. Examples of heteroaryl groups include pyrrolyl, furyl, thienyl, pyridyl, imidazopyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl , Isothiazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, indolyl group, isoindolyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothienyl group, indolizinyl group, quinolidinyl group, quinolyl group, isoquinolyl Group, cinnolyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, benzimidazolyl group, benzoxazolyl group, benzthiazolyl group, indazolyl group, benzisoxazolyl group Benzisothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 9-phenylcarbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl And xanthenyl group. Among these, pyridyl group, imidazopyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, substituted with aryl group or heterocyclic group at 9-position Preferred are carbazolyl group, phenanthrolinyl group, and quinazolinyl group.
複素環基の環形成原子数は、3~30であり、好ましくは5~24であり、より好ましくは5~18である。
ヘテロアリール基の環形成原子数は、5~30であり、好ましくは5~24であり、より好ましくは5~18である。
ヘテロアリール基の炭素原子以外の環形成原子としては、窒素原子、酸素原子又は硫黄原子が好ましい。
The number of ring-forming atoms of the heterocyclic group is from 3 to 30, preferably from 5 to 24, more preferably from 5 to 18.
The number of ring-forming atoms of the heteroaryl group is 5 to 30, preferably 5 to 24, more preferably 5 to 18.
The ring-forming atom other than the carbon atom of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
ヘテロアリーレン基は、前記ヘテロアリール基からさらに1つの水素原子又は置換基が除去された2価の基である。 The heteroarylene group is a divalent group obtained by further removing one hydrogen atom or substituent from the heteroaryl group.
また、本明細書において、複素環基は、例えば、下記一般式(XY-1)~(XY-18)で表される部分構造から誘導される基であってもよい。 In the present specification, the heterocyclic group may be a group derived from a partial structure represented by the following general formulas (XY-1) to (XY-18), for example.
前記一般式(XY-1)~(XY-18)中、XA及びYAは、それぞれ独立に、ヘテロ原子であり、酸素原子、硫黄原子、セレン原子、ケイ素原子、またはゲルマニウム原子であることが好ましい。前記一般式(XY-1)~(XY-18)で表される部分構造は、任意の位置で結合手を有して複素環基となり、この複素環基は、置換基を有していてもよい。 In the general formulas (XY-1) to (XY-18), X A and Y A are each independently a hetero atom, and an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, or a germanium atom Is preferred. The partial structures represented by the general formulas (XY-1) to (XY-18) have a bond at an arbitrary position to be a heterocyclic group, and this heterocyclic group has a substituent. Also good.
アルキル基及びアリール基から選ばれる置換基を有するモノ置換アミノ基は、-NH(Y10)又は-NH(Y20)で表され、Y10及びY20は上記の通りである。
アルキル基及びアリール基から選ばれる置換基を有するジ置換アミノ基は、-N(Y10)2、-N(Y20)2又は-N(Y10)(Y20)で表され、Y10及びY20は上記の通りである。Y10又はY20が2つある場合は、互いに同一であっても、異なっていてもよい。
The mono-substituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —NH (Y 10 ) or —NH (Y 20 ), and Y 10 and Y 20 are as described above.
The disubstituted amino group having a substituent selected from an alkyl group and an aryl group is represented by —N (Y 10 ) 2 , —N (Y 20 ) 2 or —N (Y 10 ) (Y 20 ), and Y 10 And Y 20 are as described above. When two Y 10 or Y 20 are present, they may be the same as or different from each other.
アルキル基及びアリール基から選ばれる置換基を有するモノ置換シリル基は、-SiH2(Y10)又は-SiH2(Y20)で表される。
アルキル基及びアリール基から選ばれる置換基を有するジ置換シリル基は、-SiH(Y10)2、-SiH(Y20)2又は-SiH(Y10)(Y20)で表される。
アルキル基及びアリール基から選ばれる置換基を有するトリ置換シリル基は、-Si(Y10)3、-Si(Y20)3、-Si(Y10)2(Y20)又は-Si(Y10)(Y20)2で表される。Y10及びY20は前記の通りであり、Y10又はY20がそれぞれ複数存在する場合は、互いに同一であっても、異なっていてもよい。
The mono-substituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH 2 (Y 10 ) or —SiH 2 (Y 20 ).
The disubstituted silyl group having a substituent selected from an alkyl group and an aryl group is represented by —SiH (Y 10 ) 2 , —SiH (Y 20 ) 2 or —SiH (Y 10 ) (Y 20 ).
The tri-substituted silyl group having a substituent selected from an alkyl group and an aryl group is -Si (Y 10 ) 3 , -Si (Y 20 ) 3 , -Si (Y 10 ) 2 (Y 20 ) or -Si (Y 10 ) (Y 20 ) 2 . Y 10 and Y 20 are as described above, and when there are a plurality of Y 10 or Y 20 s , they may be the same as or different from each other.
アルキル基及びアリール基から選ばれる置換基を有する置換スルホニル基は、-S(=O)2-Y10又は-S(=O)2-Y20で表され、Y10及びY20は前記の通りである。 The substituted sulfonyl group having a substituent selected from an alkyl group and an aryl group is represented by —S (═O) 2 —Y 10 or —S (═O) 2 —Y 20 , and Y 10 and Y 20 are the above-mentioned Street.
アルキル基及びアリール基から選ばれる置換基を有するジ置換ホスホリル基は、-O-P(=O)(Y10)2、-O-P(=O)(Y20)2又は-O-P(=O)(Y10)(Y20)で表される。Y10及びY20は前記の通りであり、Y10又はY20がそれぞれ2つ存在する場合は、互いに同一であっても、異なっていてもよい。 The di-substituted phosphoryl group having a substituent selected from an alkyl group and an aryl group is -OP (= O) (Y 10 ) 2 , -OP (= O) (Y 20 ) 2 or -OP (= O) represented by (Y 10) (Y 20) . Y 10 and Y 20 are as described above, and when two Y 10 or Y 20 are present, they may be the same as or different from each other.
アルキル基を有するアルキルスルホニルオキシ基は、-O-S(=O)2(Y10)で表され、Y10は前記の通りである。 The alkylsulfonyloxy group having an alkyl group is represented by —O—S (═O) 2 (Y 10 ), and Y 10 is as described above.
アリール基から選ばれる置換基を有するアリールスルホニルオキシ基は、-O-S(=O)2(Y20)で表され、Y20は前記の通りである。 The arylsulfonyloxy group having a substituent selected from an aryl group is represented by —O—S (═O) 2 (Y 20 ), and Y 20 is as described above.
(電子機器)
本発明の一態様である電子機器は、前記本発明の一態様である有機エレクトロルミネッセンス素子を搭載している。
本発明の一態様である有機エレクトロルミネッセンス素子は、様々な電子機器に使用できる。例えば本発明の一態様である有機エレクトロルミネッセンス素子は、平面発光体、バックライト、計器類等の光源、表示板、及び標識灯等に利用できる。平面発光体としては、壁掛けテレビのフラットパネルディスプレイ等が挙げられる。バックライトとしては、複写機、プリンター、及び液晶ディスプレイ等のバックライトが挙げられる。
また、本発明の化合物は、有機EL素子だけでなく、電子写真感光体、光電変換素子、太陽電池、イメージセンサー等の分野においても使用できる。
(Electronics)
An electronic device which is one embodiment of the present invention includes the organic electroluminescence element which is one embodiment of the present invention.
The organic electroluminescent element which is one embodiment of the present invention can be used for various electronic devices. For example, the organic electroluminescence element which is one embodiment of the present invention can be used for a planar light emitter, a backlight, a light source such as an instrument, a display board, a marker lamp, and the like. Examples of the flat light emitter include a flat panel display of a wall-mounted television. Examples of the backlight include backlights such as copying machines, printers, and liquid crystal displays.
Moreover, the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.
〔実施形態の変形〕
なお、本発明は、上述の実施形態に限定されず、本発明の目的を達成できる範囲での変更、改良等は、本発明に含まれる。
[Modification of Embodiment]
In addition, this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are contained in this invention.
前記実施形態では、発光層に組成物が含まれている態様を例に挙げて説明した。他の態様としては、例えば、発光層以外の有機層のうちの1層に組成物が含まれている態様の有機EL素子が挙げられる。例えば、陽極と、陰極と、前記陽極と前記陰極との間に含まれた発光層と、前記発光層と前記陰極との間に含まれた電子輸送帯域を備え、前記電子輸送帯域は、前記実施形態に係る組成物を含む有機EL素子の態様が例示される。 In the above embodiment, the mode in which the composition is included in the light emitting layer is described as an example. As another aspect, the organic EL element of the aspect by which the composition is contained in one layer of organic layers other than a light emitting layer is mentioned, for example. For example, an anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport zone included between the light-emitting layer and the cathode, The aspect of the organic EL element containing the composition which concerns on embodiment is illustrated.
例えば、発光層は、1層に限られず、複数の発光層が積層されていてもよい。有機EL素子が複数の発光層を有する場合、少なくとも1つの発光層が上記実施形態で説明した条件を満たしていればよい。例えば、その他の発光層が、蛍光発光型の発光層であっても、三重項励起状態から直接基底状態への電子遷移による発光を利用した燐光発光型の発光層であってもよい。
また、有機EL素子が複数の発光層を有する場合、これらの発光層が互いに隣接して設けられていてもよいし、中間層を介して複数の発光ユニットが積層された、いわゆるタンデム型の有機EL素子であってもよい。
For example, the light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked. When the organic EL element has a plurality of light emitting layers, it is sufficient that at least one light emitting layer satisfies the conditions described in the above embodiment. For example, the other light-emitting layer may be a fluorescent light-emitting layer or a phosphorescent light-emitting layer that utilizes light emission by electron transition from a triplet excited state to a direct ground state.
In addition, when the organic EL element has a plurality of light emitting layers, these light emitting layers may be provided adjacent to each other, or a so-called tandem organic material in which a plurality of light emitting units are stacked via an intermediate layer. It may be an EL element.
また、例えば、発光層の陽極側、及び陰極側の少なくとも一方に障壁層を隣接させて設けてもよい。障壁層は、発光層に接して配置され、正孔、電子、及び励起子の少なくともいずれかを阻止することが好ましい。
例えば、発光層の陰極側で接して障壁層が配置された場合、当該障壁層は、電子を輸送し、かつ正孔が当該障壁層よりも陰極側の層(例えば、電子輸送層)に到達することを阻止する。有機EL素子が、電子輸送層を含む場合は、発光層と電子輸送層との間に当該障壁層を含むことが好ましい。
また、発光層の陽極側で接して障壁層が配置された場合、当該障壁層は、正孔を輸送し、かつ電子が当該障壁層よりも陽極側の層(例えば、正孔輸送層)に到達することを阻止する。有機EL素子が、正孔輸送層を含む場合は、発光層と正孔輸送層との間に当該障壁層を含むことが好ましい。
また、励起エネルギーが発光層からその周辺層に漏れ出さないように、障壁層を発光層に隣接させて設けてもよい。発光層で生成した励起子が、当該障壁層よりも電極側の層(例えば、電子輸送層や正孔輸送層)に移動することを阻止する。
発光層と障壁層とは接合していることが好ましい。
Further, for example, a barrier layer may be provided adjacent to at least one of the anode side and the cathode side of the light emitting layer. The barrier layer is preferably disposed in contact with the light emitting layer and blocks at least one of holes, electrons, and excitons.
For example, when a barrier layer is disposed in contact with the cathode side of the light-emitting layer, the barrier layer transports electrons, and holes reach a layer on the cathode side of the barrier layer (for example, an electron transport layer). To stop doing. When an organic EL element contains an electron carrying layer, it is preferable to contain the said barrier layer between a light emitting layer and an electron carrying layer.
Further, when a barrier layer is disposed in contact with the anode side of the light emitting layer, the barrier layer transports holes, and the electrons are directed to a layer on the anode side of the barrier layer (for example, a hole transport layer). Stop reaching. When the organic EL element includes a hole transport layer, it is preferable to include the barrier layer between the light emitting layer and the hole transport layer.
Further, a barrier layer may be provided adjacent to the light emitting layer so that excitation energy does not leak from the light emitting layer to the peripheral layer. The excitons generated in the light emitting layer are prevented from moving to a layer (for example, an electron transport layer or a hole transport layer) closer to the electrode than the barrier layer.
The light emitting layer and the barrier layer are preferably joined.
その他、本発明の実施における具体的な構造、及び形状等は、本発明の目的を達成できる範囲で他の構造等としてもよい。 In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.
以下、本発明に係る実施例を説明する。本発明はこれらの実施例によって何ら限定されない。 Hereinafter, examples according to the present invention will be described. The present invention is not limited by these examples.
<化合物>
有機EL素子の製造に用いた化合物を以下に示す。
<Compound>
The compound used for manufacture of an organic EL element is shown below.
<有機EL素子の作製>
有機EL素子を以下のように作製した。
<Production of organic EL element>
An organic EL element was produced as follows.
(実施例1)
化合物PGH-P1を1.1g測り取り、化合物PGH-N1を1.1g測り取り、これら2つの化合物を乳鉢で混合した。混合後、混合物2gを、真空蒸着装置用の石英製のるつぼに充填した。るつぼ中の化合物PGH-P1と化合物PGH-N1との混合物の一部を採取し、採取物をテトラヒドロフランに溶解し、HPLC(High Performance Liquid Chromatography)で検出された各成分のピーク面積値から化合物PGH-P1と化合物PGH-N1との比率を測定したところ、質量比(初期比率)は、化合物PGH-P1:化合物PGH-N1=5:5であった。
この化合物PGH-P1と化合物PGH-N1との混合物を充填したるつぼ、化合物HATを充填したるつぼ、化合物HT-1を充填したるつぼ、化合物HT-2を充填したるつぼ、化合物PGD-1を充填したるつぼ、化合物ET-1を充填したるつぼ、並びに8-キノリノラトリチウム(Liq)を充填したるつぼを真空蒸着装置にセットした。
Example 1
1.1 g of compound PGH-P1 was measured, 1.1 g of compound PGH-N1 was measured, and these two compounds were mixed in a mortar. After mixing, 2 g of the mixture was filled in a quartz crucible for a vacuum evaporation apparatus. A part of the mixture of compound PGH-P1 and compound PGH-N1 in the crucible was collected, the collected material was dissolved in tetrahydrofuran, and the compound PGH was calculated from the peak area values of each component detected by HPLC (High Performance Liquid Chromatography). When the ratio of -P1 to compound PGH-N1 was measured, the mass ratio (initial ratio) was compound PGH-P1: compound PGH-N1 = 5: 5.
A crucible filled with the mixture of compound PGH-P1 and compound PGH-N1, a crucible filled with compound HAT, a crucible filled with compound HT-1, a crucible filled with compound HT-2, and filled with compound PGD-1 The crucible, the crucible filled with compound ET-1, and the crucible filled with 8-quinolinolatolithium (Liq) were set in a vacuum deposition apparatus.
25mm×75mm×1.1mm厚のITO透明電極(陽極)付きガラス基板(ジオマテック社製)をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間行なった。ITOの膜厚は、130nmとした。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、一方をマスクで保護した後、まず透明電極ラインが形成されている側の面上に前記透明電極を覆うようにして化合物HATを蒸着して膜厚10nmのHAT膜を成膜し、正孔注入層を形成した。
次に、この正孔注入層の上に、化合物HT-1を蒸着して膜厚110nmのHT-1膜を成膜し、第一正孔輸送層を形成した。
次に、この第一正孔輸送層の上に、化合物HT-2を蒸着して膜厚35nmのHT-2膜を成膜し、第二正孔輸送層を形成した。
次に、この第二正孔輸送層の上に、化合物PGH-P1と化合物PGH-N1との混合物、及び化合物PGD-1を共蒸着により成膜し、膜厚40nmの発光層を形成した。発光層に含まれる化合物PGD-1の濃度は、5質量%とした。
この発光層の成膜に続けて、化合物ET-1と8-キノリノラトリチウム(Liq)とを50:50の質量比で共蒸着により成膜し、膜厚30nmの電子輸送層を形成した。
この電子輸送層上にLiqを蒸着して、膜厚1nmの電子注入層を形成した。
この電子注入層上に金属Alを蒸着して、膜厚80nmの金属陰極を形成した。
このようにして作製した有機EL素子を、蒸着初期の有機EL素子とした。
A glass substrate (manufactured by Geomat Co.) with an ITO transparent electrode (anode) having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The film thickness of ITO was 130 nm. After mounting the glass substrate with the transparent electrode line after cleaning on the substrate holder of the vacuum deposition apparatus and protecting one with a mask, first cover the transparent electrode on the surface where the transparent electrode line is formed. Compound HAT was vapor-deposited to form a HAT film having a thickness of 10 nm to form a hole injection layer.
Next, a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
Next, a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
Next, a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm. The concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
Subsequent to the formation of the light-emitting layer, the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. .
Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm.
Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm.
The organic EL device produced in this way was used as an organic EL device in the initial stage of vapor deposition.
有機EL素子を作製した後、ITO基板をチャンバーの外に退避させ、化合物PGH-P1と化合物PGH-N1との混合物の蒸着を、るつぼ内の材料の質量が0.4g(残量20質量%)になるまで連続して続けた。その後、ITO基板をチャンバーに戻し、既に作製済の有機EL素子部をマスクで保護した後、透明電極ラインが形成されている側の面上に前記透明電極を覆うようにして化合物HATを蒸着して膜厚10nmのHAT膜を成膜し、正孔注入層を形成した。
次に、この正孔注入層の上に、化合物HT-1を蒸着して膜厚110nmのHT-1膜を成膜し、第一正孔輸送層を形成した。
次に、この第一正孔輸送層の上に、化合物HT-2を蒸着して膜厚35nmのHT-2膜を成膜し、第二正孔輸送層を形成した。
次に、この第二正孔輸送層の上に、化合物PGH-P1と化合物PGH-N1との混合物、及び化合物PGD-1を共蒸着により成膜し、膜厚40nmの発光層を形成した。発光層に含まれる化合物PGD-1の濃度は、5質量%とした。
この発光層の成膜に続けて、化合物ET-1と8-キノリノラトリチウム(Liq)とを50:50の質量比で共蒸着により成膜し、膜厚30nmの電子輸送層を形成した。
この電子輸送層上にLiqを蒸着して、膜厚1nmの電子注入層を形成した。
この電子注入層上に金属Alを蒸着して、膜厚80nmの金属陰極を形成した。
このようにして作製した有機EL素子を、蒸着終期の有機EL素子とした。
最後に蒸着装置からるつぼ残渣を取り出し、るつぼ残渣をテトラヒドロフランに溶解し、HPLCで検出された各成分のピーク面積値から化合物PGH-P1と化合物PGH-N1との比率(残渣比率)を求めた。
After manufacturing the organic EL element, the ITO substrate is retracted out of the chamber, and the mixture of the compound PGH-P1 and the compound PGH-N1 is evaporated to a mass of 0.4 g (the remaining amount is 20% by mass). ) Continued until. Thereafter, the ITO substrate is returned to the chamber, and the already prepared organic EL element part is protected with a mask, and then the compound HAT is vapor deposited so as to cover the transparent electrode on the surface on which the transparent electrode line is formed. A HAT film having a thickness of 10 nm was formed to form a hole injection layer.
Next, a compound HT-1 was vapor-deposited on the hole injection layer to form a 110 nm-thick HT-1 film, thereby forming a first hole transport layer.
Next, a compound HT-2 was vapor-deposited on the first hole transport layer to form an HT-2 film having a thickness of 35 nm, thereby forming a second hole transport layer.
Next, a mixture of compound PGH-P1 and compound PGH-N1 and compound PGD-1 were formed on the second hole transport layer by co-evaporation to form a light-emitting layer having a thickness of 40 nm. The concentration of the compound PGD-1 contained in the light emitting layer was 5% by mass.
Subsequent to the formation of the light-emitting layer, the compound ET-1 and 8-quinolinolatolithium (Liq) were formed by co-evaporation at a mass ratio of 50:50 to form an electron transport layer having a thickness of 30 nm. .
Liq was vapor-deposited on this electron transport layer to form an electron injection layer having a thickness of 1 nm.
Metal Al was vapor-deposited on the electron injection layer to form a metal cathode having a thickness of 80 nm.
The organic EL device produced in this way was used as the organic EL device at the end of vapor deposition.
Finally, the crucible residue was taken out from the vapor deposition apparatus, the crucible residue was dissolved in tetrahydrofuran, and the ratio (residue ratio) between compound PGH-P1 and compound PGH-N1 was determined from the peak area values of each component detected by HPLC.
表1に、初期(蒸着前)のるつぼ中の化合物PGH-P1と化合物PGH-N1との比率(初期比率)、及び蒸着後のるつぼ中の化合物PGH-P1と化合物PGH-N1との比率(残渣比率)を示す。 Table 1 shows the ratio (initial ratio) of the compound PGH-P1 and the compound PGH-N1 in the crucible in the initial stage (before deposition), and the ratio of the compound PGH-P1 and the compound PGH-N1 in the crucible after deposition ( Residue ratio).
(実施例2)
実施例2は、実施例1の発光層における化合物PGH-N1に代えて、化合物PGH-N2を用いたこと以外、実施例1と同様にして実施した。
表1に、初期(蒸着前)のるつぼ中の化合物PGH-P1と化合物PGH-N2との比率(初期比率)、及び蒸着後のるつぼ中の化合物PGH-P1と化合物PGH-N2との比率(残渣比率)を示す。
(Example 2)
Example 2 was carried out in the same manner as Example 1 except that compound PGH-N2 was used instead of compound PGH-N1 in the light emitting layer of Example 1.
Table 1 shows the ratio (initial ratio) of compound PGH-P1 and compound PGH-N2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-P1 and compound PGH-N2 in the crucible after vapor deposition ( Residue ratio).
(比較例1)
比較例1は、実施例1の発光層における化合物PGH-P1に代えて、化合物PGH-C1を用い、化合物PGH-N1に代えて、化合物PGH-C2を用いたこと以外、実施例1と同様にして実施した。
表1に、初期(蒸着前)のるつぼ中の化合物PGH-C1と化合物PGH-C2との比率(初期比率)、及び蒸着後のるつぼ中の化合物PGH-C1と化合物PGH-C2との比率(残渣比率)を示す。
(Comparative Example 1)
Comparative Example 1 was the same as Example 1 except that compound PGH-C1 was used instead of compound PGH-P1 in the light emitting layer of Example 1, and compound PGH-C2 was used instead of compound PGH-N1. Was carried out.
Table 1 shows the ratio (initial ratio) of compound PGH-C1 and compound PGH-C2 in the initial (before vapor deposition) crucible, and the ratio of compound PGH-C1 and compound PGH-C2 in the crucible after vapor deposition ( Residue ratio).
実施例1に係る蒸着初期の有機EL素子において、発光層中の化合物PGH-P1と化合物PGH-N1との質量比(フィルム比率)をHPLCにて分析したところ、化合物PGH-P1:化合物PGH-N1=5:5であった。 In the organic EL device in the initial stage of vapor deposition according to Example 1, the mass ratio (film ratio) of the compound PGH-P1 and the compound PGH-N1 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-P1: the compound PGH- N1 = 5: 5.
実施例2に係る蒸着初期の有機EL素子において、発光層中の化合物PGH-P1と化合物PGH-N2との質量比(フィルム比率)をHPLCにて分析したところ、化合物PGH-P1:化合物PGH-N2=5:5であった。 In the organic EL element in the initial stage of vapor deposition according to Example 2, the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N2 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-P1: the compound PGH- N2 = 5: 5.
比較例1に係る蒸着初期の有機EL素子において、発光層中の化合物PGH-C1と化合物PGH-C2との質量比(フィルム比率)をHPLCにて分析したところ、化合物PGH-C1:化合物PGH-C2=6:4であった。 In the organic EL device in the initial stage of vapor deposition according to Comparative Example 1, the mass ratio (film ratio) between the compound PGH-C1 and the compound PGH-C2 in the light emitting layer was analyzed by HPLC. As a result, the compound PGH-C1: the compound PGH- C2 = 6: 4.
実施例1の有機EL素子(蒸着初期)に関して、発光層中の化合物PGH-P1と化合物PGH-N1との質量比(フィルム比率)は、初期(蒸着前)のるつぼ中の化合物PGH-P1と化合物PGH-N1との質量比(初期比率)と同様の比率であった。
また、実施例2の有機EL素子(蒸着初期)に関して、発光層中の化合物PGH-P1と化合物PGH-N2との質量比(フィルム比率)は、初期(蒸着前)のるつぼ中の化合物PGH-P1と化合物PGH-N2との質量比(初期比率)と同様の比率であった。
一方で、比較例1の有機EL素子(蒸着初期)に関して、発光層中の化合物PGH-C1と化合物PGH-C2との質量比(フィルム比率)は、初期(蒸着前)のるつぼ中の化合物PGH-C1と化合物PGH-C2との質量比(初期比率)と大きく異なっていた。比較例1では、るつぼ中には化合物PGH-C1と化合物PGH-C2とが5:5の質量比で混合されていたが、膜中の質量比は6:4であり、発光層中の比率は、材料の仕込み比率と同等に成膜されていないことが分かった。
Regarding the organic EL device of Example 1 (initial stage of vapor deposition), the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N1 in the light emitting layer was the same as that of the compound PGH-P1 in the initial crucible (before vapor deposition). The ratio was the same as the mass ratio (initial ratio) with compound PGH-N1.
Further, regarding the organic EL device of Example 2 (initial stage of vapor deposition), the mass ratio (film ratio) between the compound PGH-P1 and the compound PGH-N2 in the light emitting layer was the compound PGH- in the initial crucible (before vapor deposition). The ratio was the same as the mass ratio (initial ratio) between P1 and compound PGH-N2.
On the other hand, regarding the organic EL element of Comparative Example 1 (initial stage of vapor deposition), the mass ratio (film ratio) of the compound PGH-C1 and the compound PGH-C2 in the light emitting layer was the compound PGH in the crucible at the initial stage (before vapor deposition). The mass ratio (initial ratio) of -C1 and compound PGH-C2 was significantly different. In Comparative Example 1, compound PGH-C1 and compound PGH-C2 were mixed in a mass ratio of 5: 5 in the crucible, but the mass ratio in the film was 6: 4, and the ratio in the light emitting layer It was found that the film was not formed at the same rate as the material charge ratio.
<有機EL素子の評価>
実施例1、実施例2及び比較例1において作製した蒸着初期の有機EL素子、及び蒸着終期の有機EL素子について、以下の評価を行った。評価結果を表2に示す。
<Evaluation of organic EL element>
The following evaluation was performed about the organic EL element of the vapor deposition initial stage produced in Example 1, Example 2, and the comparative example 1, and the organic EL element of the vapor deposition final stage. The evaluation results are shown in Table 2.
・駆動電圧V
電流密度が10mA/cm2となるようにITO透明電極と金属Al陰極との間に通電したときの電圧(単位:V)を計測した。
・ Drive voltage V
The voltage (unit: V) when energized between the ITO transparent electrode and the metal Al cathode was measured so that the current density was 10 mA / cm 2 .
・外部量子効率EQE
電流密度が10mA/cm2となるように素子に電圧を印加した時の分光放射輝度スペクトルを分光放射輝度計CS-1000(コニカミノルタ社製)で計測した。得られた分光放射輝度スペクトルから、ランバシアン放射を行なったと仮定し、外部量子効率EQE(単位:%)を算出した。
・ External quantum efficiency EQE
A spectral radiance spectrum when a voltage was applied to the device so that the current density was 10 mA / cm 2 was measured with a spectral radiance meter CS-1000 (manufactured by Konica Minolta). The external quantum efficiency EQE (unit:%) was calculated from the obtained spectral radiance spectrum, assuming that Lambtian radiation was performed.
実施例1及び実施例2によれば、蒸着初期の有機EL素子及び蒸着終期の有機EL素子に関して、素子性能のばらつきが、比較例1に比べて少ないことが分かった。前記一般式(1)で表される第一の化合物と前記一般式(2)で表される第二の化合物とを含む組成物を用いることで、有機エレクトロルミネッセンス素子の性能を維持しながら、1つの蒸着源から材料の比率を安定的に蒸着させることが可能であることが分かった。 According to Example 1 and Example 2, it was found that there was less variation in device performance as compared to Comparative Example 1 with respect to the organic EL element at the initial stage of vapor deposition and the organic EL element at the end of the vapor deposition. While maintaining the performance of the organic electroluminescence device by using the composition containing the first compound represented by the general formula (1) and the second compound represented by the general formula (2), It has been found that it is possible to stably deposit the ratio of materials from one deposition source.
1…有機EL素子、3…陽極、4…陰極、5…発光層、7…正孔輸送層、8…電子輸送層。
DESCRIPTION OF
Claims (18)
少なくとも下記一般式(1)で表される第一の化合物及び下記一般式(2)で表される第二の化合物が含有される組成物。
(前記一般式(1)中、
R1、R2、R3及びR4は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
A1及びA2のうち、一方が、下記一般式(1a)で表される置換基であり、他方が、下記一般式(1b)で表される部分構造を含む置換基である。)
(前記一般式(1a)中、X1、X2、X3、X4及びX5は、それぞれ独立して、CRX又は窒素原子を示す。RXは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRXは、互いに同一であるか、又は異なる。)
(前記一般式(1b)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
X9、X10、X11、X12、X13、X14、X15、X16、X17及びX18は、それぞれ独立して、CRZ又は窒素原子を示す。RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。)
(前記一般式(2)中、R5、R6、R7及びR8は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
eは、0、1、2、3又は4である。
fは、0、1、2又は3である。
gは、0、1、2又は3である。
hは、0、1、2、3又は4である。
eが2以上の場合、複数のR5は、互いに同一であるか、又は異なる。
fが2以上の場合、複数のR6は、互いに同一であるか、又は異なる。
gが2以上の場合、複数のR7は、互いに同一であるか、又は異なる。
hが2以上の場合、複数のR8は、互いに同一であるか、又は異なる。
A3及びA4のうち、一方が、下記一般式(2a)で表される置換基であり、他方が、下記一般式(2b)で表される置換基である。)
(前記一般式(2a)中、R9は、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
iは0、1、2、3、4又は5である。)
(前記一般式(2b)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。) A composition in which two or more compounds are mixed,
A composition containing at least a first compound represented by the following general formula (1) and a second compound represented by the following general formula (2).
(In the general formula (1),
R 1 , R 2 , R 3 and R 4 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
One of A 1 and A 2 is a substituent represented by the following general formula (1a), and the other is a substituent including a partial structure represented by the following general formula (1b). )
(In the general formula (1a), X 1, X 2, X 3, X 4 and X 5 are each independently, .R X indicating the CR X or a nitrogen atom,
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R X are the same as or different from each other. )
(In the general formula (1b), X 6, X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom,
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 and X 18 each independently represent CR Z or a nitrogen atom. R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other. )
(In the general formula (2), R 5 , R 6 , R 7 and R 8 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
e is 0, 1, 2, 3 or 4;
f is 0, 1, 2 or 3.
g is 0, 1, 2 or 3.
h is 0, 1, 2, 3 or 4.
When e is 2 or more, the plurality of R 5 are the same as or different from each other.
When f is 2 or more, the plurality of R 6 are the same as or different from each other.
When g is 2 or more, the plurality of R 7 are the same as or different from each other.
When h is 2 or more, the plurality of R 8 are the same as or different from each other.
One of A 3 and A 4 is a substituent represented by the following general formula (2a), and the other is a substituent represented by the following general formula (2b). )
(In the general formula (2a), R 9 is
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
i is 0, 1, 2, 3, 4 or 5. )
(In the general formula (2b), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
前記一般式(1)中、A1及びA2のうち、一方が、前記一般式(1a)で表される置換基であり、他方が、下記一般式(1c)で表される置換基である、組成物。
(前記一般式(1c)中、X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19、X20、X21、X22及びX23は、それぞれ独立して、CRZ又は窒素原子を示す。RZは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
複数のRZは、互いに同一であるか、又は異なる。
X19、X20、X21、X22及びX23の少なくとも1つはCRZであり、少なくとも1つのRZは、*と結合する単結合である。) The composition of claim 1, wherein
In the general formula (1), one of A 1 and A 2 is a substituent represented by the general formula (1a), and the other is a substituent represented by the following general formula (1c). There is a composition.
(In the general formula (1c), X 6, X 7 and X 8 are each independently, .R Y indicating the CR Y or a nitrogen atom,
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 , X 20 , X 21 , X 22 and X 23 are each independently shows a CR Z or a nitrogen atom. R Z is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
The plurality of R Z are the same as or different from each other.
At least one of X 19 , X 20 , X 21 , X 22 and X 23 is CR Z , and at least one R Z is a single bond bonded to *. )
前記第一の化合物が、下記一般式(3)で表される化合物である、組成物。
(前記一般式(3)中、
R1、R2、R3、R4、R14及びR15は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
aは、0、1、2、3又は4である。
bは、0、1、2又は3である。
cは、0、1、2又は3である。
dは、0、1、2、3又は4である。
pは、0、1、2、3、4又は5である。
qは、0、1、2、3、4又は5である。
aが2以上の場合、複数のR1は、互いに同一であるか、又は異なる。
bが2以上の場合、複数のR2は、互いに同一であるか、又は異なる。
cが2以上の場合、複数のR3は、互いに同一であるか、又は異なる。
dが2以上の場合、複数のR4は、互いに同一であるか、又は異なる。
pが2以上の場合、複数のR14は、互いに同一であるか、又は異なる。
qが2以上の場合、複数のR15は、互いに同一であるか、又は異なる。
B1及びB2は、下記一般式(4)で表される置換基を示す。
rは、0又は1である。
sは、0又は1である。
ただし、r+s=1である。)
(前記一般式(4)中、
X6、X7及びX8は、それぞれ独立して、CRY又は窒素原子を示す。RYは、
水素原子、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
炭素数1~25のアルキル基で置換されたシリル基、又は
シアノ基を示す。
X6、X7及びX8のうち少なくとも2つは窒素原子である。
R16及びR17は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、又は
シアノ基を示す。
tは、0、1、2、3、4又は5である。
uは、0、1、2、3、4又は5である。
tが2以上の場合、複数のR16は、互いに同一であるか、又は異なる。
uが2以上の場合、複数のR17は、互いに同一であるか、又は異なる。) The composition according to claim 1 or claim 2,
The composition wherein the first compound is a compound represented by the following general formula (3).
(In the general formula (3),
R 1 , R 2 , R 3 , R 4 , R 14 and R 15 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
a is 0, 1, 2, 3 or 4.
b is 0, 1, 2 or 3.
c is 0, 1, 2 or 3.
d is 0, 1, 2, 3 or 4.
p is 0, 1, 2, 3, 4 or 5.
q is 0, 1, 2, 3, 4 or 5.
When a is 2 or more, the plurality of R 1 are the same as or different from each other.
When b is 2 or more, the plurality of R 2 are the same as or different from each other.
When c is 2 or more, the plurality of R 3 are the same as or different from each other.
When d is 2 or more, the plurality of R 4 are the same as or different from each other.
When p is 2 or more, the plurality of R 14 are the same as or different from each other.
When q is 2 or more, the plurality of R 15 are the same as or different from each other.
B 1 and B 2 represent a substituent represented by the following general formula (4).
r is 0 or 1.
s is 0 or 1.
However, r + s = 1. )
(In the general formula (4),
X 6, X 7 and X 8 are each independently a CR Y or a nitrogen atom. R Y is
Hydrogen atom,
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A silyl group substituted with an alkyl group having 1 to 25 carbon atoms, or a cyano group.
At least two of X 6 , X 7 and X 8 are nitrogen atoms.
R 16 and R 17 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms or a cyano group.
t is 0, 1, 2, 3, 4 or 5.
u is 0, 1, 2, 3, 4 or 5.
When t is 2 or more, the plurality of R 16 are the same as or different from each other.
When u is 2 or more, the plurality of R 17 are the same as or different from each other. )
前記一般式(4)におけるX6、X7及びX8が、窒素原子である、組成物。 The composition of claim 3, wherein
The composition in which X 6 , X 7 and X 8 in the general formula (4) are nitrogen atoms.
r=1、s=0である、組成物。 The composition according to claim 3 or claim 4,
A composition wherein r = 1 and s = 0.
前記第二の化合物において、A3及びA4のうち、一方が、前記一般式(2a)で表される置換基であり、他方が、下記一般式(5)で表される置換基である、組成物。
(前記一般式(5)中、R10、R11、R12及びR13は、それぞれ独立して、
ハロゲン原子、
置換もしくは無置換の炭素数1~25のアルキル基、
置換もしくは無置換の環形成炭素数3~25のシクロアルキル基、
置換もしくは無置換の環形成炭素数6~24のアリール基、
置換もしくは無置換の環形成原子数3~30の複素環基、
炭素数1~25のアルキル基及び環形成炭素数6~24のアリール基からなる群から選択される1以上の基で置換されたシリル基、又は
シアノ基を示す。
jは、0、1、2、3又は4である。
kは、0、1、2又は3である。
lは、0、1、2、3、4又は5である。
mは、0、1、2、3、4又は5である。
jが2以上の場合、複数のR10は、互いに同一であるか、又は異なる。
kが2以上の場合、複数のR11は、互いに同一であるか、又は異なる。
lが2以上の場合、複数のR12は、互いに同一であるか、又は異なる。
mが2以上の場合、複数のR13は、互いに同一であるか、又は異なる。) In the composition according to any one of claims 1 to 5,
In the second compound, one of A 3 and A 4 is a substituent represented by the general formula (2a), and the other is a substituent represented by the following general formula (5). ,Composition.
(In the general formula (5), R 10 , R 11 , R 12 and R 13 are each independently
Halogen atoms,
A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 25 ring carbon atoms,
A substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 3 to 30 ring atoms;
A silyl group substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 25 carbon atoms and an aryl group having 6 to 24 ring carbon atoms, or a cyano group.
j is 0, 1, 2, 3 or 4;
k is 0, 1, 2 or 3.
l is 0, 1, 2, 3, 4 or 5.
m is 0, 1, 2, 3, 4 or 5.
When j is 2 or more, the plurality of R 10 are the same as or different from each other.
When k is 2 or more, the plurality of R 11 are the same as or different from each other.
When l is 2 or more, the plurality of R 12 are the same as or different from each other.
When m is 2 or more, the plurality of R 13 are the same as or different from each other. )
a、b、c、d、e、f、g、h、i、j、k、l及びmが、0である、組成物。 In the composition according to any one of claims 1 to 6,
A composition wherein a, b, c, d, e, f, g, h, i, j, k, l and m are 0.
前記有機層は、請求項1から請求項7のいずれか一項に記載の組成物を含む、
有機エレクトロルミネッセンス素子。 An anode, a cathode, and an organic layer included between the anode and the cathode,
The organic layer includes the composition according to any one of claims 1 to 7,
Organic electroluminescence device.
前記有機層は、複数の層で構成され、
前記組成物は、前記複数の層のうちの1層に含まれている、有機エレクトロルミネッセンス素子。 In the organic electroluminescent element according to claim 10,
The organic layer is composed of a plurality of layers,
The said composition is an organic electroluminescent element contained in one layer of the said some layer.
前記有機層は、発光層を含み、
前記発光層は、前記組成物を含有する、有機エレクトロルミネッセンス素子。 In the organic electroluminescence device according to claim 10 or 11,
The organic layer includes a light emitting layer,
The said light emitting layer is an organic electroluminescent element containing the said composition.
前記発光層が、さらに発光材料を含有する、有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 12,
An organic electroluminescence device, wherein the light emitting layer further contains a light emitting material.
前記発光層は、前記発光材料として燐光発光材料を含有し、
前記燐光発光材料は、イリジウム、オスミウム、及び白金からなる群から選択されるいずれかの金属原子のオルトメタル化錯体である、有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 13,
The light emitting layer contains a phosphorescent light emitting material as the light emitting material,
The organic light-emitting device, wherein the phosphorescent material is an orthometalated complex of any metal atom selected from the group consisting of iridium, osmium, and platinum.
前記陽極と前記発光層との間に、さらに正孔輸送層を有する、有機エレクトロルミネッセンス素子。 The organic electroluminescent element according to any one of claims 12 to 14,
An organic electroluminescence device further comprising a hole transport layer between the anode and the light emitting layer.
前記陰極と前記発光層との間に、さらに電子輸送層を有する、有機エレクトロルミネッセンス素子。 In the organic electroluminescent element according to any one of claims 12 to 15,
An organic electroluminescence device further comprising an electron transport layer between the cathode and the light emitting layer.
前記電子輸送帯域は、請求項1から請求項7のいずれか一項に記載の組成物を含む、
有機エレクトロルミネッセンス素子。 An anode, a cathode, a light-emitting layer included between the anode and the cathode, and an electron transport band included between the light-emitting layer and the cathode,
The electron transport zone comprises the composition according to any one of claims 1 to 7,
Organic electroluminescence device.
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| JP2017104012A JP2020143169A (en) | 2017-05-25 | 2017-05-25 | Composition, material for organic electroluminescence element, composition film, organic electroluminescence element and electronic apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11053437B2 (en) | 2019-06-28 | 2021-07-06 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent devices, organic electroluminescent device and electronic device |
| CN114514234A (en) * | 2019-10-01 | 2022-05-17 | 出光兴产株式会社 | Compound, material for organic electroluminescent element, and electronic device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114930561B (en) | 2020-12-11 | 2023-12-26 | 京东方科技集团股份有限公司 | Organic electroluminescent devices and display devices |
| KR102487491B1 (en) * | 2022-06-13 | 2023-01-12 | 솔루스첨단소재 주식회사 | Pellet for organic electroluminescent device and organic electroluminescent device using the same |
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| WO2014017484A1 (en) * | 2012-07-25 | 2014-01-30 | 東レ株式会社 | Light emitting element material and light emitting element |
| JP2014110348A (en) * | 2012-12-03 | 2014-06-12 | Idemitsu Kosan Co Ltd | Organic electroluminescent element |
| JP2014157947A (en) * | 2013-02-15 | 2014-08-28 | Idemitsu Kosan Co Ltd | Organic electroluminescence device and electronic device |
| US20170117486A1 (en) * | 2015-10-27 | 2017-04-27 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US20170194569A1 (en) * | 2015-12-23 | 2017-07-06 | Samsung Display Co., Ltd | Organic light-emitting device |
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- 2017-05-25 JP JP2017104012A patent/JP2020143169A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014017484A1 (en) * | 2012-07-25 | 2014-01-30 | 東レ株式会社 | Light emitting element material and light emitting element |
| JP2014110348A (en) * | 2012-12-03 | 2014-06-12 | Idemitsu Kosan Co Ltd | Organic electroluminescent element |
| JP2014157947A (en) * | 2013-02-15 | 2014-08-28 | Idemitsu Kosan Co Ltd | Organic electroluminescence device and electronic device |
| US20170117486A1 (en) * | 2015-10-27 | 2017-04-27 | Samsung Display Co., Ltd. | Organic light-emitting device |
| US20170194569A1 (en) * | 2015-12-23 | 2017-07-06 | Samsung Display Co., Ltd | Organic light-emitting device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11053437B2 (en) | 2019-06-28 | 2021-07-06 | Idemitsu Kosan Co., Ltd. | Compound, material for organic electroluminescent devices, organic electroluminescent device and electronic device |
| CN114514234A (en) * | 2019-10-01 | 2022-05-17 | 出光兴产株式会社 | Compound, material for organic electroluminescent element, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2020143169A (en) | 2020-09-10 |
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