WO2016076375A1 - Élément électroluminescent organique et procédé de fabrication de celui-ci - Google Patents

Élément électroluminescent organique et procédé de fabrication de celui-ci Download PDF

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WO2016076375A1
WO2016076375A1 PCT/JP2015/081794 JP2015081794W WO2016076375A1 WO 2016076375 A1 WO2016076375 A1 WO 2016076375A1 JP 2015081794 W JP2015081794 W JP 2015081794W WO 2016076375 A1 WO2016076375 A1 WO 2016076375A1
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charge transporting
transporting compound
organic
compound
layer
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PCT/JP2015/081794
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English (en)
Japanese (ja)
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石塚　健一
重昭 舟生
直紀 浅野
大輔 龍崎
啓 高井良
優規 吉成
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日立化成株式会社
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Priority to JP2016559097A priority Critical patent/JP6418247B2/ja
Priority to KR1020177010524A priority patent/KR101952526B1/ko
Priority to CN201580059401.7A priority patent/CN107078227B/zh
Publication of WO2016076375A1 publication Critical patent/WO2016076375A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • 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]
    • H10K50/14—Carrier transporting layers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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]
    • H10K50/17—Carrier injection layers

Definitions

  • Embodiments of the present invention relate to an organic electroluminescent element (also referred to as “organic EL element”), a method for manufacturing an organic electroluminescent element, a display element, a lighting device, and a display device.
  • organic electroluminescent element also referred to as “organic EL element”
  • a method for manufacturing an organic electroluminescent element a display element, a lighting device, and a display device.
  • Organic EL elements are attracting attention as large-area solid-state light source applications, for example, as an alternative to incandescent lamps and gas-filled lamps. It is also attracting attention as the most powerful self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.
  • LCD liquid crystal display
  • FPD flat panel display
  • Organic EL elements are roughly classified into two types, low molecular organic EL elements and high molecular organic EL elements, from the organic materials used.
  • the polymer organic EL element a polymer compound is used as an organic material
  • the low molecular organic EL element a low molecular compound is used.
  • the manufacturing method of the organic EL element includes a dry process in which film formation is mainly performed in a vacuum system, and a wet process in which film formation is performed by plate printing such as relief printing and intaglio printing, and plateless printing such as inkjet. It is roughly divided into two.
  • the present inventors have found an element configuration suitable for improving the lifetime characteristics of the organic EL element, and have completed the present invention.
  • the embodiment of the present invention has an anode, a charge transporting layer, a light emitting layer, and a cathode in this order, and the charge transporting layer contains the charge transporting compound (A) and the charge transporting compound (B).
  • the ratio of the content of the charge transporting compound (B) to the content of B1 is B1 / A1 and B2 / A2, respectively, and the content of the charge transporting compound (B) in the second region and the third region It is related with the organic electroluminescent element which satisfy
  • another embodiment of the present invention includes an anode, a charge transport layer, a light emitting layer, and a cathode in this order, and the charge transport layer includes one or more of a charge transport compound and a solvent.
  • the ratio of the content of (B) is B1 / A1 and B2 / A2, respectively, and the charge transporting compound (A) with respect to the content of the charge transporting compound (B) in the second region and the third region ) Content ratio A If the / B2 and A3 / B3, it satisfies the following formula (I) and Formula (II), an organic electroluminescent device.
  • Another embodiment of the present invention is an organic electroluminescence device having an anode, a charge transporting layer, a light emitting layer, and a cathode in this order, and the charge transporting layer is arranged in order from the anode side.
  • the present invention relates to an organic electroluminescence device comprising a compound (A) and a charge transporting compound (B), wherein the third organic layer contains the charge transporting compound (B).
  • Another embodiment of the present invention is an organic electroluminescence device having an anode, a charge transporting layer, a light emitting layer, and a cathode in this order, and the charge transporting layer is arranged in order from the anode side.
  • One organic layer, a second organic layer, and a third organic layer wherein the first organic layer is formed of a composition containing a charge transporting compound (A) and a solvent, The second organic layer is formed of a composition containing the charge transporting compound (A), the charge transporting compound (B), and a solvent, and the third organic layer is formed of the charge transporting compound (
  • the present invention relates to an organic electroluminescent device formed of a composition containing B) and a solvent.
  • Another embodiment of the present invention is a method for producing an organic electroluminescent device having an anode, a charge transporting layer, a light emitting layer, and a cathode in this order, wherein the charge transporting layer comprises the charge transporting compound.
  • the charge transporting layer contains a charge transporting compound (A) and a charge transporting compound (B), and In order from the anode side, the first region, the second region, and the third region, the content of the charge transporting compound (A) in the first region and the second region with respect to the content
  • the ratio of the content of the charge transporting compound (B) is B1 / A1 and B2 / A2, respectively, and the charge transporting with respect to the content of the charge transporting compound (B) in the second region and the third region.
  • the chemical compound (A) If ratio of the respectively A2 / B2 and A3 / B3, satisfies the following formula (I) and Formula (II), a method for manufacturing an organic electroluminescent element.
  • another embodiment of the present invention includes an anode, a charge transporting layer, a light emitting layer, and a cathode, and the charge transporting layer comprises, in order from the anode side, a first organic layer and a second organic layer.
  • another embodiment of the present invention relates to a display element and an illuminating device including any one of the organic electroluminescence elements, and a display device including the illuminating device and a liquid crystal element as a display unit.
  • the present invention is related to the subject matter described in Japanese Patent Application No. 2014-228922 filed on November 11, 2014, the disclosure of which is incorporated herein by reference.
  • an organic EL element with improved lifetime characteristics and a method for manufacturing the same.
  • the organic EL device includes an anode, a charge transport layer, a light emitting layer, and a cathode in this order, and may further include any other layer.
  • the charge transport layer is formed using one or more compositions containing a charge transport compound and a solvent.
  • the charge transporting layer contains a charge transporting compound (A) and a charge transporting compound (B).
  • the charge transporting layer may be formed by using a compound having a polymerizable substituent in at least one of the charge transporting compound (A) and / or the charge transporting compound (B).
  • the charge transporting layer of the present embodiment contains the charge transporting compound (A) and / or the charge transporting compound (B) and at least one of the charge transporting compound (A) and the charge transporting compound (B).
  • a layer containing a polymer also referred to as “cured product” is also included.
  • the form of the charge transporting compound (A) and / or the charge transporting compound (B) contained in the charge transporting layer these and the compounds derived from these, for example, polymers, reactants, decomposition products, etc. And so on.
  • the charge transporting layer has a first region, a second region, and a third region in order from the anode side.
  • the ratio of the content of the charge transporting compound (B) to the content of the charge transporting compound (A) in the first region and the second region is B1 / A1 and B2 / A2, respectively.
  • the ratio of the content of the charge transporting compound (A) to the content of the charge transporting compound (B) in the three regions is A2 / B2 and A3 / B3, respectively, the following formulas (I) and (II) Satisfy the relationship.
  • the charge transport layer has a first organic layer, a second organic layer, and a third organic layer in this order from the anode side.
  • the first organic layer is formed of a composition containing a charge transporting compound (A) and a solvent
  • the second organic layer is composed of a charge transporting compound (A) and a charge transporting compound (B).
  • the third organic layer is formed of a composition containing the charge transporting compound (B) and a solvent.
  • the first region, the second region, and the third region each mean a portion in the charge transporting layer. There is not necessarily an interface between regions. That is, in one embodiment, there is an interface between the regions, and in another embodiment, there is no interface between the regions. In yet another embodiment, there is an interface between one of the first region and the second region and between the second region and the third region, and the other is an interface. Does not exist.
  • the presence of the “interface” can be confirmed by, for example, a transmission electron microscope (TEM). Specifically, the cross section of the charge transporting layer is observed with a TEM to confirm the presence or absence of a boundary line.
  • TEM transmission electron microscope
  • each region exists as an independent layer. That is, the charge transporting layer has a first organic layer as the first region, a second organic layer as the second region, and a third organic layer as the third region.
  • the charge transporting layer has a first region, a second region, and a third region that satisfy the relationship of the formulas (I) and (II).
  • TOF-SIMS temporal secondary ion mass spectrometry
  • the cross section of the charge transporting layer is subjected to surface analysis by TOF-SIMS, and the distribution of the ratio of the constituent elements is obtained in the depth direction of the charge transporting layer.
  • the cross section is preferably a surface obtained by obliquely cutting the surface of the charge transporting layer at a shallow angle with respect to the surface.
  • the content distribution of the charge transporting compound (A) and the charge transporting compound (B) is obtained using the distribution of the ratio of the constituent elements.
  • the charge transporting compound (A) and / or the charge transporting compound (B) contains at least one of the charge transporting compound (A) and the charge transporting compound (B) (for example, a charge transporting compound). Even if it exists as a cured product containing (A) and a charge transporting compound (B)), the charge transporting compound (A) and the charge transporting are performed according to the distribution of the ratio of the constituent elements obtained by TOF-SIMS. The distribution of the content of the functional compound (B) is determined.
  • the charge transporting layer may be divided into each region so as to satisfy the formula (I) and the formula (II). it can.
  • the interface when an interface can be confirmed in the charge transporting layer, the interface is set as a boundary between the regions.
  • the charge transporting layer may be divided into three equal parts, and each may be used as each region.
  • the interface is set as a boundary between the first region and the second region, or the second region and the third region.
  • the remaining charge transporting layer may be divided into two equal parts to form the remaining two regions. In either case, the three regions are divided so that no interface exists in each region.
  • the values of B2 / A2 and A2 / B2 are preferably 2/8 or more, more preferably 3/7 or more, from the viewpoint of improving the charge transportability by allowing the charge transporting compound to exist in a well-balanced manner, and 4/6 or more. Is more preferable. Further, from the same viewpoint, the values of B2 / A2 and A2 / B2 are preferably 8/2 or less, more preferably 7/3 or less, and even more preferably 6/4 or less.
  • the values of B1 / A1 and A3 / B3 are preferably less than 3/7, preferably less than 2/8 from the viewpoint of using a material excellent in compatibility with the lower layer (for example, the anode) or the upper layer (for example, the light emitting layer). Is more preferable, and less than 1/9 is still more preferable. Moreover, the value of B1 / A1 and A3 / B3 is 0 or more, and a minimum is not specifically limited.
  • the first region, the second region, and the third region are formed using, for example, a composition containing a charge transporting compound and a solvent.
  • a composition containing a charge transporting compound and a solvent An example of a method for forming a region is shown below. However, the method for forming the region is not limited to the following.
  • the charge transporting layer is formed using a composition containing the charge transporting compound (A), the charge transporting compound (B), and a solvent.
  • the type of the substituent that the charge transporting compound (A) has is different from the type of the substituent that the charge transporting compound (B) has.
  • a linear, cyclic, or branched alkyl group a linear, cyclic, or branched alkyl group in which a part of hydrogen atoms are fluorine-substituted;
  • the alkyl group preferably has 10 to 22 carbon atoms.
  • the charge transporting compound (A) When a charge transporting layer is formed on the anode with this composition, the charge transporting compound (B) can be unevenly distributed or localized on the light emitting layer side, and as a result, the first region, the second region, and A third region can be formed.
  • each region may be an organic layer
  • the first region, the second region, and the third region can be formed according to the organic layer forming method described below.
  • the charge transport layer has a first organic layer, a second organic layer, and a third organic layer. Preferred examples of the first organic layer, the second organic layer, and the third organic layer will be described below.
  • the first organic layer is formed by, for example, a first composition containing at least the charge transporting compound (A) and a solvent.
  • the charge transporting compound (A) preferably has a polymerizable substituent from the viewpoint of imparting solvent resistance to the organic layer.
  • the first composition preferably contains an ionic compound from the viewpoint of improving the curability or charge transportability of the charge transporting compound (A).
  • the first organic layer forms a coating film using a first composition containing at least the charge transporting compound (A) and the solvent, and further an ionic compound, and then cures the coating film. Can be obtained.
  • the first organic layer is preferably a hole injection layer of an organic EL element.
  • the thickness of the first organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 5 nm or more, from the viewpoint of covering unevenness caused by the anode and suppressing short circuit. Moreover, from a viewpoint of making the electrical resistance of an organic layer small, 500 nm or less is preferable, 300 nm or less is more preferable, and 200 nm or less is still more preferable.
  • the second organic layer is formed by, for example, a second composition containing at least the charge transporting compound (A), the charge transporting compound (B), and a solvent.
  • the charge transporting compound (A) and / or the charge transporting compound (B) preferably has a polymerizable substituent from the viewpoint of imparting solvent resistance to the organic layer.
  • the second organic layer forms a coating film using a second composition containing at least the charge transporting compound (A), the charge transporting compound (B), and a solvent, and then the coating film is formed. It is obtained by curing.
  • the second organic layer is preferably provided adjacent to the first organic layer.
  • the second composition may contain an ionic compound from the viewpoint of improving the curability or charge transportability of the charge transporting compound (A) and / or the charge transporting compound (B). Good. In other embodiments, the second composition may not contain an ionic compound in consideration of the influence on the adjacent layer.
  • the thickness of the second organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more, from the viewpoint of improving the charge transport efficiency. Moreover, from a viewpoint of making the electrical resistance of an organic layer small, 500 nm or less is preferable, 300 nm or less is more preferable, and 200 nm or less is still more preferable.
  • the third organic layer is formed of, for example, a composition containing at least the charge transporting compound (B) and a solvent.
  • the charge transporting compound (B) preferably has a polymerizable substituent from the viewpoint of imparting solvent resistance to the organic layer.
  • the third organic layer is obtained by forming a coating film using a composition containing at least the charge transporting compound (B) and a solvent, and then curing the coating film.
  • the third organic layer is preferably provided adjacent to the second organic layer.
  • the third composition may contain an ionic compound from the viewpoint of improving the curability or charge transportability of the charge transport compound (B).
  • the third composition may not contain an ionic compound in consideration of the influence on the adjacent layer.
  • the first organic layer is preferably a hole transport layer of an organic EL element.
  • the thickness of the third organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more, from the viewpoint of improving the charge transport efficiency. Moreover, from a viewpoint of making the electrical resistance of an organic layer small, 500 nm or less is preferable, 300 nm or less is more preferable, and 200 nm or less is still more preferable.
  • the charge transporting compound is not particularly limited as long as it has an ability to transport charges. Holes are preferred as the charge to be transported.
  • the charge transporting compound may be a commercially available one, or one synthesized by a method known to those skilled in the art, and is not particularly limited.
  • the absolute value of the work function of the anode, the charge transporting compound (A), the charge transporting compound (B), and the light emitting layer material It is preferable that the absolute value of the highest occupied orbital (HOMO) level satisfies the relationship of the following formula (III).
  • charge transporting compound (A) a material used for forming the hole injecting layer can be selected, and as the charge transporting compound (B), a material used for forming the hole transporting layer can be selected and used.
  • the description regarding the charge transporting compound applies to the charge transporting compound (A) and the charge transporting compound (B).
  • the charge transport compound (B) is a compound different from the charge transport compound (A).
  • the charge transporting compound has one or two or more structural units having a charge transporting property.
  • the structural unit having charge transporting properties is not particularly limited as long as it contains an atomic group having the ability to transport charges.
  • the structural unit having a charge transporting property may include an amine ring structure (also referred to as an “aromatic amine”) structure, a carbazole structure, or a thiophene structure as an atomic group from the viewpoint of having a high hole transporting property. preferable.
  • aromatic amine triarylamine is preferable, and triphenylamine is more preferable.
  • the charge transporting compound may be either a low molecular compound having one structural unit or a high molecular compound having a plurality of structural units (meaning “polymer or oligomer”). From the viewpoint of easily obtaining a high purity material, a low molecular weight compound is preferable. From the viewpoint of easy production of the composition and excellent film formability, a polymer compound is preferable. Furthermore, from the viewpoint that both advantages can be obtained, it is also possible to use a mixture of a low molecular compound and a high molecular compound.
  • the structural units (1a) to (84a), which are specific examples of the structural unit having hole transportability, are listed below.
  • E represents a hydrogen atom or a substituent, and for example, each independently represents —R 1 , —OR 2 , —SR 3 , —OCOR 4 , —COOR 5 , —SiR 6 R 7 R 8 , —OSiR. 9
  • R 10 R 11 represents any group selected from the group consisting of the following formulas (1) to (3), a halogen atom, and a group having a polymerizable substituent.
  • R 1 to R 14 each independently represents a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms.
  • the hydrogen atoms in R 1 to R 14 and formulas (1) to (3) may be substituted.
  • the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, and an arylthio group.
  • a, b and c each represents an integer of 1 or more, preferably an integer of 1 to 8, more preferably an integer of
  • each Ar independently represents an aryl group or heteroaryl group having 2 to 30 carbon atoms, or an arylene group or heteroarylene group having 2 to 30 carbon atoms.
  • Ar may have a substituent, and examples of the substituent include the same groups as those described above for E.
  • X and Z each independently represent a divalent linking group and are not particularly limited.
  • x represents an integer of 0-2.
  • Y represents a trivalent linking group and is not particularly limited.
  • a group obtained by removing two hydrogen atoms from a group having two or more hydrogen atoms in the above E (excluding a group having a polymerizable substituent) can be mentioned.
  • examples of R include the same groups as those described above.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • examples of the halogen atom include atoms similar to these.
  • examples of the alkyl group include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, A cycloheptyl group, a cyclooctyl group, etc. are mentioned.
  • examples of the alkyl group include groups similar to these.
  • the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon
  • the heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic compound having a hetero atom. It is.
  • the aryl group include phenyl, biphenyl-yl, terphenyl-yl, triphenylbenzene-yl, naphthalen-yl, anthracen-yl, tetracene-yl, fluoren-yl, phenanthrene-yl and the like.
  • heteroaryl group examples include pyridine-yl, pyrazin-yl, quinolin-yl, isoquinolin-yl, acridine-yl, phenanthroline-yl, furan-yl, pyrrol-yl, thiophen-yl, carbazol-yl, oxazole- Yl, oxadiazol-yl, thiadiazol-yl, triazol-yl, benzoxazol-yl, benzooxadiazol-yl, benzothiadiazol-yl, benzotriazol-yl, benzothiophen-yl and the like.
  • examples of the aryl group and heteroaryl group include groups similar to these.
  • an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon
  • a heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic compound having a hetero atom. It is.
  • the arylene group include phenylene, biphenyl-diyl, terphenyl-diyl, triphenylbenzene-diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, and the like.
  • heteroarylene group examples include pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, carbazole-diyl, oxazole- Examples include diyl, oxadiazole-diyl, thiadiazole-diyl, triazole-diyl, benzoxazole-diyl, benzooxadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, and benzothiophene-diyl.
  • examples of the arylene group and the heteroarylene group include the same groups.
  • Structural units (a1) to (a6) which are preferred specific examples of the structural unit having a hole transporting property, are listed below.
  • the phenyl group, the phenylene group, the carbazole-triyl group, and the thiophene-diyl group may have a substituent, and examples of the substituent include the same groups as those described above for E.
  • the low molecular compound which is an embodiment of the charge transporting compound has, for example, one of the structural units (1a) to (84a). In this case, E is bonded to the bond.
  • the polymer compound may have only one type of structural unit selected from a unit having an aromatic amine structure, a unit having a carbazole structure, and a unit having a thiophene structure as a structural unit having charge transporting properties. Or you may have 2 or more types.
  • the polymer compound preferably has a unit having an aromatic amine structure and / or a unit having a carbazole structure.
  • the polymer compound is represented by any one of the above-mentioned arylene group or heteroarylene group or the above-mentioned linking group groups (A) and (B) as a copolymerized unit in addition to the above-mentioned units for adjusting electrical characteristics. May have a structural unit.
  • the polymer compound may have only one type of other copolymer unit or two or more types.
  • the polymer compound may be either a linear polymer compound having no branched chain or a branched polymer compound having a branched chain.
  • the branched chain has at least one structural unit constituting the polymer compound. It is also possible to use a linear polymer compound and a branched polymer compound in combination. From the viewpoint that the molecular weight and physical properties of the composition can be easily controlled precisely, a linear polymer compound is preferable, and from the viewpoint that the molecular weight can be easily increased, a branched polymer compound is preferable.
  • the branched polymer compound is also preferable from the viewpoint of enhancing the durability of the organic EL element.
  • the polymer compound having a branched chain means that the polymer compound has a branched portion on the polymer or oligomer chain and has three or more terminals.
  • the polymer compound has, for example, a structural unit serving as a branch starting point (also referred to as a “branch starting structural unit”) as a branching portion.
  • the polymer compound may have only one kind of branch origin structural unit, or may have two or more kinds.
  • the structural units (1b) to (11b), which are specific examples of the branch start structural unit, are listed below.
  • the structural units (2b) to (4b) correspond to structural units having an aromatic amine structure
  • the structural units (5b) to (8b) correspond to structural units having a carbazole structure.
  • W represents a trivalent linking group, and examples thereof include a group in which one hydrogen atom is further removed from an arylene group or heteroarylene group having 2 to 30 carbon atoms.
  • Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group.
  • Y represents a divalent linking group and is not particularly limited. For example, in E (excluding a group having a polymerizable substituent), a group in which one hydrogen atom is further removed from a group having one or more hydrogen atoms, or the above linking group group (C ). Z represents any of a carbon atom, a silicon atom, or a phosphorus atom.
  • the structural units (1b) to (11b) may have a substituent, and examples of the substituent include the same groups as those described above for E.
  • the structural unit at the end of the polymer compound is not particularly limited.
  • the structural unit which has an aromatic hydrocarbon structure or an aromatic compound structure the structural unit (1c) shown below is mentioned, for example.
  • the polymer compound may have only one type of terminal structural unit, or may have two or more types.
  • Ar represents an aryl group or heteroaryl group having 2 to 30 carbon atoms. From the viewpoint of easy introduction of a polymerizable substituent at the terminal, Ar is, for example, an aryl group, preferably a phenyl group. Ar may have a substituent, and examples of the substituent include the same groups as those described above for E.
  • the polymerizable substituent refers to a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction.
  • the cured product of the charge transporting compound is obtained by the polymerization reaction, the solubility of the charge transporting compound in the solvent is changed, and a laminated structure can be easily formed.
  • the position where the polymer compound has a polymerizable substituent is not particularly limited. Any position where a bond can be formed between two or more molecules by causing a polymerization reaction may be used. Even if the polymer compound has a polymerizable substituent in the terminal structural unit or a polymerizable substituent in the structural unit other than the terminal, the terminal structural unit and the structural unit other than the terminal You may have in both. Preferably, it has a polymerizable substituent in at least the terminal structural unit.
  • Polymerizable substituents include a group having a carbon-carbon multiple bond; a group having a cyclic structure (excluding a group having an aromatic heterocyclic structure); a group having an aromatic heterocyclic structure; and a siloxane derivative A group; a combination of groups capable of forming an ester bond or an amide bond, and the like.
  • Examples of the group having a carbon-carbon multiple bond include a group having a carbon-carbon double bond and a group having a carbon-carbon triple bond, and specifically include an acryloyl group, an acryloyloxy group, an acryloylamino group, and a methacryloyl group.
  • Examples of the group having a cyclic structure include a group having a cyclic alkyl structure, a group having a cyclic ether structure, a lactone group (a group having a cyclic ester structure), a lactam group (a group having a cyclic amide structure), and the like.
  • a group having a cyclic alkyl structure a group having a cyclic ether structure
  • a lactone group a group having a cyclic ester structure
  • lactam group a group having a cyclic amide structure
  • the like are cyclopropyl group, cyclobutyl group, cardene group (1,2-dihydrobenzocyclobutene group), epoxy group (oxiranyl group), oxetane group (oxetanyl group), diketene group, episulfide group, ⁇ -lactone group, ⁇ -Lactone group, ⁇ -lactam group, ⁇ -lact
  • Examples of the group having an aromatic heterocyclic structure include a furan-yl group, a pyrrole-yl group, a thiophene-yl group, and a silole-yl group.
  • Examples of the combination of groups capable of forming an ester bond or an amide bond include a combination of a carboxyl group and a hydroxyl group, or a combination of a carboxyl group and an amino group.
  • the number of polymerizable substituents per molecule of the polymer compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of excellent curability.
  • the number of polymerizable substituents is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of the stability of the polymer compound.
  • the polymer compound may have a “polymerizable substituent” as a “group having a polymerizable substituent”.
  • the group having a polymerizable substituent has an alkylene moiety, and the polymerizable substituent is bonded to the alkylene moiety.
  • the alkylene moiety include linear alkylene moieties such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene.
  • the alkylene moiety preferably has 1 to 8 carbon atoms.
  • the polymer compound, particularly the charge transporting compound (A) has a hydrophilic moiety and a polymerizable substituent. It is preferred that the group is bonded to the hydrophilic site.
  • the hydrophilic moiety include linear hydrophilic moieties such as an oxyalkylene structure such as an oxymethylene structure and an oxyethylene structure; and a polyalkyleneoxy structure such as a polyoxymethylene structure and a polyoxyethylene structure.
  • the number of carbon atoms in the hydrophilic portion is preferably 1-8.
  • the group having a polymerizable substituent is an atomic group having the ability to transport an alkylene part or a hydrophilic part, a polymerizable substituent and / or charge.
  • the connecting part may include an ether bond, an ester bond, or the like.
  • examples of the “group having a polymerizable substituent” include the “polymerizable substituent” itself.
  • the polymer compound preferably has a polymerizable substituent at the end of the molecular chain.
  • the polymer compound may have a structural unit having a “group having a polymerizable substituent” as a terminal structural unit.
  • Specific examples include the structural unit (1c) having any of the groups represented by the substituent groups (A) to (N).
  • the polymer compound may be a homopolymer having one type of structural unit or a copolymer having two or more types of structural units.
  • the copolymer may be an alternating, random, block, or graft copolymer, or a copolymer having an intermediate structure thereof, for example, a block property. It may be a random random copolymer.
  • the ratio of the total number of structural units (1a) to (84a) to the total number of structural units in the polymer compound is sufficient for charge transportability. 10% or more is preferable, 20% or more is more preferable, and 30% or more is more preferable.
  • the ratio of the total number of the structural units (1a) to (84a) in one embodiment can be set to 100% from the viewpoint of obtaining high charge injection property and charge transport property. In another embodiment, it is preferably 95% or less, more preferably 90% or less, and still more preferably 85% or less from the viewpoint of enhancing durability while imparting charge transportability.
  • the “ratio of structural units” can be obtained from the charged ratio (molar ratio) of monomers corresponding to each structural unit used for synthesizing the polymer compound.
  • the ratio of the total number of structural units (1b) to (11b) to the total number of structural units in the polymer compound is unevenness caused by the anode. Is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more. Further, the ratio of the total number of structural units (1b) to (11b) is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less, from the viewpoint of satisfactory synthesis of the polymer compound.
  • the ratio of the structural unit (1c) to the total number of structural units in the polymer compound is preferably 5% or more from the viewpoint of improving solubility, film formability, and the like. 10% or more is more preferable, and 15% or more is more preferable.
  • the proportion of the structural unit (1c) is preferably 95% or less, more preferably 90% or less, and still more preferably 85% or less, from the viewpoint of preventing a decrease in charge transportability.
  • the ratio of the polymerizable substituent to the total number of structural units in the polymer compound is preferably 0.1% or more, preferably 1% or more from the viewpoint of introducing two or more polymerizable substituents into the polymer compound. Is more preferable, and 3% or more is still more preferable.
  • the range is also preferable from the viewpoint of efficiently curing the polymer compound.
  • the ratio of the polymerizable substituent is preferably 70% or less, more preferably 60% or less, and still more preferably 50% or less from the viewpoint of obtaining good charge transportability.
  • the said range is preferable also from a viewpoint of obtaining the high molecular compound which has sufficient molecular weight.
  • the “ratio of polymerizable substituents” here is the ratio of structural units having polymerizable substituents.
  • the number average molecular weight of the polymer compound is not particularly limited, and can be appropriately adjusted in consideration of solubility in a solvent, film forming property, and the like.
  • the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more, from the viewpoint of excellent charge transportability. Further, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the composition. Is more preferable.
  • a number average molecular weight means the number average molecular weight of standard polystyrene conversion by gel permeation chromatography (GPC).
  • the weight average molecular weight of a high molecular compound is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more, from the viewpoint of excellent charge transportability.
  • the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 400,000 or less from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the composition. Is more preferable.
  • a weight average molecular weight means the weight average molecular weight of standard polystyrene conversion by gel permeation chromatography.
  • the polymer compound can be produced by various synthetic methods known to those skilled in the art, and is not particularly limited.
  • each monomer used for the synthesis of a polymer compound has an aromatic ring
  • a polymer compound is produced by coupling monomers having an aromatic ring
  • Suzuki Pd-catalyzed cross-coupling reaction
  • the Suzuki reaction is preferable in that a polymer compound can be easily produced by using desired aromatic rings in a bonding reaction.
  • a Pd (0) compound or a Pd (II) compound is mainly used as a Pd catalyst.
  • Ni compounds are used, and both can be used.
  • Pd (PPh 3 ) 4 tetrakis (triphenylphosphine) palladium (0)
  • Pd (dppf) Cl 2 [1,1′-bis (diphenylphosphino) ferrocene] palladium (II)
  • Pd compounds having a phosphine ligand such as dichloride and Pd (dppe) Cl 2 ([1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride) can be used directly.
  • phosphine ligand As the phosphine ligand at this time, known phosphine compounds such as P (t-Bu) 3 (tris (t-butyl) phosphine), tributylphosphine, P (c-hex) 3 (tricyclohexylphosphine), A phosphine compound or the like can be used.
  • the concentration of the Pd catalyst may be adjusted to an arbitrary range of, for example, about 0.01 to 5 mol% with respect to the monomer to be reacted.
  • the reaction solvent an organic solvent or a mixed solvent system of water and an organic solvent is mainly used.
  • the organic solvent include dimethoxyethane, toluene, anisole, tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide and the like. Can be used.
  • alkali metal carbonates such as Na 2 CO 3 and K 2 CO 3
  • alkali metal hydroxides such as NaOH and KOH
  • TMAH tetramethylammonium hydroxide
  • Water-soluble organic bases such as TEAH (tetraethylammonium hydroxide) can also be used. It is also possible to promote the reaction by adding a phase transfer catalyst.
  • phase transfer catalysts include TBAB (tetrabutylammonium bromide), Aliquat (registered trademark) 336 (manufactured by Sigma Aldrich Japan GK, a mixture of trioctylmethylammonium chloride and tricaprylylmethylammonium chloride), and the like. .
  • each monomer monomers corresponding to the structural units exemplified above can be used.
  • a method of obtaining a polymer compound having a target polymerizable substituent a method using a monomer having a polymerizable substituent in the synthesis of the polymer compound, or a precursor polymer compound (target Examples include a method of synthesizing a polymer compound having no polymerizable substituent and introducing the polymerizable substituent into the obtained precursor polymer compound.
  • Introduction of a polymerizable substituent can be appropriately performed by a known method depending on the kind of the polymerizable substituent.
  • a method of introducing an acryloyl group or a methacryloyl group using a reaction between a hydroxyl group and a carboxyl group For example, a method of introducing an acryloyl group or a methacryloyl group using a reaction between a hydroxyl group and a carboxyl group; a method of obtaining an epoxy group from a vinyl group using a percarboxylic acid; an ether using a reaction between a hydroxyl group and a halide Examples thereof include a method of introducing various polymerizable substituents by releasing the bond.
  • the charge transporting compound (A) preferably has a polymerizable substituent.
  • the polymerizable substituent of the charge transporting compound (A) is preferably a group having a cyclic structure or a group having a carbon-carbon multiple bond from the viewpoint of excellent reactivity.
  • a group having a cyclic structure a group having a cyclic ether structure is more preferable, an epoxy group or an oxetane group is further preferable, and an oxetane group is particularly preferable.
  • the group having a carbon-carbon multiple bond is more preferably a group having a carbon-carbon double bond, and an acryloyl group, an acryloyloxy group, a methacryloyl group, a methacryloyloxy group, a vinyloxy group, a styryl group, or a vinyl group
  • An acryloyl group, a methacryloyl group, a styryl group, or a vinyl group is particularly preferable.
  • the charge transporting compound (A) preferably has two or more polymerizable substituents from the viewpoint of excellent curability.
  • the polymer compound as the charge transporting compound (A) is composed of a unit having an aromatic amine structure and / or a unit having a carbazole structure as a main structural unit (from the viewpoint of obtaining high hole injecting property and hole transporting property ( A compound having a main skeleton) is preferable.
  • the ratio of the total number of units having an aromatic amine structure and / or carbazole structure to the total number of structural units in the polymer compound (excluding the terminal structural unit) is 40% or more.
  • 45% or more is more preferable, and 50% or more is further preferable.
  • the ratio of the total number of units having an aromatic amine structure and / or carbazole structure may be 100%.
  • the charge transporting compound (A) preferably has a branching origin structural unit.
  • a branching origin structural unit possessed by the charge transporting compound (A) from the viewpoint of excellent charge transportability, a unit corresponding to a structural unit having an aromatic amine structure or a structural unit having a carbazole structure (for example, a structural unit ( 2b) to (4b) or (5b) to (8b)) are preferred.
  • At least one of E in the charge transporting compound (A) is preferably —R 1 or —OR 2 .
  • R 1 and R 2 are preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group having 6 to 30 carbon atoms.
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • the aryl group is preferably a phenyl group.
  • the substituent is preferably a halogen atom from the viewpoint of obtaining an organic EL device having excellent lifetime characteristics.
  • Examples of monomers when the charge transporting compound (A) is produced by the Suzuki reaction are shown below.
  • the synthesis method and monomer of the charge transporting compound (A) are not limited thereto.
  • each R is independently a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; an aryl group or heteroaryl group having 2 to 30 carbon atoms; A linear, cyclic or branched alkoxy group; a halogen atom; or a group having a polymerizable substituent.
  • the charge transporting compound (B) Similarly to the charge transporting compound (A), the charge transporting compound (B) preferably has a polymerizable substituent.
  • the polymerizable substituent of the charge transporting compound (B) may be the same as or different from that of the charge transporting compound (A). In one embodiment, the same polymerizable substituent is preferable from the viewpoint of obtaining excellent curability. In another embodiment, different polymerizable substituents are preferable from the viewpoint of obtaining excellent durability.
  • a group having a cyclic structure or a carbon-carbon multiple bond may be used from the viewpoint of excellent reactivity and obtaining an organic EL device having excellent lifetime characteristics.
  • the group having is preferable.
  • a group having a cyclic structure a group having a cyclic ether structure is more preferable, an epoxy group or an oxetane group is further preferable, and an oxetane group is particularly preferable.
  • the group having a carbon-carbon multiple bond is more preferably a group having a carbon-carbon double bond, and an acryloyl group, an acryloyloxy group, a methacryloyl group, a methacryloyloxy group, a vinyloxy group, a styryl group, or a vinyl group
  • An acryloyl group, a methacryloyl group, a styryl group, or a vinyl group is particularly preferable.
  • the charge transporting compound (B) preferably has two or more polymerizable substituents from the viewpoint of excellent curability and durability.
  • the polymer compound as the charge transporting compound (B) is preferably a compound having a unit having an aromatic amine structure and / or a unit having a carbazole structure from the viewpoint of having a high hole transporting property. Further, from the viewpoint of enhancing durability, heat resistance, etc., a compound containing a structural unit other than a unit having an aromatic amine structure and a unit having a carbazole structure may be used. From this viewpoint, the ratio of the total number of units having an aromatic amine structure and / or carbazole structure to the total number of structural units in the polymer compound (excluding the terminal structural unit) is 5% or more. Preferably, 10% or more is more preferable, and 15% or more is still more preferable.
  • the ratio of the total number of structural units other than units having an aromatic amine structure and units having a carbazole structure to the total number of structural units in the polymer compound (excluding the terminal structural unit) maintains the hole transport property. In view of this, it is preferably 95% or less, more preferably 90% or less, and still more preferably 85% or less.
  • the charge transporting compound (B) preferably has a branching origin structural unit.
  • the branching origin structural unit possessed by the charge transporting compound (B) from the viewpoint of enhancing durability, heat resistance and the like, structural units other than units having an aromatic amine structure and units having a carbazole structure (for example, structural units ( 1b), (9b) to (11b), preferably a unit corresponding to the structural unit (11b)).
  • At least one of E in the charge transporting compound (B) is preferably —R 1 or —OR 2 .
  • R 1 and R 2 are preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group having 6 to 30 carbon atoms.
  • the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
  • the aryl group is preferably a phenyl group.
  • the substituent is preferably a halogen atom from the viewpoint of obtaining an organic EL device having excellent lifetime characteristics.
  • Examples of the monomer for producing the polymer compound as the charge transporting compound (B) by the Suzuki reaction include the monomers exemplified in the charge transporting compound (A) and the monomers shown below. Preferably, at least one selected from the monomers shown below is used.
  • the synthesis method and monomer of the charge transporting compound (B) are not limited thereto.
  • composition contains at least a charge transporting compound and a solvent, and may further contain an ionic compound.
  • the composition may be commercially available or prepared by a method known to those skilled in the art.
  • the description regarding a composition here is applied about a 1st composition, a 2nd composition, and a 3rd composition.
  • solvent examples include water and an organic solvent.
  • organic solvent include alcohols such as methanol, ethanol, and isopropyl alcohol; alkanes such as pentane, hexane, and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, and diphenylmethane; Aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxy Aromatic ethers such as toluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylani
  • the content of the solvent in the composition can be determined in consideration of applying various film forming methods.
  • the content of the solvent is preferably such that the ratio of the charge transporting compound to the total mass of the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass. % Is more preferable.
  • the content of the solvent is preferably such that the ratio of the charge transporting compound to the total mass of the solvent is 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. Further preferred.
  • ionic compounds examples include compounds that can act as electron acceptors for charge transporting compounds (hereinafter referred to as “electron accepting compounds”), and can act as polymerization initiators for charge transporting compounds.
  • electron accepting compounds compounds that can act as electron acceptors for charge transporting compounds
  • polymerization initiator a compound that can act as both an electron accepting compound and a polymerization initiator are included.
  • any of an inorganic substance and an organic substance can be used.
  • the electron-accepting compound described in JP-A-2003-031365 and JP-A-2006-233162 Japanese Patent No. 3957635 And Super Bronsted acid compounds and derivatives thereof described in the above publication.
  • compounds having a perfluoroaryl group or a perfluoroalkyl group are preferred.
  • an onium salt containing one kind selected from the following cations and one kind selected from the following anions can also be preferably used.
  • cation examples include H + , carbenium ion, ammonium ion, anilinium ion, pyridinium ion, imidazolium ion, pyrrolidinium ion, quinolinium ion, imonium ion, aminium ion, oxonium ion, and pyrylium ion.
  • anion examples include halogen ions such as F ⁇ , Cl ⁇ , Br ⁇ and I ⁇ ; OH ⁇ ; ClO 4 ⁇ ; FSO 3 ⁇ , ClSO 3 ⁇ , CH 3 SO 3 ⁇ , C 6 H 5 SO 3 ⁇ .
  • CF 3 SO 3 - sulfonate ion such as; HSO 4 -, SO 4 sulfate ions of 2-like; HCO 3 -, CO 3 carbonate ions of 2-like; H 2 PO 4 -, HPO 4 2 -, phosphate ions of PO 4 3- and the like; PF 6 -, PF 5 OH - fluorophosphate ions such as; [(CF 3 CF 2) 3 PF 3] -, [(CF 3 CF 2 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 2 PF 4 ] ⁇ , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] -, [((CF
  • fluoroalkane methide of imide ion such as BF 4 - , B (C 6 F 5 ) 4 ⁇ , B (C 6 H 4 CF 3 ) 4 ⁇ and the like; Boron ions such as SbF 6 ⁇ and SbF 5 OH ⁇ ; AsF 6 ⁇ and AsF 5 OH - fluoroarsenate periodate ions such as; AlCl 4 -, BiF 6 -, and the like.
  • fluorophosphate ions such as PF 6 ⁇ and PF 5 OH — ; [(CF 3 CF 2 ) 3 PF 3 ] ⁇ , [( CF 3 CF 2 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 2 PF 4 ] ⁇ , [((CF 3 ) 2 Fluorinated alkyl fluorophosphate ions such as CFCF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CFCF 2 ) 2 PF 4 ] ⁇ ; (CF 3 SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) Fluoroalkanesulfonylmethides such as 2 N ⁇ , imide ions; borate ions such as BF 4 ;
  • the composition further comprises other additives such as polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, anti-reducing agents, oxidizing agents, reducing agents, surface modifiers, emulsifiers. , An antifoaming agent, a dispersing agent, a surfactant, an electron accepting compound and the like may be contained.
  • the composition can be preferably used as an ink composition.
  • the first composition for forming the first organic layer contains at least the charge transporting compound (A) and a solvent, and may further contain an ionic compound.
  • the content of the charge transporting compound (A) in the first composition is preferably 0.01% by mass or more based on the total mass of the composition, from the viewpoint of adjusting the viscosity, film formability, and the like of the composition. 0.05 mass% or more is more preferable, and 0.1 mass% or more is still more preferable.
  • the content of the charge transporting compound (A) is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass or less in the total mass of the composition from the viewpoint of suppressing aggregation, precipitation, and the like. Is more preferable.
  • the content of the ionic compound is from the viewpoint of causing sufficient polymerization or improving the charge transportability, with respect to the total mass of the charge transportable compound (A), 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable. Further, the content of the ionic compound is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass with respect to the total mass of the charge transporting compound (A) from the viewpoints of film formability and heat resistance. % Or less is more preferable.
  • the first composition may contain the charge transporting compound (B) as long as the effects of the present embodiment are not impaired.
  • the ratio between the content of the charge transporting compound (A) and the content of the charge transporting compound (B) in the first composition charge transporting compound (B) [mass%] / charge transporting compound) (A) [% by mass]) is preferably less than 3/7, more preferably less than 2/8, and even more preferably less than 1/9 from the viewpoint of using a material excellent in compatibility with the lower layer.
  • the lower limit is not particularly limited and is 0 or more.
  • composition for forming the second organic layer contains at least a charge transporting compound (A), a charge transporting compound (B) and a solvent, and may further contain an ionic compound.
  • the second composition contains an ionic compound from the viewpoint of facilitating the curing of the charge transporting compound (A) and / or the charge transporting compound (B) or improving the charge transporting property. It is preferable to contain. On the other hand, in another embodiment, it is preferable that a 2nd composition does not contain an ionic compound from a viewpoint of avoiding the influence on the upper layer or lower layer of an ionic compound and its decomposition product. In consideration of the curability of the charge transporting compounds (A) and (B), the charge transporting property, the influence on the adjacent layer, etc., an ionic compound can be appropriately used for the second composition. It can be selected as appropriate.
  • the content of the charge transporting compound (A) in the second composition is preferably 0.005% by mass or more based on the total mass of the composition from the viewpoint of adjusting the viscosity, film formability, and the like of the composition. 0.025 mass% or more is more preferable, and 0.05 mass% or more is still more preferable. Further, the content of the charge transporting compound (A) is preferably 25% by mass or less, more preferably 22.5% by mass or less, and more preferably 20% by mass in the total mass of the composition from the viewpoint of suppressing aggregation, precipitation and the like. % Or less is more preferable.
  • the content of the charge transporting compound (B) in the second composition is preferably 0.005% by mass or more based on the total mass of the composition from the viewpoint of adjusting the viscosity, film formability, etc. of the composition. 0.025 mass% or more is more preferable, and 0.05 mass% or more is still more preferable. Further, the content of the charge transporting compound (B) is preferably 25% by mass or less, more preferably 22.5% by mass or less, and more preferably 20% by mass in the total mass of the composition from the viewpoint of suppressing aggregation, precipitation and the like. % Or less is more preferable.
  • the mass ratio (charge transporting compound (A) / charge transporting compound (B)) between the content of the charge transporting compound (A) and the content of the charge transporting compound (B) in the second composition is: From the viewpoint of improving the charge transportability by allowing the charge transporting compound to exist in a balanced manner, it is preferably 2/8 or more, more preferably 3/7 or more, and even more preferably 4/6 or more.
  • the mass ratio (charge transporting compound (A) / charge transporting compound (B)) is preferably 8/2 or less, more preferably 7/3 or less, and even more preferably 6/4 or less, from the same viewpoint. .
  • the content of the ionic compound is such that the charge transporting compounds (A) and (B) are all contained from the viewpoint of causing sufficient polymerization or improving the charge transporting property.
  • 0.1 mass% or more is preferable with respect to mass, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable.
  • the content of the ionic compound is preferably 50% by mass or less, more preferably 45% by mass or less, with respect to the total mass of the charge transporting compounds (A) and (B), from the viewpoints of film formability and heat resistance.
  • 40 mass% or less is more preferable.
  • the composition for forming the third organic layer contains at least the charge transporting compound (B) and a solvent, and may further contain an ionic compound.
  • the third composition preferably contains an ionic compound from the viewpoint of facilitating curing of the charge transporting compound (B) or improving the charge transporting property.
  • a 3rd composition does not contain an ionic compound from a viewpoint of avoiding the influence on the upper layer or lower layer of an ionic compound and its decomposition product.
  • an ionic compound can be appropriately used in consideration of the curability of the charge transporting compound (B), the charge transporting property, the influence on the adjacent layer, and the like, and the type thereof can also be selected as appropriate.
  • the content of the charge transporting compound (B) in the third composition is preferably 0.01% by mass or more based on the total mass of the composition, from the viewpoint of adjusting the viscosity, film formability, and the like of the composition. 0.05 mass% or more is more preferable, and 0.1 mass% or more is still more preferable. Moreover, from a viewpoint of suppressing aggregation, precipitation, etc., 50 mass% or less is preferable in the total mass of a composition, 45 mass% or less is more preferable, and 40 mass% or less is still more preferable.
  • the content of the ionic compound is from the viewpoint of causing sufficient polymerization or increasing the charge transportability, with respect to the total mass of the charge transportable compound (B), 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable.
  • the content of the charge transporting compound (B) is 50% by mass or less based on the total mass of the charge transporting compound (B), from the viewpoint of film formability and heat resistance. Preferably, 45 mass% or less is more preferable, and 40 mass% or less is still more preferable.
  • the third composition may contain the charge transporting compound (A) as long as the effects of the present embodiment are not impaired.
  • the ratio between the content of the charge transporting compound (A) and the content of the charge transporting compound (B) in the third composition charge transporting compound (A) [mass%] / charge transporting compound (B) [% by mass]) is preferably less than 3/7, more preferably less than 2/8, and even more preferably less than 1/9 from the viewpoint of using a material excellent in compatibility with the upper layer.
  • the lower limit is not particularly limited and is 0 or more.
  • composition set A 1st composition, a 2nd composition, and a 3rd composition can be used as a composition set which combined 3 types. By using the composition set, the first organic layer, the second organic layer, and the third organic layer can be easily formed.
  • Method for forming organic layer examples include spin coating method; casting method; immersion method; letterpress printing, intaglio printing, offset printing, planographic printing, letterpress reverse offset printing, screen printing, gravure printing, and the like.
  • printing methods such as plate printing method; plateless printing method such as inkjet method.
  • the obtained film may be dried by a hot plate or an oven to remove the solvent.
  • the trigger for initiating the polymerization is generally a method such as light irradiation or heating, and is not particularly limited, but heating is preferred from the viewpoint of simple process.
  • a light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a light emitting diode, or sunlight can be used.
  • the wavelength of the irradiated light is, for example, 200 to 800 nm.
  • a heating device such as a hot plate or an oven can be used.
  • the heating temperature and time are not particularly limited as long as the polymerization reaction can proceed sufficiently.
  • About temperature from a viewpoint which can apply a various board
  • the time is preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less.
  • the viewpoint of allowing the polymerization to proceed completely it is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 minutes or longer.
  • the organic EL element which is an embodiment of the present invention is not limited, and details are not clear, but one reason for obtaining an organic EL element having excellent characteristics is presumed as follows. That is, in one embodiment of the organic EL device, the charge transporting layer contains the charge transporting compound (A) and the charge transporting compound (B), and in the order from the anode side, the formula (I) and the formula The first region, the second region, and the third region satisfying the relationship (II).
  • the charge transporting layer is formed of a composition containing a charge transporting compound and a solvent, and in order from the anode side, the first region satisfying the relationship of the formulas (I) and (II), It has a second region and a third region.
  • the charge transporting layer includes a first organic layer containing the charge transporting compound (A), the charge transporting compound (A), and the charge transporting compound (B). And a third organic layer containing the charge transporting compound (B).
  • the charge transporting layer is a first organic layer formed of a composition containing the charge transporting compound (A) and a solvent, the charge transporting compound (A), the charge transporting compound (B) and the solvent. And a third organic layer formed by the charge transporting compound (B).
  • FIGS. 1 An example of an organic EL element which is an embodiment of the present invention is shown in FIGS.
  • the organic EL element shown in FIG. 1 has an anode 1, a charge transport layer 2, a light emitting layer 3, and a cathode 4 in this order, and the charge transport layer 2 includes a first region 2 a, a first layer in order from the anode side. It has the 2nd area
  • the organic EL element shown in FIG. 2 has an anode 1, a charge transporting layer 2, a light emitting layer 3, and a cathode 4 in this order, and the charge transporting layer 2 is a first organic layer in order from the anode side.
  • the charge transporting compound (A) is indicated by a black circle A and the charge transporting compound (B) is indicated by a white circle B in order to schematically represent the size of the content.
  • Black circles A and white circles B in FIGS. 1 and 2 do not mean that the charge transporting compound (A) and the charge transporting compound (B) are present in the form of a circle or a sphere in the organic layer.
  • the organic EL element may have other layers between these layers or as an upper layer or a lower layer of the anode or the cathode. Examples of other layers include an electron injection layer and an electron transport layer.
  • the organic EL element usually has a substrate. In FIG. 3, an example of the conventional organic EL element provided with the electron carrying layer 8 and the electron injection layer 9 is shown. Hereinafter, each layer will be described. The first region, the second region, and the third region, and the first organic layer, the second organic layer, and the third organic layer are as described above.
  • the material used for the light emitting layer may be a low molecular compound or a high molecular compound, and a dendrimer or the like can also be used.
  • Low molecular weight compounds that utilize fluorescence include perylene, coumarin, rubrene, quinacridone, dye dyes for dye laser (eg, rhodamine, DCM1, etc.), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq 3 )), Stilbene, and derivatives thereof.
  • polymer compound using fluorescence emission examples include polyfluorene, polyphenylene, polyphenylene vinylene (PPV), polyvinyl carbazole (PVK), fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, derivatives thereof, and A mixture of these can be suitably used.
  • phosphorescent organic EL elements have been actively developed to increase the efficiency of organic EL elements.
  • the phosphorescent organic EL element not only singlet state energy but also triplet state energy can be used, and the internal quantum yield can be increased up to 100% in principle.
  • phosphorescence is emitted by doping a host material with a metal complex phosphorescent material containing a heavy metal such as platinum or iridium as a dopant that emits phosphorescence (M. (A. Baldo et al., Nature, vol. 395, p. 151 (1998); M. A. Baldo et al., Applied Physics Letters, vol. 75, p. 4 (1999); M. A. Baldo et al., Nature, vol. 403, (See p. 750) (2000).)
  • a phosphorescent material can be used for the light emitting layer from the viewpoint of high efficiency.
  • a metal complex containing a central metal such as Ir or Pt can be preferably used.
  • Ir complex for example, FIr (pic) [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C 2 ] picolinate] that emits blue light, and green light emission.
  • Ir (ppy) 3 [Factris (2-phenylpyridine) iridium] (see M. A. Baldo et al., Nature, vol. 403, p.
  • Pt complex examples include 2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-forphine platinum (PtOEP) that emits red light.
  • PtOEP 23H-forphine platinum
  • the phosphorescent material low molecular weight compounds or dendritic species such as iridium nuclear dendrimers can be used. Moreover, these derivatives can also be used conveniently.
  • a phosphorescent material is included in the light emitting layer, it is preferable to include a host material in addition to the phosphorescent material.
  • the host material may be a low molecular compound or a high molecular compound, and a dendrimer or the like can also be used.
  • low molecular weight compounds examples include ⁇ -NPD (N, N′-Di (1-naphthyl) -N, N′-diphenylbenzidine) and CBP (4,4′-Bis (carbazol-9-yl) -biphenyl).
  • MCP (1,3-Bis (9-carbazolyl) benzene
  • CDBP (4,4′-Bis (carbazol-9-yl) -2,2′-dimethylbiphenyl) and the like
  • polymer compound for example, polyvinyl carbazole, polyphenylene, polyfluorene, or the like can be used. These derivatives can also be used.
  • the light emitting layer may be formed by a vapor deposition method or a coating method.
  • an organic EL element can be manufactured cheaply and it is more preferable.
  • the light emitting layer can be formed by applying a solution containing a phosphorescent material and, if necessary, a host material on a desired substrate by a known method.
  • the coating method include spin coating method; casting method; dipping method; letterpress printing, intaglio printing, offset printing, planographic printing, letterpress inversion offset printing, screen printing, gravure printing and other plate printing methods; ink jet method, etc. Examples include plateless printing.
  • the cathode material is preferably a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF.
  • anode material As the anode material, a metal (eg, Au) or other material having metal conductivity can be used.
  • the other materials include oxides (for example, ITO: indium oxide / tin oxide) and conductive polymers (for example, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).
  • Electrode transport layer electron injection layer
  • the electron transport layer and the electron injection layer include phenanthroline derivatives (for example, 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)), bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives.
  • Thiopyran dioxide derivatives heterocyclic tetracarboxylic anhydrides such as naphthalene and perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives (eg 2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq 3 ), Bis (2-methyl-8 -quinolinolato) -4-phenylphenolate aluminum (III) (BAlq)).
  • oxadiazole derivatives eg 2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)
  • PBD oxadiazole derivatives
  • aluminum complexes eg
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group, and the like can also be used.
  • the substrate that can be used for the organic EL element the kind of glass, plastic, or the like is not particularly limited.
  • the substrate is preferably a flexible substrate.
  • a transparent substrate is preferable, and glass, quartz, a light transmissive resin film, and the like are preferably used.
  • flexibility can be imparted to the organic EL element (that is, a flexible substrate), which is particularly preferable.
  • the resin film examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PES polyethersulfone
  • TAC the film which consists of cellulose acetate propionate (CAP) etc. is mentioned.
  • an inorganic substance such as silicon oxide or silicon nitride may be laminated on the resin film in order to suppress permeation of water vapor, oxygen and the like.
  • the organic EL element may be sealed in order to reduce the influence of outside air and extend the life.
  • a material used for sealing glass, epoxy resin, acrylic resin, plastic films such as PET and PEN, inorganic materials such as silicon oxide and silicon nitride, and the like can be used.
  • the sealing method is not particularly limited. For example, a method of directly forming on the organic EL element by vacuum deposition, sputtering, coating method, or the like, a method of bonding glass or a plastic film to the organic EL element with an adhesive, or the like. It can be used.
  • the color of light emitted from the organic EL element is not particularly limited, but the white light-emitting element is preferable because it can be used for various lighting devices such as home lighting, interior lighting, clocks, and liquid crystal backlights.
  • a plurality of light emitting colors can be simultaneously emitted and mixed using a plurality of light emitting materials.
  • White luminescence is obtained.
  • a combination of a plurality of emission colors is not particularly limited, but includes three emission maximum wavelengths of blue, green, and red, two emission maximum wavelengths of blue and yellow, yellow green and orange, etc. The thing containing is mentioned.
  • the emission color can be controlled by adjusting the type and amount of the phosphorescent material.
  • the display element which is embodiment of this invention is equipped with the organic EL element of the said embodiment.
  • a color display element can be obtained by using the organic EL element as an element corresponding to each pixel of red, green, and blue (RGB).
  • Image formation includes a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged and driven in each element.
  • the former is preferably used for displaying characters and the like because the structure is simple but the number of vertical pixels is limited.
  • the latter is preferably used for high-quality displays because the drive voltage is low and current is small, and a bright high-definition image is obtained.
  • the illuminating device which is embodiment of this invention is equipped with the organic EL element of the said embodiment.
  • the display apparatus which is embodiment of this invention is equipped with the illuminating device and the liquid crystal element as a display means.
  • the above-described illumination device may be used as a backlight (white light source), and a display device using a liquid crystal element as a display unit, that is, a liquid crystal display device may be used.
  • This configuration is a configuration in which only the backlight is replaced with the above-described illumination device in a known liquid crystal display device, and a known technique can be diverted to the liquid crystal element portion.
  • the molecular weight was measured by GPC (polystyrene conversion) using THF as an eluent.
  • the resulting charge transporting compound 1 had a number average molecular weight of 7,800 and a weight average molecular weight of 31,000.
  • the charge transporting compound 1 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) having an alkyl group (derived from the monomer C1), and oxetane.
  • the structural unit (1c) having a group (derived from the monomer C2) was present, and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.
  • the number average molecular weight and the weight average molecular weight were measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent.
  • the measurement conditions are as follows. Liquid feed pump: L-6050 Hitachi High-Technologies UV-Vis detector: L-3000 Hitachi High-Technologies columns: Gelpack (R) GL-A160S / GL-A150S Hitachi Chemical Co., Ltd. Eluent: THF (for HPLC, without stabilizer) Wako Pure Chemical Industries, Ltd. Flow rate: 1 mL / min Column temperature: Room temperature molecular weight standard: Standard polystyrene
  • the charge transporting compound 2 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) having an alkyl group (derived from the monomer C1), vinyl,
  • the structural unit (1c) having a group (derived from the monomer C3) had a proportion of each structural unit of 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.
  • the charge transporting compound 3 includes a structural unit (1a) (derived from the monomer A), a structural unit (11b) (derived from the monomer B2), a structural unit (1c) having an alkyl group (derived from the monomer C1), and oxetane.
  • the structural unit (1c) having a group (derived from the monomer C2) was present, and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 71.4%.
  • the charge transporting compound 4 includes a structural unit (1a) (derived from the monomer A), a structural unit (11b) (derived from the monomer B2), a structural unit (1c) having an alkyl group (derived from the monomer C1), vinyl,
  • the structural unit (1c) having a group (derived from the monomer C3) had a proportion of each structural unit of 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 71.4%.
  • the charge transporting compound 5 includes a structural unit (1a) (derived from the monomer A), a structural unit (6b) (derived from the monomer B3), a structural unit (1c) having an alkyl group (derived from the monomer C1), and oxetane.
  • the structural unit (1c) having a group (derived from the monomer C2) was present, and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.
  • the charge transporting compound 6 includes a structural unit (1a) (derived from the monomer A), a structural unit (6b) (derived from the monomer B3), a structural unit (1c) having an alkyl group (derived from the monomer C1), vinyl,
  • the structural unit (1c) having a group (derived from the monomer C3) had a proportion of each structural unit of 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.
  • the charge transporting compound 7 includes a structural unit (1a) (derived from the monomer A), a structural unit (1b) (derived from the monomer B4), a structural unit (1c) having an alkyl group (derived from the monomer C1), and oxetane.
  • the structural unit (1c) having a group (derived from the monomer C2) was present, and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 71.4%.
  • the charge transporting compound 8 includes a structural unit (1a) (derived from the monomer A), a structural unit (1b) (derived from the monomer B4), a structural unit (1c) having an alkyl group (derived from the monomer C1), vinyl
  • the structural unit (1c) having a group (derived from the monomer C3) had a proportion of each structural unit of 45.5%, 18.2%, 27.3%, and 9.1%.
  • the ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 71.4%.
  • Example 1 Under a nitrogen atmosphere, charge transporting compound 1 (10.0 mg), the following ionic compound 1 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ⁇ 1 , and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a first organic A layer (30 nm) was formed.
  • charge transporting compound 1 (10.0 mg), charge transporting compound 3 (10.0 mg), and toluene (4.6 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated on the first organic layer formed as described above at a rotation speed of 3,000 min ⁇ 1 and then cured by heating on a hot plate at 200 ° C. for 10 minutes to obtain a second organic layer. (30 nm) was formed.
  • the second organic layer could be formed without dissolving the first organic layer.
  • charge transporting compound 3 (10.0 mg) and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated at a rotation speed of 3,000 min ⁇ 1 and then cured by heating on a hot plate at 200 ° C. for 10 minutes to obtain a third organic layer. (30 nm) was formed.
  • the third organic layer could be formed without dissolving the second organic layer.
  • the substrate obtained above was transferred into a vacuum evaporation machine, and CBP: Ir (ppy) 3 (94: 6, 30 nm), BAlq (10 nm), Alq 3 (30 nm), LiF (on the third organic layer) 0.8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to manufacture an organic EL element.
  • Example 2 An organic EL device was produced in the same manner as in Example 1 except that the charge transporting compound 3 was changed to the charge transporting compound 5.
  • Example 3 An organic EL device was produced in the same manner as in Example 1 except that the charge transporting compound 3 was changed to the charge transporting compound 7.
  • Example 1 Under a nitrogen atmosphere, charge transporting compound 3 (20.0 mg) and toluene (1.5 mL) were mixed to prepare an ink composition.
  • the ink composition used for the second organic layer was changed to the ink composition to form the second organic layer (60 nm), and the third organic layer was not formed.
  • an organic EL device was produced. The second organic layer could be formed without dissolving the first organic layer.
  • Comparative Example 2 An organic EL device was produced in the same manner as in Comparative Example 1 except that the charge transporting compound 3 was changed to the charge transporting compound 5. The second organic layer could be formed without dissolving the first organic layer.
  • Table 1 summarizes the layer structure of the charge transporting layer of the organic EL devices produced in Examples 1 to 3 and Comparative Examples 1 to 4.
  • the charge transport layers of the organic EL devices of Examples 1 to 3 satisfied the relationship of the formulas (I) and (II).
  • Example 4 Under a nitrogen atmosphere, charge transporting compound 2 (10.0 mg), the following ionic compound 2 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ⁇ 1 , and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a first organic A layer (30 nm) was formed.
  • charge transporting compound 2 (10.0 mg), charge transporting compound 4 (10.0 mg), and toluene (4.6 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated on the first organic layer formed as described above at a rotation speed of 3,000 min ⁇ 1 and then cured by heating on a hot plate at 200 ° C. for 10 minutes to obtain a second organic layer. (30 nm) was formed.
  • the second organic layer could be formed without dissolving the first organic layer.
  • charge transporting compound 4 (10.0 mg) and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated at a rotation speed of 3,000 min ⁇ 1 and then cured by heating on a hot plate at 200 ° C. for 10 minutes to obtain a third organic layer. (30 nm) was formed.
  • the third organic layer could be formed without dissolving the second organic layer.
  • the substrate obtained above was transferred into a vacuum evaporation machine, and CBP: Ir (ppy) 3 (94: 6, 30 nm), BAlq (10 nm), Alq 3 (30 nm), LiF (on the third organic layer) 0.8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to manufacture an organic EL element.
  • Example 5 An organic EL device was produced in the same manner as in Example 4, except that the charge transporting compound 4 was changed to the charge transporting compound 6.
  • Example 6 An organic EL device was produced in the same manner as in Example 4 except that the charge transporting compound 4 was changed to the charge transporting compound 8.
  • Table 3 shows the layer structure of the organic EL elements produced in Examples 4 to 6 together with the layer structure of the organic EL elements produced in Examples 1 to 3.
  • the charge transport layers of the organic EL devices of Examples 4 to 6 satisfied the relationship of the formulas (I) and (II).
  • Example 7 ⁇ Production and Evaluation 3 of Organic EL Element> [Example 7]
  • the charge transporting compound 1 used for forming the first organic layer was changed to the charge transporting compound 7, and the charge transporting compound 7 used for forming the third organic layer was changed to the charge transporting compound 1.
  • An organic EL device was produced in the same manner except that it was changed to.
  • Example 5 Under a nitrogen atmosphere, charge transporting compound 1 (20.0 mg) and toluene (1.5 mL) were mixed to prepare an ink composition.
  • the ink composition used for the second organic layer was changed to the ink composition to form the second organic layer (60 nm), and the third organic layer was not formed.
  • an organic EL device was produced. The second organic layer could be formed without dissolving the first organic layer.
  • Table 5 shows the layer structure of the organic EL elements prepared in Example 7 and Comparative Example 5 together with the layer structure of the organic EL elements prepared in Example 3 and Comparative Example 3.
  • the charge transport layer of the organic EL device of Example 7 satisfied the relationship of the formulas (I) and (II).
  • Example 7 As shown in Table 6, in Example 7, as compared with Comparative Example 5, an element having excellent driving stability and an improved light emission lifetime was obtained.
  • Example 7 From comparison between Example 3 and Example 7, when the ratio of the unit having an aromatic amine structure and / or the unit having a carbazole structure in the charge transporting compound (A) is high, driving stability is further improved. I understand that. Furthermore, it can be seen that when the proportion of the unit having an aromatic amine structure and / or the unit having a carbazole structure in the charge transporting compound (A) is high, the effect of improving the light emission efficiency can be obtained.
  • Example 8 Under a nitrogen atmosphere, charge transporting compound 1 (10.0 mg), the ionic compound 1 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ⁇ 1 , and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a first organic A layer (30 nm) was formed.
  • charge transporting compound 1 (10.0 mg), charge transporting compound 3 (10.0 mg), and toluene (4.6 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated at a rotation speed of 3,000 min ⁇ 1 and cured by heating on a hot plate at 200 ° C. for 10 minutes. (30 nm) was formed.
  • the second organic layer could be formed without dissolving the first organic layer.
  • the charge transporting compound 3 (10.0 mg) and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition was spin-coated at a rotation speed of 3,000 min ⁇ 1 and cured by heating on a hot plate at 200 ° C. for 10 minutes to obtain a third organic layer. (30 nm) was formed.
  • the third organic layer could be formed without dissolving the second organic layer.
  • CDBP 15.0 mg
  • FIr (pic) 0.9 mg
  • Ir (ppy) 3 0.9 mg
  • (btp) 2 Ir (acac) 1.2 mg
  • Dichlorobenzene 0.5 mL
  • the ink composition was spin-coated at a rotation speed of 3,000 min ⁇ 1 and dried by heating at 80 ° C. for 5 minutes on a hot plate to form a light emitting layer (40 nm).
  • the light emitting layer could be formed without dissolving the third organic layer.
  • the glass substrate was transferred into a vacuum deposition machine, and BAlq (10 nm), Alq 3 (30 nm), LiF (0.5 nm), and Al (100 nm) were formed in this order on the light emitting layer by a vapor deposition method. Then, the sealing process was performed and the white organic EL element was produced.
  • the white organic EL element could be used as a lighting device.
  • the charge transporting layer of the white organic EL element satisfied the relationship of formula (I) and formula (II).
  • Example 6 Under a nitrogen atmosphere, charge transporting compound 3 (10.0 mg) and toluene (2.3 mL) were mixed to prepare an ink composition.
  • the ink composition used for the second organic layer was changed to the ink composition to form the second organic layer (30 nm), and the third organic layer was not formed.
  • a white organic EL device was produced.
  • the second organic layer could be formed without dissolving the first organic layer, and the light emitting layer could be formed without dissolving the second organic layer.
  • the white organic EL element could be used as a lighting device.
  • Example 8 A voltage was applied to the white organic EL elements obtained in Example 8 and Comparative Example 6, and the light emission lifetime (luminance half-life) was measured with an initial luminance of 1,000 cd / m 2 .
  • the light emission lifetime of Example 8 was 1, the light emission lifetime of Comparative Example 6 was 0.5.
  • the driving voltage at a luminance of 1,000 cd / m 2 in Example 8 was 1, it was 1.13 in Comparative Example 6.
  • the white organic EL device of Example 8 showed excellent light emission lifetime and driving voltage.
  • the organic EL device according to the embodiment of the present invention is manufactured using a wet process, and has a feature that cost reduction and area increase are easy. Furthermore, the organic EL device according to the embodiment of the present invention is manufactured using a wet process, and has a specific charge transporting layer, thereby sufficiently covering unevenness caused by the anode, and the charge transporting layer. Since the charge transfer barrier can be relaxed, the charge transport property and durability are excellent as a whole.

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Abstract

　L'invention concerne un élément électroluminescent (EL), lequel possède, dans l'ordre, un anode, une couche de transport de charge, une couche émettrice de lumière et une cathode, la couche de transport de charge étant formée au moyen d'au moins une ou d'au moins deux sortes de compositions contenant un composé transporteur de charge et un solvant. Cette couche de transport de charge contient un composé (A) transporteur de charge et un composé (B) transporteur de charge et possède, dans l'ordre à partir du côté anode, une première région, une deuxième région et une troisième région. Les proportions entre la teneur en composé (B) transporteur de charge et la teneur en composé (A) transporteur de charge dans les première et deuxième régions susmentionnées sont respectivement B1/A1 et B2/A2, et lorsque les proportions entre la teneur en composé (A) transporteur de charge et la teneur en composé (B) transporteur de charge dans les deuxième et troisième régions susmentionnées sont respectivement A2/B2 et A3/B3, alors, les relations représentées par les formules (I) et (II) sont satisfaites.
PCT/JP2015/081794 2014-11-11 2015-11-11 Élément électroluminescent organique et procédé de fabrication de celui-ci WO2016076375A1 (fr)

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Cited By (9)

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WO2018020571A1 (fr) * 2016-07-26 2018-02-01 日立化成株式会社 Matériau électronique organique
WO2018021381A1 (fr) * 2016-07-26 2018-02-01 日立化成株式会社 Matériau électronique organique
JP2018133454A (ja) * 2017-02-15 2018-08-23 富士ゼロックス株式会社 有機電界発光素子用の組成物、電荷輸送性膜、及び有機電界発光素子
WO2019082390A1 (fr) * 2017-10-27 2019-05-02 日立化成株式会社 Polymère à transport de charges et élément électronique organique
WO2019097714A1 (fr) * 2017-11-20 2019-05-23 日立化成株式会社 Procédé de fabrication d'un film mince organique, film mince organique et son utilisation
CN110352508A (zh) * 2017-03-02 2019-10-18 日立化成株式会社 有机电子材料及其利用
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WO2020217521A1 (fr) * 2019-04-26 2020-10-29 日立化成株式会社 Matériau électronique organique et procédé de production de polymère de transport de charge

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