JP2016115756A - Organic electronics material and organic electronics element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronics material suitable to a wet processing capable of improving life characteristics of an organic electronics element.SOLUTION: The organic electronics material contains a charge transport polymer or oligomer which has, at least at one end thereof, a fused polycyclic aromatic hydrocarbon part having three or more benzene rings.SELECTED DRAWING: None

Description

  Embodiments described herein relate generally to an organic electronics material, an ink composition, an organic layer, an organic electronics element, an organic electroluminescence element (also referred to as “organic EL element”), a display element, a lighting device, and a display device.

  Organic EL devices are attracting attention as large-area solid-state light source applications as alternatives to, for example, incandescent lamps and gas-filled lamps. It is also attracting attention as the most powerful self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.

  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 (see, for example, Patent Document 1 and Non-Patent Document 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, regarding the characteristics of the organic EL element, further improvement is desired in the organic EL element including an organic layer manufactured by using a wet process.

  In view of the above, an embodiment of the present invention aims to provide an organic electronics material suitable for a wet process and suitable for improving the lifetime characteristics of an organic electronics element. Another object of the present invention is to provide an ink composition and an organic layer suitable for improving the life characteristics of an organic electronic device. Still another object of the present invention is to provide an organic electronics element, an organic EL element, a display element, a lighting device, and a display device that have excellent lifetime characteristics.

  As a result of intensive studies, the present inventors have found an organic electronic material suitable for a wet process and suitable for improving the life characteristics of an organic EL element, and has completed the present invention.

  That is, an embodiment of the present invention relates to an organic electronic material containing a charge transporting polymer or oligomer having a condensed polycyclic aromatic hydrocarbon moiety having three or more benzene rings at at least one terminal.

  In one embodiment, the charge transporting polymer or oligomer has 3 or more termini. Preferably, the charge transporting polymer or oligomer has the condensed polycyclic aromatic hydrocarbon moiety at 25% or more terminals based on the total number of terminals.

  In one embodiment, the condensed polycyclic aromatic hydrocarbon moiety is an anthracene moiety, a tetracene moiety, a pentacene moiety, a phenanthrene moiety, a chrysene moiety, a triphenylene moiety, a tetraphen moiety, a pyrene moiety, a picene moiety, a pentaphen moiety, or a perylene moiety. , At least one selected from the group consisting of a pentahelicene moiety, a hexahelicene moiety, a heptahelicene moiety, and a coronene moiety. Preferably, the condensed polycyclic aromatic hydrocarbon moiety includes a condensed polycyclic aromatic hydrocarbon moiety having 3 to 6 benzene rings.

  In one embodiment, the charge transporting polymer or oligomer further has a polymerizable substituent.

  Another embodiment of the present invention relates to an ink composition comprising any one of the organic electronic materials and a solvent.

  In addition, another embodiment of the present invention relates to an organic layer formed using any one of the organic electronic materials or the ink composition.

  Moreover, other embodiment of this invention is related with the organic electronics element and organic electroluminescent element which have at least 1 said organic layer. In one embodiment, the organic electroluminescent device further includes a flexible substrate. In one Embodiment, the said organic electroluminescent element further has a resin film board | substrate.

  Furthermore, another embodiment of the present invention relates to a display element and a lighting device including any one of the organic electroluminescence elements, and a display device including the lighting device and a liquid crystal element as a display unit.

  According to the organic electronics material, the ink composition, and the organic layer which are the embodiments of the present invention, an organic electronics element having excellent life characteristics can be provided. In addition, the organic electronics element, the organic EL element, the display element, the lighting device, and the display device according to the embodiment of the present invention have excellent life characteristics.

It is a cross-sectional schematic diagram which shows an example of the organic EL element which is embodiment of this invention.

An embodiment of the present invention will be described.
<Organic electronics materials>
The organic electronics material which is an embodiment of the present invention contains a charge transporting polymer or oligomer having a condensed polycyclic aromatic hydrocarbon moiety having three or more benzene rings at at least one terminal. The organic electronic material may contain only one kind or two or more kinds of charge transporting polymers or oligomers. The charge transporting polymer or oligomer is preferable in that the film forming property in the wet process is excellent as compared with the low molecular compound.

[Charge transporting polymer or oligomer]
Charge transporting polymers or oligomers have the ability to transport charge. Holes are preferred as the charge to be transported.

(Structural unit with charge transport property)
The charge transporting polymer or oligomer has a structural unit having charge transporting properties. The structural unit having charge transporting properties is not particularly limited as long as it contains an atomic group having the ability to transport charges. The structural unit having a charge transporting property may include an amine ring structure (also referred to as an “aromatic amine”) structure, a carbazole structure, or a thiophene structure as an atomic group from the viewpoint of having a high hole transporting property. preferable. As the aromatic amine, triarylamine is preferable, and triphenylamine is more preferable.

  The charge transporting polymer or oligomer has only one type of structural unit selected from a unit having an aromatic amine structure, a unit having a carbazole structure, and a unit having a thiophene structure as a structural unit having charge transporting properties. Or you may have 2 or more types. The charge transporting polymer or oligomer preferably has units having an aromatic amine structure and / or units 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, a group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in the above E (excluding a group having a polymerizable substituent), 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.

(Copolymerized unit)
In order to adjust electrical characteristics, the charge transporting polymer or oligomer may be any one of the above arylene group or heteroarylene group, or the above linking group groups (A) and (B) as a copolymerized unit in addition to the above unit. It may have a structural unit represented by The charge transporting polymer or oligomer may have only one type of other copolymer unit or two or more types.

(Branch structure)
The charge transporting polymer or oligomer may be either a linear polymer or oligomer having no branched chain, or a branched polymer or oligomer having a branched chain. The branched chain has at least one structural unit constituting a charge transporting polymer or oligomer. It is also possible to use a linear polymer or oligomer in combination with a branched polymer or oligomer. From the viewpoint of easily controlling the molecular weight and the physical properties of the composition, a linear polymer or oligomer is preferable, and from the viewpoint of easily increasing the molecular weight, a branched polymer or oligomer is preferable. A branched polymer or oligomer is also preferable from the viewpoint of enhancing the durability of the organic electronic element.

  The charge transporting polymer or oligomer having a branched chain means that the charge transporting polymer or oligomer has a branched portion on the polymer or oligomer chain and has three or more terminals. The charge transporting polymer or oligomer has, for example, a structural unit serving as a branch starting point (also referred to as “branch starting structural unit”) as a branched portion. The charge transporting polymer or oligomer 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, in E (excluding a group having a polymerizable substituent), a group in which one hydrogen atom is further removed from a group having one or more hydrogen atoms, or the above linking group group (C ).
Z represents any of a carbon atom, a silicon atom, or a phosphorus atom.
The structural units (1b) to (11b) may have a substituent, and examples of the substituent include the same groups as those described above for E.

(Terminal structure)
The charge transporting polymer or oligomer has a condensed polycyclic aromatic hydrocarbon moiety at at least one terminal. The charge transporting polymer or oligomer may have only one kind or two or more kinds of condensed polycyclic aromatic hydrocarbon moieties. By containing a condensed polycyclic aromatic hydrocarbon moiety at the terminal, the electron transport property of the charge transporting polymer or oligomer is improved, that is, the stability to electrons is improved, and as a result, it is high as an organic electronic material. It is thought that performance can be demonstrated.

  In the present embodiment, the “condensed polycyclic aromatic hydrocarbon” is a hydrocarbon compound having three or more benzene rings and further having a ring other than the benzene ring. Each ring shares two or more atoms with other rings. The “condensed polycyclic aromatic hydrocarbon moiety” refers to an atomic group obtained by removing one hydrogen atom from a condensed polycyclic aromatic hydrocarbon. The fused polycyclic aromatic hydrocarbon moiety may be substituted or unsubstituted.

  Examples of the condensed polycyclic aromatic hydrocarbon moiety include a moiety where a benzene ring is linearly linked (for example, an anthracene moiety) and a moiety where a benzene ring is nonlinearly linked (for example, a phenanthrene moiety). Examples of the condensed polycyclic aromatic hydrocarbon moiety include a moiety where the benzene ring is directly linked (for example, an anthracene moiety) and a moiety where the benzene ring is linked via another cyclic hydrocarbon (for example, a fluoranthene moiety). )including.

  The number of benzene rings contained in the condensed ring of the condensed polycyclic aromatic hydrocarbon moiety is preferably 8 or less, more preferably 7 or less, from the viewpoint of solubility in a solvent at the time of polymer or oligomer synthesis. 6 or less is more preferable.

  Examples of the substituent that the condensed polycyclic aromatic hydrocarbon may have include, for example, a linear, cyclic, or branched alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1). -10); linear, cyclic, or branched alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 15 and even more preferably 1 to 10); and phenyl groups. From the viewpoint of excellent solubility and stability, a linear, cyclic, or branched alkyl group and a phenyl group are preferred.

  In a preferred embodiment, the fused polycyclic aromatic hydrocarbon is anthracene (3), tetracene (4), pentacene (5), phenanthrene (3), chrysene (4), triphenylene (4), tetraphen (4 ), Pyrene (4), picene (5), pentaphen (5), perylene (5), pentahelicene (5), hexahelicene (6), heptahelicene (7), coronene (7), fluoranthene (3), aceto Phenanthrylene (3), Asanthrene (3), Asanthrylene (3), Pleiaden (4), Tetraphenylene (4), Collanthrene (4), Dibenzoanthracene (5), Benzopyrene (5), Rubicene ( 5), hexaphen (6), hexacene (6), trinaphthylene (7), heptaphen (7), heptacene (7), pyran Ren (8), and is selected from the group consisting of ovalene (10). In the above, the numbers in parentheses represent the number of benzene rings contained in the condensed polycyclic aromatic hydrocarbon. Although not particularly limited, when the condensed polycyclic aromatic hydrocarbon includes one selected from the group consisting of anthracene, phenanthrene, triphenylene, and pyrene, it is easy to obtain excellent durability. More preferable.

Examples of the condensed polycyclic aromatic hydrocarbon moiety include the following structural unit (1c).
<Structural unit (1c)>

In the formula, Ar ¹ represents a condensed polycyclic aromatic hydrocarbon group having 3 to 6 benzene rings. Ar ¹ is unsubstituted or has a substituent. Examples of the substituent include a linear, cyclic, or branched alkyl group (preferably having a carbon number of 1-20, more preferably 1-15, still more preferably 1-10); a linear, cyclic, or branched alkoxy group. (Preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms); a phenyl group and the like.

  The structural units (c1) to (c8), which are preferred specific examples of the condensed polycyclic aromatic hydrocarbon moiety, are listed below.

  In one embodiment, the charge transporting polymer or oligomer may have a site other than the condensed polycyclic aromatic hydrocarbon site (hereinafter, also referred to as “other end site”) at the terminal. The charge transporting polymer or oligomer may have only one or two or more other terminal sites. Other terminal sites are not particularly limited. For example, the structural unit represented by any of the above (1a) to (84a) (E is bonded to the terminal bond), or a structural unit having an aromatic hydrocarbon structure or an aromatic compound structure Is mentioned. Examples of the structural unit having an aromatic hydrocarbon structure or an aromatic compound structure include the structural unit (1d) shown below. The structural unit (1d) has a structure different from the condensed polycyclic aromatic hydrocarbon moiety.

<Structural unit (1d)>

In the formula, Ar ² represents an aryl group or heteroaryl group having 2 to 30 carbon atoms. From the viewpoint of easy introduction of a polymerizable substituent at the terminal, Ar ² is, for example, an aryl group, preferably a phenyl group. Ar ² may have a substituent, and examples of the substituent include the same groups as those described above for E.

  The ratio of the condensed polycyclic aromatic hydrocarbon moiety at all terminals of the charge transporting polymer or oligomer is preferably 25% or more, more preferably 30 based on the total number of terminals from the viewpoint of improving the characteristics of the organic electronic device. % Or more, more preferably 35% or more. The upper limit is not particularly limited and is 100% or less.

  The ratio at all terminals can be determined by the charge ratio (molar ratio) of the monomer corresponding to the terminal structural unit used to synthesize the charge transporting polymer or oligomer.

  When the charge transporting polymer or oligomer has other terminal sites, the ratio of the other terminal sites in all terminals is preferably 75% or less, based on the total number of terminals, from the viewpoint of improving the characteristics of the organic electronics element. Preferably it is 70% or less, More preferably, it is 65% or less. The lower limit is not particularly limited, but it can be set to, for example, 5% or more in consideration of introduction of a polymerizable substituent described later, introduction of a substituent for improving film formability, wettability, and the like.

(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. The cured product of the charge transporting compound is obtained by the polymerization reaction, the solubility of the charge transporting compound in the solvent is changed, and a laminated structure can be easily formed.

  The position where the charge transporting polymer or oligomer 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. The charge transporting polymer or oligomer may have a polymerizable substituent in the terminal structural unit, or may have a polymerizable substituent in the structural unit other than the terminal, or other than the terminal structural unit and the terminal. It may be present in both of the structural units. Preferably, it has a polymerizable substituent in at least the terminal structural unit.

  The polymerizable substituent includes a group having a carbon-carbon multiple bond; a group having a cyclic structure (excluding a group having an aromatic heterocyclic structure); a group having an aromatic heterocyclic structure; and a siloxane derivative. A group; a combination of groups capable of forming an ester bond or an amide bond, and the like.

  Examples of the group having a carbon-carbon multiple bond include a group having a carbon-carbon double bond and a group having a carbon-carbon triple bond, and specifically include an acryloyl group, an acryloyloxy group, an acryloylamino group, and a methacryloyl group. 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.

  The number of polymerizable substituents per molecule of the charge transporting polymer or oligomer is preferably 2 or more, more preferably 3 or more, from the viewpoint of excellent curability. The number of polymerizable substituents is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of the stability of the charge transporting polymer or oligomer.

  The charge transporting polymer or oligomer 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 alkylene moiety. Preferably it is. Examples of the alkylene moiety include linear alkylene moieties such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene. The alkylene moiety preferably has 1 to 8 carbon atoms.

  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.

  In addition, from the viewpoint of facilitating preparation of a charge transporting polymer or oligomer, the group having a polymerizable substituent has an ability to transport a polymerizable substituent and / or charge with an alkylene or hydrophilic part. The connecting portion with the atomic group may have 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. In the present embodiment, examples of the “group having a polymerizable substituent” include the “polymerizable substituent” itself.
<Substituent groups (A) to (N)>

  The charge transporting polymer or oligomer preferably has a polymerizable substituent at the end of the molecular chain. In this case, the charge transporting polymer or oligomer may have a structural unit having a polymerizable substituent as a terminal structural unit. Specific examples include the structural unit (1d) having any of the groups represented by the substituent groups (A) to (N).

  When the charge transporting polymer or oligomer has a structural unit having a polymerizable substituent as the terminal structural unit, the proportion of the structural unit at all terminals is determined from the viewpoint of curability of the charge transporting polymer or oligomer. Based on the number of terminals, it is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more. The proportion of the structural unit at all terminals is preferably 75% or less, more preferably 70% or less, and even more preferably 65% or less, based on the number of all terminals, from the viewpoint of improving the characteristics of the organic electronics element. .

  The charge transporting polymer or oligomer may be a homopolymer having one type of structural unit or a copolymer having two or more types of structural units. When the charge transporting polymer or oligomer is a copolymer, the copolymer may be an alternating, random, block or graft copolymer, or a copolymer having an intermediate structure thereof, such as a block. It may be a random copolymer having properties.

  When the charge transporting polymer or oligomer has any 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 charge transporting polymer or oligomer is From the viewpoint of obtaining sufficient charge transportability, 10% or more is preferable, 20% or more is more preferable, and 30% or more is even more preferable. 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 charge injection property and charge transport property in one embodiment. In another embodiment, it is preferably 95% or less, more preferably 90% or less, and still more preferably 85% or less from the viewpoint of enhancing durability while imparting charge transportability.

  The “ratio of structural units” can be determined by the charge ratio (molar ratio) of monomers corresponding to each structural unit used for synthesizing the charge transporting polymer or oligomer.

  When the charge transporting polymer or oligomer has any 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 charge transporting polymer or oligomer is From the viewpoint of sufficiently covering the unevenness caused by the anode, it 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 more preferably 30% or less from the viewpoint of satisfactorily synthesizing the charge transporting polymer or oligomer. Further preferred.

  When the charge transporting polymer or oligomer has the structural unit (1c), the ratio of the structural unit (1c) to the total number of structural units in the charge transporting polymer or oligomer is 5% from the viewpoint of improving the characteristics of the organic electronic device. The above is preferable, 10% or more is more preferable, and 15% or more is still 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.

  When the charge transporting polymer or oligomer has the structural unit (1d), the ratio of the structural unit (1d) to the total number of structural units in the charge transporting polymer or oligomer is from the viewpoint of improving solubility, film formability, and the like. 5% or more is preferable, 10% or more is more preferable, and 15% or more is still more preferable. The proportion of the structural unit (1d) 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 charge transporting polymer or oligomer has a structural unit having an aromatic amine structure and / or a structural unit having a carbazole structure as a main structural unit (main skeleton) from the viewpoint of having a high hole injection property, hole transporting property, etc. It is preferable that it is a compound to make. In addition, the charge transporting polymer or oligomer is preferably a compound having at least two polymerizable substituents from the viewpoint of facilitating multilayering. From the viewpoint of having excellent curability, the polymerizable substituent is preferably a group having a cyclic ether structure, a group having a carbon-carbon multiple bond, or the like.

  The number average molecular weight of the charge transporting polymer or oligomer can be appropriately adjusted in consideration of solubility in a solvent, film formability, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more, from the viewpoint of excellent charge transportability. Further, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the composition. Is more preferable. A number average molecular weight means the number average molecular weight of standard polystyrene conversion by gel permeation chromatography (GPC).

  The weight average molecular weight of the charge transporting polymer or oligomer can be appropriately adjusted in consideration of solubility in a solvent, film formability, and the like. 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 charge transportability. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 400,000 or less from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the composition. Is more preferable. A weight average molecular weight means the weight average molecular weight of standard polystyrene conversion by gel permeation chromatography (GPC).

  The charge transporting polymer or oligomer can be synthesized by methods known to those skilled in the art. Although not particularly limited, the charge transporting polymer or oligomer is, for example, a monomer for forming a structural unit having a charge transporting property and a terminal for forming a condensed polycyclic aromatic hydrocarbon moiety at the terminal. It can be produced by polymerizing with a monomer. The monomer for forming the structural unit having charge transporting property includes at least a monomer having two or more substituents capable of forming a bond with each other, and can optionally form a bond with the monomer. A monomer having one substituent is included as a monomer for forming a terminal. A monomer for forming a condensed polycyclic aromatic hydrocarbon moiety at the terminal has one substituent capable of forming a bond with a monomer for forming a structural unit having a charge transporting property.

  In one embodiment, a method known in the art can be applied to the polymerization reaction. For example, a Suzuki coupling reaction in which a bond is formed between a boronic acid and a halogen such as bromine using a Pd (0) or Pd (II) compound as a catalyst can be applied. For a specific method for synthesizing the charge transporting polymer or oligomer using the Suzuki coupling reaction, for example, the description in International Publication No. 2010/140553 can be referred to.

  The content of the charge transporting polymer or oligomer in the organic electronic material is preferably 50% by mass or more, more preferably 55% by mass or more, based on the total mass of the organic electronic material, from the viewpoint of developing high charge transporting property. 60 mass% or more is still more preferable. The upper limit of the content of the charge transporting polymer or oligomer is not particularly limited, and may be 100% by mass. In consideration of the fact that the organic electronic material contains an additive described later, for example, 99.99. It is also possible to make it 5 mass% or less.

[Additive]
In this embodiment, the organic electronic material contains at least a charge transporting polymer or oligomer. In one embodiment, the organic electronics material may include various additives well known in the art as additives for organic electronics materials in addition to the charge transporting polymer or oligomer. For example, the organic material has an electron accepting compound that can act as an electron acceptor, an electron donating compound that can act as an electron donor, for a charge transporting polymer or oligomer, in order to adjust charge transportability, It may further contain a radical polymerization initiator, a cationic polymerization initiator and the like that can act as a polymerization initiator. When the organic electronic material contains a hole-transporting polymer or oligomer and further contains an electron-accepting compound, it is preferable in that it is easy to obtain excellent hole-transporting properties.

(Electron-accepting compound)
As the electron-accepting compound, specifically, both inorganic and organic materials can be used. For example, an electron-accepting compound described in JP 2003-031365 A, JP 2006-233162 A, etc., Super Bronsted acid compound described in Japanese Patent No. 3957635, JP 2012-72310 A, etc. And derivatives can be used. For example, an onium salt containing at least one selected from the following cations and at least one selected from the following anions can also be used. When the charge transporting polymer or oligomer has a polymerizable substituent, the onium salt can be preferably used also from the viewpoint of improving the curability of the charge transporting polymer or oligomer.

(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, tropium ion, cation with transition metal, etc., carbenium ion, ammonium ion, anilinium ion, aminium ion, iodonium ion , Sulfonium ion, tropylium ion and the like are preferable. From the viewpoint of achieving both charge transport properties and storage stability, ammonium ions, anilinium ions, iodonium ions, sulfonium ions, and the like are more preferable, and iodonium ions are still 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. Among _{^{them, 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) 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}} - , etc. fluoroantimonic acid ion are preferable, such as, Borate ions Ri preferred.

In one embodiment, it is preferable to use an onium salt having an anion containing an electron-withdrawing substituent as the electron-accepting compound. Specific examples of the compound include the following compounds.

  When using an electron-accepting compound, the content thereof is preferably 0.01% by mass or more, and 0.1% by mass with respect to the total mass of the organic electronic material from the viewpoint of improving the charge transport property of the organic electronic material. The above is more preferable, and 0.5% by mass or more is still more preferable. Moreover, from a viewpoint of maintaining favorable film formability, 50 mass% or less is preferable with respect to the total mass of the organic electronic material, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

<Ink composition>
The ink composition according to the embodiment of the present invention includes the organic electronic material according to the embodiment and a solvent. As the solvent, a solvent capable of forming a coating layer using an organic electronic material can be used. Preferably, a solvent capable of dissolving the organic electronic material can be used. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

[solvent]
Examples of the solvent include water and organic solvents. 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. The solvent preferably contains one or more selected from the group consisting of aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers.

  The content of the solvent in the ink composition can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the charge transporting polymer or oligomer to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% An amount of at least mass% is more preferred. The content of the solvent is preferably such that the ratio of the charge transporting polymer or oligomer to the solvent is 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. Is more preferable.

(Other additives)
The ink composition may further contain other various additives. Specific examples of various additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, antioxidants, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents. , Dispersants, surfactants and the like.

<Organic layer>
The organic layer which is an embodiment of the present invention is a layer formed using the organic electronic material or ink composition of the above embodiment. According to the ink composition, the organic layer can be satisfactorily formed by a coating method. Examples of the method for applying the ink composition include spin coating method; casting method; dipping method; relief printing, intaglio printing, offset printing, planographic printing, relief printing, offset printing, screen printing, gravure printing, and the like. A known method such as a plateless printing method such as an inkjet method may be used. Moreover, when forming an organic layer by the apply | coating method, after apply | coating an ink composition, the obtained apply | coated layer may be dried with a hotplate or oven, and a solvent may be removed.

  When the charge transporting polymer or oligomer has a polymerizable substituent, the coating layer can be cured by polymerization, so that it is easy to add an organic layer by a coating method to form a multilayer. As a trigger for initiating polymerization of the charge transporting polymer or oligomer, a method such as light irradiation or heating is generally used. Although there is no restriction | limiting in particular, From the viewpoint that a process is simple, the method by a heating is preferable.

  When using the light irradiation method, 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 the heating time can be adjusted as long as the polymerization reaction can be sufficiently advanced. Although there is no particular limitation, the heating temperature is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower. By setting the temperature range, various substrates can be applied. Further, from the viewpoint of increasing the polymerization rate of the coating layer, the heating temperature 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 heating time is preferably 2 hours or less, more preferably 1 hour or less, and even more preferably 30 minutes or less. The heating time is preferably 1 minute or longer, more preferably 3 minutes or longer, and further preferably 5 minutes or longer from the viewpoint of allowing the polymerization to proceed completely.

  From the viewpoint of improving the efficiency of hole transport, the thickness of the organic layer 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 300 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less.

<Organic electronics elements>
The organic electronics element which is embodiment of this invention has the organic layer of the said embodiment at least. Examples of the organic electronics element include an organic electroluminescence (organic EL) element, an organic thin film solar cell, and an organic light emitting transistor. The organic electronic element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

<Organic EL device>
A specific embodiment of the organic EL element will be described as an example of the organic electronics element. The organic EL element which is embodiment of this invention has the organic layer formed using the organic electronics material. The organic EL element usually has a substrate, at least a pair of an anode and a cathode, and a light emitting layer, and if necessary, such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. You may have another functional layer. One embodiment of the organic EL element has an organic layer as a light emitting layer and other functional layers. A preferred embodiment of the organic EL element has an organic layer as at least one of a hole injection layer and a hole transport layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic EL element. FIG. 1 shows the structure of an organic EL element having a multilayer organic layer composed of a light emitting layer 1 and a plurality of other functional layers. In the figure, 2 is an anode, 3 is a hole injection layer, 4 is a cathode, and 5 is an electron injection layer. Reference numeral 6 denotes a hole transport layer, 7 denotes an electron transport layer, and 8 denotes a substrate. Hereinafter, each layer will be described in detail.

(Light emitting layer)
The material used for the light emitting layer may be a low molecular compound, a polymer or an oligomer, 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. Polymers or oligomers that utilize fluorescence include polyfluorene, polyphenylene, polyphenylene vinylene (PPV), polyvinyl carbazole (PVK), fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, derivatives thereof, and A mixture of these can be suitably used.

  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 up 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, it is preferable to use a phosphorescent material 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.

  Further, in the case where a phosphorescent material is included in the light emitting layer, it is preferable that a host material is included 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. The formation of the cathode is not particularly limited, and can be performed by applying a known method.

(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)). The formation of the anode is not particularly limited, and can be performed by applying a known method.

(Other functional layers)
In addition to the light emitting layer, the organic EL element preferably has at least one layer selected from the group consisting of a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer as a functional layer. In one embodiment, it is preferable to include at least one of a hole injection layer and a hole transport layer. Hereinafter, typical functional layers will be described.

(Hole injection layer, hole transport layer)
The organic EL element preferably has an organic layer formed using an organic electronic material as at least one of a hole injection layer and a hole transport layer. In one embodiment, the organic EL element preferably has an organic layer formed using an organic electronic material as a hole transport layer. In this embodiment, the hole transport layer can be easily formed by an ink composition containing an organic electronic material. When the organic EL device further has a hole injection layer, the hole injection layer is not particularly limited and can be formed using a material well known in the art. It is also possible to use the organic electronic material of the above embodiment for the hole injection layer.

  In another embodiment, the organic EL element preferably has an organic layer formed using an organic electronic material as a hole injection layer. In this embodiment, the hole injection layer can be easily formed by an ink composition containing an organic electronics material. When the organic EL device further has a hole transport layer, the hole transport layer is not particularly limited and can be formed using a material well known in the art. It is also possible to use the organic electronic material of the above embodiment for the hole transport layer.

  In one embodiment, the ink composition is applied to form a coating layer, the coating layer is cured to form a hole injection layer, and then the ink composition is applied and applied onto the hole injection layer. The layers can be formed, dried or cured, and the hole injection layer / hole transport layer can be easily stacked.

(Electron transport layer, electron injection layer)
The formation of the electron transport layer and the electron injection layer can be performed according to a method well known in the art. Examples of materials that can be used for forming the electron transport layer and / or the electron injection layer include phenanthroline derivatives (for example, 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)), bipyridine, and the like. Derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives ( 2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), benzimidazole derivatives (1,3,5-Tris (1-Phenyl-1H-benzimidazol- 2-yl) benzene) (TPBi)), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ ), Bis (2-methyl-8-quninolinato) -4-phenylphenolate aluminum (III) ( BAlq)) etc. 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)
The board | substrate which can be used for an organic EL element is not specifically limited, Substrates, such as glass and a resin film, may be sufficient. As one embodiment, it is preferable to use a flexible substrate known in the art as a flexible substrate. As an example of the flexible substrate, a substrate including at least one selected from the group consisting of thin film glass, aluminum foil, and resin film can be given. The substrate is preferably transparent. From such a viewpoint, for example, a glass substrate, a quartz substrate, a substrate including a light-transmitting resin film, and the like are preferable. Among these, when a light-transmitting resin film is used as the substrate, it is particularly preferable because it not only has excellent transparency but also easily imparts flexibility to the organic EL element.

  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.

  When using a resin film, in order to suppress permeation | transmission of water vapor | steam, oxygen, etc., you may coat and use inorganic substances, such as a silicon oxide and a silicon nitride, on a resin film. In addition, the resin films may be used alone or in combination as a multilayer.

(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 devices such as home lighting, interior lighting, clocks, and liquid crystal backlights.

  As for the white light emitting element, it is currently difficult to emit white light with a single material. For this reason, white light emission is obtained by using a plurality of light emitting materials to simultaneously emit and mix a plurality of light emission colors. 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, and complementary colors such as blue and yellow, yellow green and orange are used. And those containing the two emission maximum wavelengths. The emission color can be controlled by adjusting the type and amount of the phosphorescent material.

<Display element, lighting device, display device>
The display element which is embodiment of this invention is equipped with the organic EL element of the said embodiment. 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 preferably used for displaying characters and the like because the structure is simple but the number of vertical pixels is limited. The latter is preferably used for high-quality displays because the drive voltage is low and current is small, and a bright high-definition image is obtained.

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element of the said embodiment. Furthermore, the display element which is embodiment of this invention is equipped with the said illuminating device and a liquid crystal element as a display means. For example, a display device using the illuminating device as a backlight (white light-emitting light source) and a liquid crystal element as a display unit, that is, a liquid crystal display device may be used. Such a configuration is a configuration in which only a backlight is replaced with the 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 Charge Transporting Polymer 1>
The following monomer A (5.0 mmol), the following monomer B1 (2.0 mmol), the following monomer D1 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further 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 resulting 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 for 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 charge transporting polymer 1.

  The number average molecular weight of the obtained charge transporting polymer 1 was 7,800, and the weight average molecular weight was 31,000. The charge transporting polymer 1 has a structural unit (1a) (derived from monomer A), a structural unit (2b) (derived from monomer B1), and a structural unit (1d) having an oxetane group (derived from monomer D1). The proportion of each structural unit was 45.5%, 18.2%, and 36.4%.

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 charge transporting polymer 2>
To the three-necked round bottom flask, add the monomer A (5.0 mmol), the following monomer B2 (2.0 mmol), the monomer D1 (1.0 mmol), the following monomer D2 (3.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 2 was synthesized in the same manner as the synthesis of the charge transporting polymer 1. The resulting charge transporting polymer 2 had a number average molecular weight of 23,100 and a weight average molecular weight of 209,400. The charge transporting polymer 2 includes a structural unit (1a) (derived from the monomer A), a structural unit (6b) (derived from the monomer B2), a structural unit (1d) having an oxetane group (derived from the monomer D1), and an alkyl group. The proportion of each structural unit was 45.5%, 18.2%, 9.1%, and 27.3%.

<Synthesis of charge transporting polymer 3>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B2 (2.0 mmol), the following monomer C1 (3.0 mmol), the monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 3 was synthesized in the same manner as the synthesis of the charge transporting polymer 1. The number average molecular weight of the obtained charge transporting polymer 3 was 8,800, and the weight average molecular weight was 25,700. The charge transporting polymer 3 includes a structural unit (1a) (derived from monomer A), a structural unit (6b) (derived from monomer B2), a structural unit (1c) (derived from monomer C1), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 4>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B2 (2.0 mmol), the following monomer C2 (3.0 mmol), the monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 4 was synthesized in the same manner as the charge transporting polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 4 was 6,600, and the weight average molecular weight was 30,000. The charge transporting polymer 4 includes a structural unit (1a) (derived from the monomer A), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C2), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 5>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B2 (2.0 mmol), the following monomer C3 (3.0 mmol), the monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 5 was synthesized in the same manner as the charge transporting polymer 1 was synthesized. The charge transporting polymer 5 obtained had a number average molecular weight of 7,400 and a weight average molecular weight of 26,200. The charge transporting polymer 5 includes a structural unit (1a) (derived from the monomer A), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C3), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 6>
To a 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 monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 6 was synthesized in the same manner as the charge transporting polymer 1 was synthesized. The resulting charge transporting polymer 6 had a number average molecular weight of 17,400 and a weight average molecular weight of 103,100. The charge transporting polymer 6 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C1), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of charge transporting polymer 7>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer C2 (3.0 mmol), the monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 7 was synthesized in the same manner as the charge transporting polymer 1 was synthesized. The resulting charge transporting polymer 7 had a number average molecular weight of 28,500 and a weight average molecular weight of 209,100. The charge transporting polymer 7 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C2), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 8>
To a three-necked round bottom flask, add the monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer C3 (3.0 mmol), the monomer D1 (1.0 mmol), and anisole (20 mL), Furthermore, the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 8 was synthesized in the same manner as the charge transporting polymer 1 was synthesized. The resulting charge transporting polymer 8 had a number average molecular weight of 20,700 and a weight average molecular weight of 142,000. The charge transporting polymer 8 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C3), and a structural unit having an oxetane group. (1d) (derived from monomer D1), and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Production of organic EL element>
[Example 1]
Under a nitrogen atmosphere, charge transporting polymer 1 (10.0 mg), the following electron-accepting compound 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 (25 nm) was formed.

Next, charge transporting polymer 3 (10.0 mg) and toluene (1.15 mL) were mixed to prepare an ink composition. On the hole injection layer formed above, the ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 200 ° C. for 10 minutes to form a hole transport layer (40 nm). ) Was formed. The hole transport layer could be formed without dissolving the hole injection layer.

The substrate obtained above was transferred into a vacuum vapor deposition machine, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (0. 8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to produce an organic EL element.

[Example 2]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 3 was changed to the charge transporting polymer 4 in the hole transport layer forming step.

[Example 3]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 3 was changed to the charge transporting polymer 5 in the hole transport layer forming step.

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

Table 1 summarizes the layer structure of the organic EL elements produced in Examples 1 to 3 and Comparative Example 1.

When voltage was applied to the organic EL elements obtained in Examples 1 to 3 and Comparative Example 1, green light emission was confirmed. For each element, the luminescence was measured lifetime (luminance half-life) in the luminous efficiency, and initial luminance 5,000 cd / ^{m 2} in the emission luminance 1,000 cd / ^{m 2.} The measurement results are shown in Table 2.

  As shown in Table 2, by using the organic electronic material according to the embodiment of the present invention for the hole transport layer, a long-life device having high luminous efficiency and excellent driving stability was obtained.

[Example 4]
Under a nitrogen atmosphere, the charge transporting polymer 6 (10.0 mg), the electron accepting compound 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 (25 nm) was formed.

Next, charge transporting polymer 2 (10.0 mg) and toluene (1.15 mL) were mixed to prepare an ink composition. On the hole injection layer formed above, the ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ and then cured by heating on a hot plate at 200 ° C. for 10 minutes to form a hole transport layer (40 nm). ) Was formed. The hole transport layer could be formed without dissolving the hole injection layer.

The substrate obtained above was transferred into a vacuum vapor deposition machine, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (0. 8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to produce an organic EL element.

[Example 5]
An organic EL device was produced in the same manner as in Example 4 except that the charge transporting polymer 6 was changed to the charge transporting polymer 7 in the hole injection layer forming step.

[Example 6]
An organic EL device was produced in the same manner as in Example 4 except that the charge transporting polymer 6 was changed to the charge transporting polymer 8 in the hole injection layer forming step.

Table 1 summarizes the layer structure of the organic EL elements produced in Examples 4 to 6 and Comparative Example 1.

When voltage was applied to the organic EL elements obtained in Examples 4 to 6 and Comparative Example 1, green light emission was confirmed. For each element, the luminescence was measured lifetime (luminance half-life) in the luminous efficiency, and initial luminance 5,000 cd / ^{m 2} in the emission luminance 1,000 cd / ^{m 2.} Table 4 shows the measurement results.

  As shown in Table 4, by using the organic electronics material according to the embodiment of the present invention for the hole injection layer, a long-life device having high light emission efficiency and excellent driving stability was obtained.

<Production of white organic EL element (lighting device)>
[Example 7]
Under a nitrogen atmosphere, charge transporting polymer 1 (10.0 mg), the electron accepting compound 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 (25 nm) was formed.

Next, charge transporting polymer 1 (10.0 mg), charge transporting polymer 4 (10.0 mg), and toluene (1.15 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.

Next, in nitrogen, CDBP (15.0 mg), FIr (pic) (0.9 mg), Ir (ppy) ₃ (0.9 mg), (btp) ₂ Ir (acac) (1.2 mg), and di Chlorobenzene (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 and dried by heating on a hot plate at 80 ° C. for 5 minutes 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 evaporator, and BAlq (10 nm), TPBi (30 nm), LiF (0.5 nm), and Al (100 nm) were formed in this order on the light emitting layer by the evaporation 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 2]
A white organic EL device was produced in the same manner as in Example 7 except that the charge transporting polymer 4 was changed to the charge transporting polymer 2. The light emitting layer could be formed without dissolving the hole transport layer. The white organic EL element could be used as a lighting device.

A voltage was applied to the white organic EL elements obtained in Example 7 and Comparative Example 2, and the light emission lifetime (luminance half-life) was measured with an initial luminance of 1,000 cd / m ² . When the light emission lifetime in Example 7 was 1, it was 0.72 in Comparative Example 2. Further, when the voltage at a luminance of 1,000 cd / m ² in Example 7 was 1, it was 1.12 in Comparative Example 2.

  The white organic EL element of Example 7 showed excellent emission lifetime and driving voltage.

  The effects of the embodiment of the present invention have been shown using the above examples. In addition to the charge transporting polymer used in the examples, it is possible to obtain an organic EL device having a long lifetime using the charge transporting polymer described above, and similarly exhibit excellent effects.

DESCRIPTION OF SYMBOLS 1 Light emitting layer 2 Anode 3 Hole injection layer 4 Cathode 5 Electron injection layer 6 Hole transport layer 7 Electron transport layer 8 Substrate

Claims (15)

  An organic electronic material comprising a charge transporting polymer or oligomer having a condensed polycyclic aromatic hydrocarbon moiety having three or more benzene rings at at least one terminal.   The organic electronic material according to claim 1, wherein the charge transporting polymer or oligomer has three or more terminals.   The organic electronic material according to claim 1 or 2, wherein the charge transporting polymer or oligomer has the condensed polycyclic aromatic hydrocarbon moiety at a terminal of 25% or more based on the total number of terminals.   The condensed polycyclic aromatic hydrocarbon moiety is an anthracene moiety, tetracene moiety, pentacene moiety, phenanthrene moiety, chrysene moiety, triphenylene moiety, tetraphen moiety, pyrene moiety, picene moiety, pentaphen moiety, perylene moiety, pentahelicene moiety, The organic electronics material according to any one of claims 1 to 3, comprising at least one selected from the group consisting of a hexahelicene moiety, a heptahelicene moiety, and a coronene moiety.   The organic electronic material according to any one of claims 1 to 4, wherein the condensed polycyclic aromatic hydrocarbon moiety includes a condensed polycyclic aromatic hydrocarbon moiety having 3 to 6 benzene rings.   The organic electronic material according to claim 1, wherein the charge transporting polymer or oligomer further has a polymerizable substituent.   An ink composition comprising the organic electronic material according to claim 1 and a solvent.   The organic layer formed using the organic electronics material in any one of Claims 1-6, or the ink composition of Claim 7.   An organic electronic device comprising at least one organic layer according to claim 8.   An organic electroluminescent device comprising at least one organic layer according to claim 8.   The organic electroluminescent element according to claim 10, further comprising a flexible substrate.   The organic electroluminescent element according to claim 10, further comprising a resin film substrate.   The display element provided with the organic electroluminescent element in any one of Claims 10-12.   The illuminating device provided with the organic electroluminescent element in any one of Claims 10-12.   A display device comprising the illumination device according to claim 14 and a liquid crystal element as display means.