JP6331462B2 - Method for manufacturing organic electronics element - Google Patents

Description

  Embodiments described herein relate generally to a method for manufacturing an organic electroluminescent element (also referred to as “organic EL element”), an organic EL element, a display element, a lighting device, and a display device.

  The organic EL element is attracting attention as a large-area solid-state light source application that can replace, for example, an incandescent lamp or a gas-filled lamp. 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.

  Organic EL elements are roughly classified into two types, low molecular organic EL elements and polymer organic EL elements, from the organic materials used. In the polymer organic EL element, a polymer compound is used as an organic material, and in the low molecular organic EL element, a low molecular compound is used. On the other hand, 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. Since simple film formation is possible, the wet process is expected as an indispensable method for future large-screen organic EL displays.

  For this reason, the development of materials suitable for wet processes has been underway, and for example, studies have been made to form a multilayer structure using a compound having a polymerizable group (for example, Patent Document 1 and Non-Patent Documents). 1).

JP 2006-279007 A

Kengo Hirose, Daisuke Kumaki, Nobuaki Koike, Satoshi Kuriyama, Seiichiro Ikehata, Shizushi Tokito, 53rd Joint Physics Conference on Applied Physics, 26p-ZK-4 (2006)

  An organic EL element manufactured using a wet process has a feature that cost reduction and area increase are easy. However, further improvement is desired for the characteristics of the organic EL element.

  In view of the above, an embodiment of the present invention aims to provide a method for easily manufacturing an organic EL element having excellent lifetime characteristics. Another object of the present invention is to provide an organic EL element having excellent lifetime characteristics, a display element using the same, a lighting device, and a display device.

  As a result of intensive studies, the present inventors have found that a specific combination of hole transporting compounds is effective in improving the lifetime characteristics of the organic EL device, and have completed the present invention.

  That is, an embodiment of the present invention is a method for producing an organic electroluminescent device in which an anode, an organic layer (1), and an organic layer (2) are arranged in this order, and further includes at least a light emitting layer and a cathode. Forming the organic layer (1) with a composition (1) containing a hole-transporting compound (1) having a polymerizable substituent (1) and a solvent; and the organic layer (2) ) Is formed by a composition (2) containing a hole-transporting compound (2) having a polymerizable substituent (2) and a solvent, the polymerizable substituent (1) and The present invention relates to a method for producing an organic electroluminescent device, which is different from the polymerizable substituent (2).

  The manufacturing method preferably includes a step of forming an anode, a step of forming the organic layer (1) with the composition (1) on the anode, and a step of forming the organic layer (1) on the organic layer (1). 2) including the step of forming the composition (2), the step of forming a light emitting layer, and the step of forming a cathode.

  In the production method, the composition (1) may further contain a polymerization initiator.

  In the manufacturing method, preferably, the step of forming the organic layer (1) includes a step of forming a coating film using the composition (1) and curing the coating film.

  In the manufacturing method, preferably, the organic layer (1) is a hole injection layer, and the organic layer (2) is a hole transport layer.

  In the production method, the polymerizable substituent (1) is preferably a group having a cyclic ether structure.

  In the production method, the polymerizable substituent (2) is preferably a group having a carbon-carbon multiple bond.

  In the production method, the polymerization initiator is preferably an onium salt.

  Moreover, other embodiment of this invention is related with the organic electroluminescent element manufactured by the said manufacturing method.

  In another embodiment of the present invention, the anode, the organic layer (1), and the organic layer (2) are arranged in this order, and further include at least a light-emitting layer and a cathode, and the organic layer (1) A hole transporting compound (2) containing a cured product of a hole transporting compound (1) having a polymerizable substituent (1), wherein the organic layer (2) has a polymerizable substituent (2). ), And the polymerizable substituent (1) is different from the polymerizable substituent (2).

  The organic electroluminescent element may further include a flexible substrate.

  The organic electroluminescent element may further include a resin film substrate.

  Furthermore, another embodiment of the present invention relates to a display element and an illuminating device provided with the organic electroluminescence element, and a display device provided with the illuminating device and a liquid crystal element as a display means.

  According to the embodiment of the present invention, it is possible to provide a method for easily manufacturing an organic electronic device having excellent lifetime characteristics. Moreover, according to other embodiment of this invention, the organic EL element which is excellent in a lifetime characteristic, a display element using the same, an illuminating device, and a display apparatus can be provided.

FIG. 1 is a schematic diagram illustrating an example of an organic EL element according to an embodiment of the present invention. FIG. 2 is a schematic view showing an example of an organic EL element according to an embodiment of the present invention.

An embodiment of the present invention will be described.
<Method for producing organic EL element>
An organic EL device manufacturing method according to an embodiment of the present invention includes an organic EL device in which an anode, an organic layer (1), and an organic layer (2) are arranged in this order, and further includes at least a light emitting layer and a cathode. It is a manufacturing method. The organic EL element may further have other arbitrary layers.

The organic layer (1) and the organic layer (2) and the composition used for forming them will be described.
[Organic layer (1)]
The organic layer (1) is formed of a composition (1) containing at least a hole transporting compound (1) having a polymerizable substituent (1) and a solvent. The composition (1) preferably contains a polymerization initiator from the viewpoint of improving curability. For example, the organic layer (1) is formed by using a composition (1) containing a hole transporting compound (1), a polymerization initiator, and a solvent, and then drying and / or drying the coating film. It is obtained by curing. The organic layer (1) is preferably a hole injection layer of an organic EL element.

[Organic layer (2)]
The organic layer (2) is formed of a composition (2) containing at least a hole transporting compound (2) having a polymerizable substituent (2) and a solvent. In one embodiment, composition (2) contains a polymerization initiator from the viewpoint of improving curability. In another embodiment, composition (2) does not contain a polymerization initiator from the viewpoint of preventing unnecessary reactions from occurring in adjacent layers. For example, the organic layer (2) is formed by using a composition (2) containing a hole transporting compound (2) and a solvent, and optionally a polymerization initiator, and then drying the coating film. / Or obtained by curing. The organic layer (2) is preferably a hole transport layer of the organic EL device.

  The organic layer (2) is preferably provided adjacent to the organic layer (1). That is, the coating film using the composition (2) is preferably formed on the organic layer (1). The organic layer (2) is preferably provided as a lower layer of the light emitting layer. That is, the light emitting layer is preferably formed on the organic layer (2).

[Composition]
The composition contains at least a hole transporting compound having a polymerizable substituent and a solvent, and may further contain a polymerization initiator. The composition may be commercially available or may be prepared by a method known to those skilled in the art, and is not particularly limited. In addition, the description regarding a composition here is applied with respect to a composition (1) and a composition (2).

[Hole transporting compound]
The hole transporting compound is not particularly limited as long as it has an ability to transport holes. The hole 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 description regarding the hole transporting compound here is applied to the hole transporting compound (1) and the hole transporting compound (2).

  The hole transporting compound has one or more structural units having a hole transporting property. The structural unit having a hole transporting property is not particularly limited as long as it contains an atomic group having the ability to transport holes. The structural unit having a hole transporting property includes, as an atomic group, an amine having an aromatic ring (also referred to as “aromatic amine”) structure, a carbazole structure, or a thiophene structure from the viewpoint of having a high hole transporting property. Is preferred. As the aromatic amine, triarylamine is preferable, and triphenylamine is more preferable.

  The hole 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, it is also possible to use a mixture of a low molecular compound and a high molecular compound from the viewpoint of obtaining the advantages of both.

  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 the structural unit having hole transportability. 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 structural units (1a) to (84a), which are specific examples of the structural unit having hole transportability, are listed below.
<Structural units (1a) to (84a)>

Wherein, E is, ^{independently, -R 1, -OR 2, -SR} 3, -OCOR 4, -COOR 5, -SiR 6 R 7 R 8, the following equation (1) to (3), a halogen atom And any group selected from the group consisting of groups having polymerizable substituents.

R ^{1 to} R ¹¹ each independently represent 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.
R ^{1 to} R ¹¹ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, and an aryl group. Alkylthio group, arylalkenyl group, arylalkynyl group, hydroxyl group, hydroxyalkyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imino group , An amide group (—NR—COR, —CO—NR ₂ (R is a hydrogen atom or an alkyl group)), an imide group (—N (CO) ₂ Ar, —Ar (CO) ₂ NR (R is a hydrogen atom or an alkyl group) Group, Ar is an arylene group)), carboxyl group, substituted carboxyl group, cyano group, hetero Reel group, and the like.
a, b and c represent an integer of 1 or more, preferably an integer of 1 to 4.
The group having a polymerizable substituent will be described later.

In the formula, 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.

In the formula, X and Z each independently represent a divalent linking group and are not particularly limited. For example, in the above 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 following linking group group (A ) To (C).
x represents an integer of 0 to 2.
Y represents a trivalent linking group and is not particularly limited. For example, 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.

<Linking group group (A) to (C)>

  In the formula, examples of R include the same groups as those described above for E.

In the present embodiment, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the following, examples of the halogen atom include atoms similar to these.

In the present embodiment, 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.
In the following, examples of the alkyl group include groups similar to these.

In the present embodiment, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and the heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic compound having a hetero atom. It is.
Examples of the aryl group include phenyl, biphenyl-yl, terphenyl-yl, triphenylbenzene-yl, naphthalene-yl, anthracenyl, tetracene-yl, fluorenyl, phenanthrene-yl and the like.
Examples of the heteroaryl group include pyridyl-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, benzothiophene-yl and the like.
In the following, examples of the aryl group and heteroaryl group include groups similar to these.

In the present embodiment, an arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and a heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic compound having a hetero atom. It is.
Examples of the arylene group include phenylene, biphenyl-diyl, terphenyl-diyl, triphenylbenzene-diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, and the like.
Examples of the heteroarylene group 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.
In the following, examples of the arylene group and the heteroarylene group include the same groups.

  The structural units (a1) to (a6), which are preferred specific examples of the structural unit having hole transportability, are listed below.

<Structural units (a1) to (a6)>

  In the formula, the phenyl group, phenylene group, and 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 one embodiment of the hole transporting compound has, for example, one of the structural units (1a) to (84a). In this case, E is bonded to the bond.

  Hereinafter, the polymer compound which is an embodiment of the hole transporting compound will be described. In addition, the description regarding a high molecular compound (for example, description of group which has a substituent which can superpose | polymerize, an illustration, etc.) is applied also to a low molecular compound in the range which does not produce contradiction.

  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 high molecular compound having a branched chain means that the high molecular compound has a branched portion on the polymer or oligomer chain. 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, and the structural units (5b) to (8b) correspond to structural units having a carbazole structure.

<Structural units (1b) to (11b)>

In the formula, 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 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, a group in which one hydrogen atom is further removed from a group having one or more hydrogen atoms in the above E (excluding a group having a polymerizable substituent), or the 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 terminal of the polymer compound is not particularly limited. For example, a structural unit represented by any of the above (1a) to (84a), or a structural unit having an aromatic hydrocarbon structure or an aromatic compound structure can be given. As a 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.

<Structural unit (1c)>

  Ar represents an aryl group or heteroaryl 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.

[Polymerizable substituent]
The polymerizable substituent (also referred to as “polymerizable substituent”) refers to a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction. By the polymerization reaction, a cured product of the polymer compound is obtained, the solubility of the polymer compound in the solvent is changed, and a laminated structure can be easily formed.

  The position at which 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.

  As the polymerizable substituent, a group having a carbon-carbon multiple bond; a group having a cyclic structure; a group having an aromatic heterocyclic structure; a group containing a siloxane derivative; an ester bond or an amide bond can be formed. And combinations of such groups.

  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. Groups, methacryloyloxy groups, methacryloylamino groups, vinyloxy groups, vinylamino groups, styryl groups, etc .; alkenyl groups such as allyl groups, butenyl groups, vinyl groups (excluding those mentioned above); alkynyl groups such as ethynyl groups Group and the like.

  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. , Cyclopropyl group, cyclobutyl group, cardene group (1,2-dihydrobenzocyclobutene group), epoxy group (oxiranyl group), oxetane group (oxetanyl group), diketene group, episulfide group, α-lactone group, β -Lactone group, (alpha) -lactam group, (beta) -lactam group, etc. are mentioned.

  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.

  From the viewpoint of excellent curability, the number of polymerizable substituents per molecule of the polymer compound is preferably 2 or more, and more preferably 3 or more. The number of polymerizable substituents is not particularly limited, but 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”. From the viewpoint of increasing the degree of freedom of the polymerizable substituent and facilitating the polymerization reaction, the group having a polymerizable substituent has an alkylene moiety, and the polymerizable substituent is bonded to the alkyl moiety. Preferably it is. Examples of the alkylene moiety include linear alkyl moieties such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and oxylene. The alkyl moiety preferably has 1 to 8 carbon atoms.

  From the viewpoint of improving the affinity with a hydrophilic electrode such as ITO, it is preferable that the group having a polymerizable substituent has a hydrophilic site, and the polymerizable substituent is bonded to the hydrophilic site. . Examples of 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 hydrophilic part preferably has 1 to 8 carbon atoms.

  Further, from the viewpoint of facilitating the preparation of the polymer compound, 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.

As specific examples of the group having a polymerizable substituent, substituent groups (A) to (N) are shown below.
<Substituent groups (A) to (N)>

  The polymer compound preferably has a polymerizable substituent at the end of the molecular chain. In this case, 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 a “group having a polymerizable substituent”.

  The polymer compound may be a homopolymer having one type of structural unit or a copolymer having two or more types of structural units. When the polymer compound is a copolymer, the copolymer may be an alternating, random, block, or graft copolymer, or a copolymer having an intermediate structure thereof, for example, a block property. Random copolymers may also be used.

  There is no restriction | limiting in particular in the number average molecular weight of a high molecular compound, It can adjust suitably in consideration of the solubility to a solvent, film forming property, etc. 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 hole 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).

  There is no restriction | limiting in particular in the weight average molecular weight of a high molecular compound, It can adjust suitably in consideration of the solubility to a solvent, film forming property, etc. The weight average molecular weight 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 hole 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.

  When the polymer compound has any one of the structural units (1a) to (84a), the ratio of the total number of the structural units (1a) to (84a) to the total number of structural units in the polymer compound is sufficient for hole transport. From the viewpoint of obtaining properties, it is preferably 10% or more, more preferably 20% or more, and still more preferably 30% or more. Further, the ratio of the total number of the structural units (1a) to (84a) can be set to 100% from the viewpoint of obtaining high hole injection property and hole transport property in one embodiment. In other embodiments, from the viewpoint of enhancing durability while imparting hole transportability, it is preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less.

  The “ratio of structural units” can be determined from the charged amount ratio (molar ratio) of monomers corresponding to each structural unit used for synthesizing the polymer compound.

  When the polymer compound has any one of the structural units (1b) to (11b), the ratio of the total number of the 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 the 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 satisfactorily synthesizing the polymer compound.

  When the polymer compound has the structural unit (1c), 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 hole transportability.

  The ratio of polymerizable substituents to the total number of structural units in the polymer compound is preferably 0.1% or more, more preferably 1% or more, and more preferably 3% or more from the viewpoint of efficiently curing the polymer compound. Further preferred. Further, 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 hole 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 polymer compound can be produced by various synthetic methods known to those skilled in the art, and is not particularly limited. For example, each monomer used for the synthesis of a polymer compound has an aromatic ring, and when a polymer compound is produced by coupling monomers having an aromatic ring, T. Yamamoto et al. Bull. Chem. Soc. Jap., 51, 7, 2091 (1978); M. Zembayashi et al., Tetrahedron. Lett., 47, 4089 (1977); Suzuki (A. Suzuki) Synthetic Communications, Vol. 11, No. 7, 513 (1981); SL Buchwald, JF Hartwig et al., Tetrahedron Lett., 21, 3609 (1995); T. Migita, The methods described in M. Kosugi, JK Stille et al., Angew. Chem. Int. Ed. Engl., 25, 508 (1986), etc. can be used. The method described in Suzuki causes a Pd-catalyzed cross-coupling reaction (usually called the “Suzuki reaction”) between an aromatic boronic acid derivative and an aromatic halide. . The Suzuki reaction is preferable in that a polymer compound can be easily produced by using desired aromatic rings in a bonding reaction.

In the Suzuki reaction, a Pd (0) compound or a Pd (II) compound is mainly used as a Pd catalyst. In recent years, Ni compounds are used, and both can be used. When a Pd compound is 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. Further, it is also possible to use a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like and mixing the precursor with a phosphine ligand in the system. it can. As the phosphine ligand in this case, known phosphine compounds such as P (t-Bu) ₃ (tris (t-butyl) phosphine), tributylphosphine, P (c-hex) ₃ (tricyclohexylphosphine), and commercially available The phosphine compound or the like can be used.

What is necessary is just to adjust the density | concentration of Pd catalyst to the arbitrary ranges, for example about 0.01-5 mol% with respect to the monomer made to react. As the reaction solvent, an organic solvent or a mixed solvent of water and an organic solvent is mainly used. As the organic solvent, dimethoxyethane, toluene, anisole, tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide and the like can be used. Further, as a base, alkali metal carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ ; alkali metal hydroxides such as NaOH and KOH; triethylamine, K ₃ PO ₄ , TMAH (tetramethylammonium hydroxide), A water-soluble organic base such as TEAH (tetraethylammonium hydroxide) can also be used. It is also possible to promote the reaction by adding a phase transfer catalyst. Typical 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. .

  As each monomer, a monomer corresponding to the structural unit exemplified above can be used. As 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 (a target polymer capable of polymerization). And the like, and a method of 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. 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.

[Hole transporting compound (1)]
The hole transporting compound (1) has a polymerizable substituent (1). From the viewpoint of excellent reactivity, the polymerizable substituent (1) is preferably a group having a cyclic structure, more preferably a group having a cyclic ether structure, and any one selected from the group consisting of an epoxy group and an oxetane group. One or more are more preferable, and an oxetane group is particularly preferable. The hole transporting compound (1) may have a polymerizable substituent other than the polymerizable substituent (1) as long as the effects of the present invention are not impaired.

Examples of monomers in the case of producing the hole transporting compound (1) by the Suzuki reaction are shown below. The synthesis method and monomer of the hole transporting compound (1) are not limited thereto.
[Example of monomer used for synthesis of hole transporting compound (1)]

  In the formula, 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 polymer compound which is the hole transporting compound (1) is mainly composed of units having an aromatic amine structure and / or units having a carbazole structure from the viewpoint of obtaining high hole injecting property and hole transporting property. It is preferable that it is a compound which has as. 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 40% or more. Preferably, 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%.

[Hole transporting compound (2)]
The hole transporting compound (2) has a polymerizable substituent (2). The polymerizable substituent (2) is a group different from the polymerizable substituent (1).

  The polymerizable substituent (2) is preferably a group having a carbon-carbon multiple bond, more preferably a group having a carbon-carbon double bond, from the viewpoint of obtaining a longer-life organic EL device, an acryloyl group, Any one or more selected from the group consisting of acryloyloxy group, methacryloyl group, methacryloyloxy group, vinyloxy group, styryl group, and vinyl group is preferable. The hole transporting compound (2) may have a polymerizable substituent other than the polymerizable substituent (2) as long as the effects of the present invention are not impaired.

  As a monomer in the case of producing the polymer compound which is the hole transporting compound (2) by the Suzuki reaction, the monomers exemplified in the hole transporting compound (1) and the monomers shown below can be mentioned. The synthesis method and monomer of the hole transporting compound (2) are not limited thereto.

[Example of monomer used for synthesis of hole transporting compound (2)]

  The polymer compound which is the hole transporting compound (2) 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. From the viewpoint of developing durability, a compound further having a structural unit other than a unit having an aromatic amine structure and a unit having a carbazole structure is preferable. 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, 15% or more is more preferable, 95% or less is preferable, 90% or less is more preferable, and 85% or less is still more preferable. The ratio of the total number of structural units other than the unit having an aromatic amine structure and the unit having a carbazole structure to the total number of structural units in the polymer compound (excluding the terminal structural unit) is preferably 5% or more, 10% or more is more preferable, 15% or more is more preferable, 95% or less is preferable, 90% or less is more preferable, and 85% or less is still more preferable.

[solvent]
Examples of the solvent contained in the composition include water and an organic solvent. Examples of the 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, and 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, and lactate n Aliphatic esters such as butyl; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like. Aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers are preferred.

[Polymerization initiator]
The polymerization initiator may be a commercially available one as long as it is a compound that can act as a polymerization initiator for the hole transporting compound (1) and the hole transporting compound (2). What was prepared may be sufficient and there is no restriction | limiting in particular.

  As the polymerization initiator, both inorganic and organic substances can be used, and examples thereof include compounds described in JP2003-031365A, JP2006-233162A, and the like. Specifically, a compound having a perfluoroaryl group, a perfluoroalkyl group or the like is preferable. Moreover, the onium salt containing the 1 type selected from the following cations and the 1 type selected from the following anions can also be used preferably.

[Cation]
Examples of the cation 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. , Chromenilium ion, xanthylium ion, iodonium ion, sulfonium ion, phosphonium ion, tropylium ion, cation with transition metal, etc., carbenium ion, ammonium ion, anilinium ion, aminium ion, iodonium ion , Sulfonium ions, and tropylium ions are preferred. From the viewpoint of achieving both curability and storage stability of the composition, ammonium ions, anilinium ions, iodonium ions, and sulfonium ions are more preferable.

[Anion]
Examples of the anion include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ and 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 PF _4] ^- a fluorinated alkyl fluorophosphate ions such ^{_{as; (CF 3 SO 2) 3}} C -, (CF 3 SO 2) 2 N - etc. fluoroalkane methide of imide ion such; BF ₄ ^{- _{, B (C 6 F 5)}} 4 -, B (C 6 H 4 CF 3) 4 - borate ions such _{^{as; SbF 6 -, SbF 5 OH}} - fluoro antimonate ion such _as; ^AsF 6 -, ^AsF ₅ OH ^- fluoroarsenate periodate ions such as; AlCl ₄ ^-, BiF ₆ ^-, and the like. From the viewpoint of curability of the composition when used in combination with the aforementioned _{^{cations, 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 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 ) ₂ N ^- fluoroalkanes methide such as, imide ion _{^{such; BF 4 -, B (C}} 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such as; SbF ₆ ^- , _SbF 5 OH ^- such as full of B is preferably antimonate ions, among others borate ions are particularly preferred.

  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.

[Composition (1)]
The composition (1) contains at least the hole transporting compound (1) and a solvent, and may further contain a polymerization initiator. The composition (1) is preferably used as a material for a hole injection layer for forming a hole injection layer.

  The content of the hole-transporting compound (1) in the composition (1) is preferably 0.01% by mass or more based on the total mass of the composition from the viewpoint of adjusting the viscosity and film-forming property 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 and precipitation, 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.

  When the composition (1) contains a polymerization initiator, the content of the polymerization initiator is 0.1% by mass with respect to the total mass of the hole transporting compound (1) from the viewpoint of causing sufficient polymerization. The above is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is more preferable. In addition, the content of the polymerization initiator is preferably 50% by mass or less, more preferably 45% by mass or less, with respect to the total mass of the hole transporting compound (1), from the viewpoint of film formability and heat resistance. A mass% or less is more preferable.

[Composition (2)]
The composition (2) contains at least the hole transporting compound (2) and a solvent, and may further contain a polymerization initiator. The composition (2) is preferably used as a material for a hole transport layer for forming a hole transport layer.

  In one embodiment, the composition (2) preferably contains a polymerization initiator from the viewpoint of facilitating curing of the hole transporting compound (2). On the other hand, in another embodiment, the composition (2) preferably does not contain a polymerization initiator from the viewpoint of preventing the polymerization initiator and its decomposition product from affecting adjacent layers (particularly the upper layer). For the composition (2), a polymerization initiator can be appropriately used in consideration of the curability of the hole transporting compound (2), the influence on the adjacent layer, etc., and the type thereof can be appropriately selected. Can do.

  The content of the hole transporting compound (2) in the composition (2) is preferably 0.01% by mass or more based on the total mass of the composition from the viewpoint of adjusting the viscosity and film-forming property 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 and precipitation, 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.

  When the composition (2) contains a polymerization initiator, the content of the polymerization initiator is 0.1% by mass with respect to the total mass of the hole transporting compound (2) from the viewpoint of causing sufficient polymerization. The above is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is more preferable. Further, the content of the polymerization initiator is preferably 50% by mass or less, more preferably 45% by mass or less, with respect to the total mass of the hole transporting compound (2), from the viewpoint of film formability and heat resistance. A mass% or less is more preferable.

[Composition of composition (1) and composition (2)]
The composition (1) and the composition (2) can be used as a composition set in which both are combined. By using the composition set, the organic layer (1) and the organic layer (2), preferably the hole injection layer and the hole transport layer, can be easily formed by a coating process.

[Method for forming organic layer]
Examples of the method for forming an organic layer using the composition 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. There are known printing methods such as plate printing method; plateless printing method such as inkjet method. Further, after film formation, 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.

  For light irradiation, 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 for heating. 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 | substrate, Preferably it is 300 degrees C or less, More preferably, it is 250 degrees C or less, More preferably, it is 200 degrees C or less. Further, from the viewpoint of increasing the polymerization rate, it is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. From the viewpoint of increasing productivity, the time is preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less. Further, from 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 thickness of the organic layer (1) is preferably 0.1 nm or more, more preferably 1 nm or more, and more preferably 5 nm or more from the viewpoint of covering the unevenness caused by the anode and suppressing a short circuit. Further preferred. Further, from the viewpoint of reducing the electric resistance of the organic layer, it is preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.

  From the viewpoint of improving the efficiency of hole transport, the thickness of the organic layer (2) is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. Further, from the viewpoint of reducing the electric resistance of the organic layer, it is preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.

<Organic EL device>
The organic EL element which is embodiment of this invention has an anode, an organic layer (1), and an organic layer (2) arrange | positioned in this order, and also has a light emitting layer and a cathode at least. In an organic EL element, an anode, an organic layer (1), an organic layer (2), a light emitting layer, and a cathode are usually arranged in this order.

  The organic EL element which is embodiment of this invention can be obtained with the manufacturing method of the said embodiment. Alternatively, in the organic EL device according to an embodiment of the present invention, the organic layer (1) includes a cured product of the hole transporting compound (1) having a polymerizable substituent (1), and the organic layer ( 2) includes a cured product of the hole transporting compound (2) having a polymerizable substituent (2), and the polymerizable substituent of the hole transporting compound (2) is the hole transporting The polymerizable compound (1) contains at least one polymerizable substituent different from the polymerizable substituent. The organic layer (1) may contain an unreacted polymerizable substituent (1). That is, in the organic layer (1), all of the hole transporting compound (1) may not be completely cured. The same applies to the organic layer (2).

  The organic EL element may have an electron injection layer, an electron transport layer, etc. as other layers. The organic EL element usually has a substrate. Examples of organic EL elements are shown in FIGS. Hereinafter, each layer will be described.

[Light emitting layer]
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. Examples of the polymer compound using fluorescence emission include polyfluorene, polyphenylene, polyphenylene vinylene (PPV), polyvinyl carbazole (PVK), fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, derivatives thereof, And mixtures thereof can be suitably used.

  On the other hand, in recent years, phosphorescent organic EL elements have been actively developed in order to increase the efficiency of organic EL elements. In 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 to 100% in principle. In a phosphorescent organic EL device, phosphorescence is extracted 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 (MA Baldo et al., Nature, vol. 395). 151 (1998); MA Baldo et al., Applied Physics Letters, vol. 75, p. 4 (1999); MA Baldo et al., Nature, vol. 403, p. 750 (2000)).

Also in the organic EL element which is the embodiment of the present invention, a phosphorescent material can be used for the light emitting layer from the viewpoint of high efficiency. As the phosphorescent material, a metal complex containing a central metal such as Ir or Pt can be preferably used. Specifically, as an Ir complex, for example, FIr (pic) [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate] that emits blue light and green light are emitted. Ir (ppy) ₃ [Factris (2-phenylpyridine) iridium] (see MA Baldo et al., Nature, vol. 403, p. 750 (2000)), or emits red light (btp) ₂ Ir (acac ) {Bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] iridium (acetyl-acetonate)} (Adachi et al., Appl. Phys. Lett., 78 no. 11, 2001, 1622), Ir (piq) ₃ [tris (1-phenylisoquinoline) iridium] and the like. Examples of the Pt complex include 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-forminplatinum (PtOEP) that emits red light. As 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.

  In the case where the light emitting layer includes a phosphorescent material, 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.

  Examples of low molecular weight compounds include α-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 can be used. As the 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.
When forming by the apply | 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. Examples of 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.

[cathode]
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]
As the anode, a metal (eg, Au) or other material having metal conductivity can be used. Examples of the other material include an oxide (for example, ITO: indium oxide / tin oxide) and a conductive polymer (for example, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[Electron transport layer, electron injection layer]
Examples of 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. , Thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives (2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), aluminum complexes (for example, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ )) and the like. Furthermore, in the oxadiazole derivative, 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 be used.

[substrate]
As 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. Further, a transparent substrate is preferable, and glass, quartz, a light transmissive resin film, and the like are preferably used. When a resin film is used, flexibility can be imparted to the organic EL element (that is, a flexible substrate), which is particularly preferable.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. (TAC), the film which consists of cellulose acetate propionate (CAP) etc. is mentioned.

  Moreover, when using a resin film, in order to suppress permeation | transmission of water vapor | steam, oxygen, etc., you may laminate | stack and use inorganic substances, such as a silicon oxide and a silicon nitride, on a resin film.

[Sealing]
The organic EL element may be sealed in order to reduce the influence of outside air and extend the life. As 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.

[Luminescent color]
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 fixtures such as home lighting, interior lighting, watches, and liquid crystal backlights.

  As a method of forming a white light emitting element, since it is currently difficult to show white light emission with a single material, 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 a combination of three emission maximum wavelengths of blue, green and red, a complementary color relationship such as blue and yellow, yellow green and orange is used. The thing containing two light emission maximum wavelengths is mentioned. The emission color can be controlled by adjusting the type and amount of the phosphorescent material.

<Display element, lighting device, display device>
A display element according to an embodiment of the present invention includes the organic EL element described above.
For example, 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 simple in structure but has a limit in the number of vertical pixels and is used for displaying characters. The latter is used for high-quality displays because the drive voltage is low and the current is small, and a bright high-definition image is obtained.

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element as stated above. Furthermore, 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 illumination device may be used as a backlight (white light emitting 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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of Pd catalyst>
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature, anisole (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed in a sample tube, anisole (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to form a catalyst. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes.

<Synthesis of hole transporting compound 1>
To a three-necked round bottom flask, add the following monomer A (5.0 mmol), the following monomer B1 (2.0 mmol), the following monomer C1 (3.0 mmol), the following monomer C2 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. After stirring for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes. The mixture was heated to reflux for 2 hours. All the operations so far were performed under a nitrogen stream.

  After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was collected by suction filtration, dissolved in toluene, and a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg with respect to 100 mg of the precipitate) was added. Stir overnight. After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The obtained precipitate was vacuum-dried to obtain a hole transporting compound 1. The molecular weight was measured by GPC (polystyrene conversion) using THF as an eluent. The number average molecular weight of the obtained hole transporting compound 1 was 7,800, and the weight average molecular weight was 31,000. The hole 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 It has a structural unit (1c) having an oxetane group (derived from the monomer C2), 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

<Synthesis of hole transporting compound 2>
To the three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer C1 (3.0 mmol), the following monomer C3 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 2 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 2 was 12,900, and the weight average molecular weight was 42,600. The hole 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), and It has a structural unit (1c) having a vinyl group (derived from the monomer C3), 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%.

<Synthesis of hole transporting compound 3>
To a three-necked round bottom flask, the monomer A (6.0 mmol), the following monomer B2 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C2 (1.0 mmol), and anisole (20 mL) were added, Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 3 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 3 was 10,300, and the weight average molecular weight was 20,400. The hole 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 It has a structural unit (1c) having an oxetane group (derived from the monomer C2), and the proportion of each structural unit was 50.0%, 16.7%, 25.0%, and 8.3%. . 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 75.0%.

<Synthesis of hole transporting compound 4>
To a three-necked round bottom flask, add the monomer A (6.0 mmol), the monomer B2 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C3 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 4 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 4 was 12,200, and the weight average molecular weight was 35,600. The hole 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), and It has a structural unit (1c) having a vinyl group (derived from monomer C3), and the proportion of each structural unit was 50.0%, 16.7%, 25.0%, and 8.3%. . 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 75.0%.

<Synthesis of hole transporting compound 5>
To the three-necked round bottom flask, add the monomer A (5.0 mmol), the following monomer B3 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C2 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 5 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 5 was 12,700, and the weight average molecular weight was 70,300. The hole 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 It has a structural unit (1c) having an oxetane group (derived from the monomer C2), 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%.

<Synthesis of hole transporting compound 6>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C3 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 6 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 6 was 12,100, and the weight average molecular weight was 43,500. The hole 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), and It has a structural unit (1c) having a vinyl group (derived from the monomer C3), 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%.

<Synthesis of hole transporting compound 7>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the following monomer B4 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C2 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 7 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 7 was 10,900, and the weight average molecular weight was 70,000. The hole 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 It has a structural unit (1c) having an oxetane group (derived from the monomer C2), 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%.

<Synthesis of hole transporting compound 8>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B4 (2.0 mmol), the monomer C1 (3.0 mmol), the monomer C3 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the hole transporting compound 8 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 8 was 12,100, and the weight average molecular weight was 76,500. The hole 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), and It has a structural unit (1c) having a vinyl group (derived from the monomer C3), 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%.

<Synthesis of precursor>
To the three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer C1 (3.0 mmol), the following monomer C4 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the precursor was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained precursor was 16,200, and the weight average molecular weight was 65,800.

<Synthesis of hole transporting compound 9>
The precursor (1.0 g), the following compound 1 (0.5 g), toluene (20 mL), and concentrated sulfuric acid (1 mL) were added to a three-necked round bottom flask and reacted for 8 hours under heating to reflux. After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The obtained precipitate was dissolved in toluene and reprecipitated from methanol to obtain a hole transporting compound 9 having a methacryloyloxy group. The number average molecular weight of the obtained hole transporting compound 9 was 16,500, and the weight average molecular weight was 66,000. The hole transporting compound 9 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 It has a structural unit (1c) having a methacryloyloxy group (derived from the monomer C4), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%. It was. 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%.

<Synthesis of hole transporting compound 10>
To the three-necked round bottom flask was added the precursor (1.0 g), the following compound 2 (0.5 g), potassium carbonate (1.0 g), a small amount of potassium iodide, and N, N-dimethylformamide (20 mL). It was. The mixture was heated and stirred at 80 ° C. for 5 hours and further at 100 ° C. for 3 hours. After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The obtained precipitate was dissolved in toluene and reprecipitated from methanol to obtain a hole transporting compound 10 having a vinyloxy group. The number average molecular weight of the obtained hole transporting compound 10 was 16,700, and the weight average molecular weight was 65,900. The hole transporting compound 10 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 It has structural units (1c) having vinyloxy groups (derived from monomer C4), and the proportions of the respective structural units were 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%.

<Production and Evaluation of Organic EL Device>
[Example 1]
In a nitrogen atmosphere, the hole transporting compound 1 (10.0 mg), the following polymerization initiator 1 (0.5 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 on a glass substrate patterned with a width of 1.6 mm of ITO, and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a hole injection layer (30 nm) was formed.

Next, the hole transporting compound 2 (20 mg) and toluene (2.3 mL) were mixed to prepare an ink composition. The ink composition was spin-coated on the hole injection layer at a rotation speed of 3,000 min ⁻¹ and then cured by heating at 200 ° C. for 10 minutes on a hot plate to form a hole transport layer (40 nm). . The hole transport layer could be formed without dissolving the hole injection layer.

The glass substrate was transferred into a vacuum evaporator, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), Alq ₃ (30 nm), LiF (0.8 nm), And Al (100 nm) was formed into a film by the vapor deposition method in this order. Then, the sealing process was performed and the organic EL element was produced.

[Example 2]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 4 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Example 3]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 6 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Example 4]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 8 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Example 5]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 9 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Example 6]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 10 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Example 7]
In the step of forming the hole transport layer in the organic EL device of Example 1, the ink composition was formed from the hole transport compound 2 (20 mg), the following polymerization initiator 2 (1.0 mg), and toluene (2.3 mL). An organic EL device was produced in the same manner except that the ink composition was changed.

[Example 8]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 4 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Example 9]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 6 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Example 10]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 8 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Example 11]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 9 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Example 12]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 10 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Example 13]
In the step of forming the hole injection layer in the organic EL device of Example 3, the ink composition was prepared from the hole transporting compound 1 (10 mg), the polymerization initiator 2 (0.5 mg), and toluene (2.3 mL). An organic EL device was produced in the same manner except that the ink composition was changed.

[Example 14]
In the step of forming the hole injection layer in the organic EL device of Example 9, the ink composition was prepared from the hole transporting compound 1 (20 mg), the polymerization initiator 2 (1.0 mg), and toluene (2.3 mL). An organic EL device was produced in the same manner except that the ink composition was changed.

[Comparative Example 1]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 1 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Comparative Example 2]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 3 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Comparative Example 3]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 5 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Comparative Example 4]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 7 in the step of forming the hole transporting layer in the organic EL device of Example 1.

[Comparative Example 5]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 1 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Comparative Example 6]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 3 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Comparative Example 7]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 5 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Comparative Example 8]
An organic EL device was produced in the same manner except that the hole transporting compound 2 was changed to the hole transporting compound 7 in the step of forming the hole transporting layer in the organic EL device of Example 7.

[Comparative Example 9]
An organic EL device was produced in the same manner except that the hole transporting compound 6 was changed to the hole transporting compound 1 in the step of forming the hole transporting layer in the organic EL device of Example 13.

[Comparative Example 10]
An organic EL device was produced in the same manner except that the hole transporting compound 6 was changed to the hole transporting compound 1 in the step of forming the hole transporting layer in the organic EL device of Example 14.

  In Table 1, the structure of the positive hole injection layer of the organic EL element produced in Examples 1-14 and Comparative Examples 1-10 and a positive hole transport layer is shown collectively.

When voltage was applied to the organic EL elements obtained in Examples 1 to 14 and Comparative Examples 1 to 10, green light emission was confirmed. For each element, the light emission efficiency at a light emission luminance of 1,000 cd / m ² and the light emission lifetime (luminance half-time) at an initial luminance of 3,000 cd / m ² were measured. The measurement results are shown in Table 2. For measurement of luminance, “BM-7” manufactured by Topcon Corporation was used.

  As shown in Table 2, in Examples 1 to 14, long-life organic EL elements having high luminous efficiency and excellent driving stability were obtained. From Examples 1 to 14, it can be seen that, in the hole transporting compounds having various structures, the effect of improving the lifetime was obtained regardless of the presence and type of the polymerization initiator.

<Production and Evaluation of White Organic EL Element (Lighting Device)>
[Example 15]
In a nitrogen atmosphere, the hole transporting compound 1 (10.0 mg), the polymerization initiator 1 (0.5 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 on a glass substrate patterned with a width of 1.6 mm of ITO, and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a hole injection layer (30 nm) was formed.

Next, the hole transporting compound 6 (20 mg) and toluene (2.3 mL) were mixed to prepare an ink composition. The ink composition was spin-coated on the hole injection layer at a rotation speed of 3,000 min ⁻¹ and then cured by heating at 200 ° C. for 10 minutes on a hot plate to form a hole transport layer (40 nm). . The hole transport layer could be formed without dissolving the hole injection layer.

Further, under nitrogen atmosphere, CDBP (15 mg), FIr (pic) (0.9 mg), Ir (ppy) ₃ (0.9 mg), (btp) ₂ Ir (acac) (1.2 mg), and dichlorobenzene (0.5 mL) was mixed to prepare an ink composition. The ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ , heated at 80 ° C. for 5 minutes and dried to form a light emitting layer (40 nm). The light emitting layer could be formed without dissolving the hole transport 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.

[Comparative Example 11]
A white organic EL device was produced in the same manner except that the hole transporting compound 6 was changed to the hole transporting compound 5 in the step of forming the hole transporting layer in the white organic EL device of Example 15.

By applying a voltage to the white organic EL device obtained in Example 15 and Comparative Example 11, measuring the emission lifetime (luminance half-life) in the voltage and the initial luminance 1,000 cd / ^{m 2} in luminance 1,000 cd / ^{m 2} did. Assuming that the voltage of Comparative Example 11 was 1.0, the voltage of Example 15 was 0.93. Further, when the light emission life of Comparative Example 11 was 1.0, the light emission life of Example 15 was 10. The white organic EL element of Example 15 had excellent driving voltage and light emission lifetime.

  The effects of the embodiment of the present invention have been shown using the above examples. In addition to the combination of hole transporting compounds used in the examples, a combination selected from the above-described hole transporting compounds (low molecular weight compounds and high molecular weight compounds) is used, and an organic EL device having a long life is used. It is possible to obtain.

  The manufacturing method which is an embodiment of the present invention is a method using two specific types of hole transporting compounds, whereby the organic layer can be easily multilayered by a wet process, and the life characteristics can be improved. An excellent organic EL element can be obtained.

1 Anode 2 Organic layer (1) (Hole injection layer)
3 Organic layer (2) (Hole transport layer)
4 Light emitting layer 5 Cathode 6 Substrate 7 Electron transport layer 8 Electron injection layer

Claims (15)

An anode, an organic layer (1), and an organic layer (2) are arranged in this order, and further a method for producing an organic electroluminescent device having at least a light emitting layer and a cathode,
Forming the organic layer (1) with a composition (1) containing a hole-transporting compound (1) having a polymerizable substituent (1) and a solvent; and the organic layer (2) A hole transporting compound (2) having a polymerizable substituent (2) and a composition (2) containing a solvent,
The polymerizable substituent and (1) the polymerizable substituent (2) and Ri is Do different,
The polymerizable substituent (1) is a group having a cyclic ether structure;
The polymerizable substituent (2), carbon - Ru Oh a group having a carbon multiple bond, a method of manufacturing an organic electroluminescent element. Forming an anode;
Forming the organic layer (1) on the anode with the composition (1);
Forming the organic layer (2) on the organic layer (1) with the composition (2);
Forming a light emitting layer; and
The manufacturing method of the organic electroluminescent element of Claim 1 including the process of forming a cathode. The manufacturing method of the organic electroluminescent element of Claim 1 or 2 in which the said composition (1) further contains a polymerization initiator. The process of forming the said organic layer (1) forms a coating film using the said composition (1), and includes the process of hardening the said coating film. Manufacturing method of organic electroluminescent element. The manufacturing method of the organic electroluminescent element as described in any one of Claims 1-4 whose said organic layer (1) is a positive hole injection layer, and whose said organic layer (2) is a positive hole transport layer. Groups having pre Kiwa like ether structure, is any one or more selected from the group consisting of an epoxy group and oxetane group, production of the organic electroluminescent element according to any one of claims 1 to 5 Method. Before Kisumi element - groups having carbon multiple bonds, acryloyl group, acryloyloxy group, is a methacryloyl group, methacryloyloxy group, vinyloxy group, styryl group, and any one or more selected from the group consisting of vinyl groups, The manufacturing method of the organic electroluminescent element as described in any one of Claims 1-6. The polymerization initiator includes an onium salt, a method of manufacturing an organic electroluminescent element according to any one of claims 3-7. The organic electroluminescent element manufactured by the manufacturing method as described in any one of Claims 1-8. The anode, the organic layer (1), and the organic layer (2) are arranged in this order, and further have at least a light emitting layer and a cathode,
The organic layer (1) contains a cured product of a hole transporting compound (1) having a polymerizable substituent (1),
The organic layer (2) contains a cured product of a hole transporting compound (2) having a polymerizable substituent (2),
The polymerizable substituent and (1) the polymerizable substituent (2) and Ri is Do different,
The polymerizable substituent (1) is a group having a cyclic ether structure;
The polymerizable substituent (2), carbon - Oh Ru a group having a carbon multiple bond, an organic electroluminescence element. The organic electroluminescent element according to claim 9 or 10, further comprising a flexible substrate. The organic electroluminescent element according to claim 9 or 10, further comprising a resin film substrate. The display element provided with the organic electroluminescent element as described in any one of Claims 9-12. The illuminating device provided with the organic electroluminescent element as described in any one of Claims 9-12.   A display device comprising the illumination device according to claim 14 and a liquid crystal element as display means.

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