TW201742876A - Organic electronic material and organic electronic element suitable for a wet type process and capable of increasing the lifetime of the organic electronic element - Google Patents

Abstract

One embodiment of the present invention relates to an organic electronic material, which comprises a charge transporting polymer or oligomer. At least one end of the charge transporting polymer or oligomer is provided with a condensed polycyclic aromatic hydrocarbon moiety. The condensed polycyclic aromatic hydrocarbon moiety is provided with three or more benzene rings. Moreover, the charge transporting polymer or oligomer is provided with three or more terminal ends. 25% or more terminal ends of the charge transporting polymer or oligomer is provided with the condensed polycyclic aromatic hydrocarbon moiety based on the total number of terminal ends. The condensed polycyclic aromatic hydrocarbon moiety is selected from the group consisting of anthracene moiety, tetracene moiety, pentacene moiety, phenanthrene moiety, chrysene moiety, triphenylene moiety, tetraphene moiety, pyrene moiety, picene moiety, pentaphene moiety, perylene moiety, and penta heliene moiety.

Description

Organic electronic materials and organic electronic components

Embodiments of the present invention relate to an organic electronic material, an ink composition, an organic layer, an organic electronic component, an organic electroluminescent device (also referred to as an "organic EL device"), a display device, an illumination device, and a display device.

The organic EL element is attracting attention in the following applications, for example, as an alternative to incandescent lamps, gas lamps, and the like; as a large-area solid-state light source. In addition, the organic EL element is also attracting attention as a self-luminous display, which is the most powerful display in place of a liquid crystal display (LCD) in the field of flat panel display (FPD).

The organic EL device is roughly classified into two types according to the organic material to be used: a low molecular organic EL device and a polymer organic EL device. The polymer type organic EL element uses a polymer compound as an organic material, and the low molecular type organic EL element uses a low molecular compound as an organic material. On the other hand, the method for producing an organic EL element is mainly divided into two types: a dry process in which a film is formed in a vacuum system; and a wet process in which film formation is performed by printing. The printing includes plate printing such as letterpress printing and die printing, and non-printing such as inkjet printing. The wet process is expected to be indispensable for a large-screen organic EL display in the future (see, for example, Patent Document 1 and Non-Patent Document 1).

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-279007

(Non-patent literature)

Non-Patent Document 1: Hirohiko Kenji, Kumamoto Daisuke, Koike Shin-Ming, Kuriyama Akira, Chishiro Seiichiro, Shih-Ching, the 53rd Joint Symposium on Applied Physics, 26p-ZK-4 (2006)

The organic EL device produced by the wet process has the advantages of being easy to reduce cost and increasing the area. However, regarding the characteristics of the organic EL element, further improvement is desired in terms of an organic EL element including an organic layer obtained by a wet process.

In view of the above problems, an object of the present invention is to provide an organic electronic material which is suitable for a wet process and which is suitable for improving the life characteristics of an organic electronic component. Furthermore, it is an object of other embodiments of the present invention to provide an ink composition and an organic layer which are suitable for improvement Life characteristics of organic electronic components. Further, another object of the present invention is to provide an organic electronic component, an organic EL device, a display device, an illumination device, and a display device, which are excellent in life characteristics.

The inventors of the present invention have made efforts to carry out research in order to solve the above problems, and as a result, have found an organic electronic material which is suitable for a wet process and is suitable for improving the life characteristics of an organic electronic component, and has completed the present invention.

In other words, an embodiment of the present invention relates to an organic electronic material comprising a charge transporting polymer or oligomer having a condensed polycyclic aromatic hydrocarbon at at least one terminal of the charge transporting polymer or oligomer In the site, the condensed polycyclic aromatic hydrocarbon moiety has three or more benzene rings.

In a preferred embodiment, the charge transporting polymer or oligomer has three or more terminals. Preferably, 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.

In a preferred embodiment, the condensed polycyclic aromatic hydrocarbon moiety comprises an anthracene moiety, a tetracene moiety, a pentacene moiety, a phenanthrene moiety, 1, 2 - chrysene, triphenylene, tetraphene, pyrene, picene, pentaphene, perylene, snail Alkene At least one selected from the group consisting of a pentahelicene site, a hexahelicene site, a heptahelicene site, and a coronene site.

In a preferred embodiment, the condensed polycyclic aromatic hydrocarbon moiety contains a condensed polycyclic aromatic hydrocarbon moiety, and the condensed polycyclic aromatic hydrocarbon moiety has 3 to 8 benzene rings.

Further, in a preferred embodiment, the charge transporting polymer or oligomer further has a substituent capable of being polymerized.

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

Further, another embodiment of the present invention relates to an organic layer formed using any of the foregoing organic electronic materials or ink compositions.

Furthermore, another embodiment of the present invention relates to an organic electronic component and an organic electroluminescent device, comprising at least one of the organic layers. In a preferred embodiment, the organic electroluminescent device further has a flexible substrate. In a preferred embodiment, the organic electroluminescent device further includes a resin film substrate.

Furthermore, another embodiment of the present invention relates to a display device and an illumination device including the above-described organic electroluminescence device, and a display device including the illumination device and a liquid crystal element as a display means.

The present invention is related to the subject matter described in Japanese Patent Application No. 2014-251848, the entire disclosure of which is incorporated herein by reference.

According to the embodiment of the present invention, that is, the organic electronic material, the ink composition, and the organic layer, it is possible to provide an organic electronic component having excellent life characteristics. Further, in the embodiment of the present invention, the organic electronic component, the organic EL device, the display device, the illumination device, and the display device are excellent in life characteristics.

1‧‧‧Lighting layer

2‧‧‧Anode

3‧‧‧ hole injection layer

4‧‧‧ cathode

5‧‧‧Electronic injection layer

6‧‧‧ hole transport layer

7‧‧‧Electronic transport layer

8‧‧‧Substrate

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device which is an embodiment of the present invention.

[Preferred form of implementing the invention]

An embodiment of the present invention will be described. The present invention is not limited by the following embodiments. Further, the preferred embodiments can be used singly or in combination.

<Organic Electronic Materials>

An organic electronic material according to an embodiment of the present invention contains a charge transporting polymer or oligomer, and has a condensed polycyclic aromatic hydrocarbon moiety at at least one terminal of the charge transporting polymer or oligomer, and the condensation The polycyclic aromatic hydrocarbon moiety has three or more benzene rings. The organic electronic material may contain only one type or two or more types of charge transporting polymers or oligomers. The charge transporting polymer or oligomer is more excellent in film forming property in a wet process than a low molecular compound.

[Charge transport polymer or oligomer]

Charge transporting polymers or oligomers have the ability to transport charge. The charge delivered is preferably a hole.

(structural unit with charge transportability)

The charge transporting polymer or oligomer has a structural unit which has charge transportability. The structural unit having charge transportability is not particularly limited as long as it contains an atomic group having a capability of transporting charges.

The charge transporting polymer or oligomer may have only one kind or have two or more structural units having charge transport properties. The structural unit having charge transportability preferably comprises a structure having a hole transporting property in the form of a radical: an amine having an aromatic ring (also referred to as an "aromatic amine") structure, a carbazole structure, a thiophene structure,茀 structure, benzene structure, or pyrrole structure.

In particular, from the viewpoint of having high hole transportability, the structural unit having charge transportability preferably contains the following structure in the form of an atomic group: an amine having an aromatic ring (also referred to as "aromatic amine" ") Structure, carbazole structure, or thiophene structure. The aromatic amine is preferably a triarylamine, more preferably triphenylamine.

The charge transporting polymer or oligomer may have only one kind or two or more of the following units as a structure of charge transporting structure Element: a structural unit selected from a unit having an aromatic amine structure, a unit having a carbazole structure, and a unit having a thiophene structure. The charge transporting polymer or oligomer preferably has a unit having an aromatic amine structure and/or a unit having a carbazole structure.

The charge transporting polymer or oligomer preferably has a structural unit in the form of at least a divalent structural unit having a hole transporting property.

The structural units (1a) to (84a), which are specific examples of the structural unit having the hole transporting property, are listed below. The following examples are examples of divalent structural units.

<Structural unit (1a)~(84a)>

In the formula, E each independently represents a hydrogen atom or a substituent. Preferably, E is independently represented by -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , and the following formulas (1) to (3), Any one selected from the group consisting of a halogen atom and a group having a substituent capable of undergoing polymerization.

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 or heteroaryl group having 2 to 30 carbon atoms.

R ¹ to R ¹¹ may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group, and an aralkyl sulfide. Alkyl, aralkenyl, arylalkynyl, hydroxy, hydroxyalkyl, amine, substituted amine, decyl, substituted alkyl, decyloxy, substituted decyloxy, halogen atom, fluorenyl, decyloxy, arylene Amino, guanamine (-NR-COR, -CO-NR ₂ (R is a hydrogen atom or an alkyl group)), fluorenylene (-N(CO) ₂ Ar, -Ar(CO) ₂ NR(R Is a hydrogen atom or an alkyl group, and Ar is an exoaryl group), a carboxyl group, a substituted carboxyl group, a cyano group, a heteroaryl group or the like. Here, the term "substitution" refers to a group which is substituted with a group having, for example, a linear, cyclic or branched alkyl group having 1 to 6 carbon atoms; or a phenyl group or a naphthyl group.

a, b and c represent an integer of 1 or more, preferably an integer of 1 to 4.

The group having a substituent which can be polymerized is as described later.

E is preferably a hydrogen atom, a substituted or unsubstituted linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a substituted or unsubstituted carbon having 2 to 30 carbon atoms. Or a heteroaryl group; more preferably a substituted or unsubstituted linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; further preferably an unsubstituted carbon number of 1 to 22 A linear, cyclic or branched alkyl group.

In the formula, Ar independently represents an aryl or heteroaryl group having 2 to 30 carbon atoms, or an extended aryl group or a heteroaryl group having 2 to 30 carbon atoms.

Ar may have a substituent, and the substituent may, for example, be the same group as the above E.

In the formula, X and Z each independently represent a divalent linking group, and are not particularly limited. For example, a group having one or more hydrogen atoms in the above E (excluding a group having a substituent capable of undergoing polymerization) may be further The group remaining after removing one hydrogen atom or the group shown in the following linking group (A) to (C).

x represents an integer from 0 to 2.

Y represents a trivalent linking group and is not particularly limited. For example, a group remaining after removing two hydrogen atoms from a group having two or more hydrogen atoms in the above E (excluding a group having a substituent capable of undergoing polymerization) may be mentioned.

<Linking group (A)~(C)>

Linking group (A)

Linking base group (B)

Linking base group (C)

In the formula, R may be, for example, the same group as the above E.

In the present embodiment, the halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the following, examples of the halogen atom may be, for example, the same atoms as described above.

In the present embodiment, examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and n-decyl group. N-undecyl, n-dodecyl, isopropyl, isobutyl, secondary butyl, tert-butyl, 2-ethylhexyl, 3,7-dimethyloctyl, cyclohexyl, ring Heptyl, cyclooctyl and the like.

In the following, examples of the alkyl group may be, for example, the same groups as those described above.

In the present embodiment, the aryl group refers to an atomic group remaining after removing one hydrogen atom from an aromatic hydrocarbon, and the term "heteroaryl group" means that one hydrogen atom is removed from an aromatic compound having a hetero atom. Atomic group.

The aryl group may, for example, be a phenyl group, a biphenyl group, a terphenyl group, a triphenylphenyl group, a naphthyl group, an anthracenyl group, a condensed tetraphenyl group, an anthracenyl group or a phenanthryl group.

The heteroaryl group may, for example, be a pyridyl group, a pyrazine group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthroline group, a furyl group, a pyrrolyl group, a thienyl group or a carbazole. Base, oxazole group, oxadiazolyl, thiadiazolyl, triazolyl, benzoxazolyl, benzooxadiazolyl, benzothiadiazolyl, benzotriazolyl, benzene And thiophene and the like.

In the following, examples of the aryl group and the heteroaryl group may be the same as those described above.

In the present embodiment, the term "aryl group" refers to an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon, and the term "heteroaryl group" means that two hydrogen atoms are removed from an aromatic compound having a hetero atom. Leave the atomic group.

Examples of the aryl group include a stretching phenyl group, a biphenyldiyl group, a biphenyldiyl group, a triphenylbenzenediyl group, a naphthalenediyl group, a fluorenyldiyl group, a fused tetraphenyldiyl group, a fluorenyldiyl group, and a phenanthrene group. Second base and so on.

Examples of the heteroaryl group include a pyridyldiyl group, a pyrazinediyl group, a quinolinediyl group, an isoquinolinyldiyl group, an acridinediyl group, a phenanthryldiyl group, a furyldiyl group, a pyrrolediyl group, and a thiophene diene. Base, carbazolediyl, oxazolidinediyl, oxadiazolediyl, thiadiazolediyl, triazolyldiyl, benzoxazolediyl, benzoxoxadiazole, benzothiadiazole Base, benzotriazolediyl, benzothiophenediyl and the like.

In the following, examples of the aryl group and the heteroaryl group may be the same as those described above.

From the viewpoint of excellent hole transportability, structural units (1a) to (8a), (15a) to (20a), (23a) to (47a), and structural units having hole transport properties are preferable. (69a) to (84a), more preferably structural units (1a) to (8a), (15a) to (20a), and (69a) to (84a), further preferably structural units (1a) to (8a) , (15a) ~ (20a) and (79a) ~ (84a). These structural units are also preferable because it is easy to synthesize a charge transporting polymer or oligomer by using a corresponding monomer.

Preferred structural examples of the structural unit having the hole transporting property, that is, the structural units (a1) to (a6) are listed below.

<Structural unit (a1)~(a6)>

In the formula, the phenyl group, the phenylene group and the thiophenediyl group may have a substituent, and examples of the substituent include the same group as the above E. When having a substituent, the substituent is preferably a linear or cyclic group having 1 to 22 carbon atoms or A branched alkyl group, or an aryl or heteroaryl group having 2 to 30 carbon atoms; more preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms.

(copolymer unit)

The charge transporting polymer or oligomer may have, in addition to the above units, the above-mentioned aryl or heteroaryl group or any of the above-mentioned linking groups (A) and (B) in order to adjust electrical properties. A structural unit as shown, as a copolymerization unit. The charge transporting polymer or oligomer may have only one or two or more other copolymerized units.

(branched structure)

a charge transporting polymer or oligomer, which may be a linear polymer or oligomer having no branch (side chain) or a branching polymer or oligomer having a branch Any one. The branched chain has at least one structural unit constituting the charge transporting polymer or oligomer, and preferably has two or more.

It is also possible to use a linear polymer or oligomer together with a branched polymer or oligomer. From the viewpoint of easily controlling the molecular weight of the molecular weight and the physical properties of the composition, a linear polymer or oligomer is preferred, and from the viewpoint of easily increasing the molecular weight, a branched polymer or Oligomer. Branched polymers or oligomers are also preferred from the viewpoint of improving the durability of the organic electronic component.

The charge transporting polymer or oligomer does not have a branch, and means that the charge transporting polymer or oligomer has two terminals. By "end" is meant the end of a polymer or oligomer chain.

The charge transporting polymer or oligomer having a branch means that the charge transporting polymer or oligomer has a branching 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 (also referred to as a "branched starting point structural unit") which serves as a branching starting point as a branching portion. The charge transporting polymer or oligomer may have only one kind or have two or more branching starting point structural units.

The branch starting point structural unit is a trivalent or higher structural unit, and is preferably a trivalent to hexavalent structural unit from the viewpoint of improving durability, and more preferably a trivalent or tetravalent structural unit. As described above, the charge transporting polymer or oligomer preferably has a structural unit in the form of at least a divalent structural unit having a hole transporting property. The charge transporting polymer or oligomer may further have a structural unit in the form of a branching starting structural unit having a hole transporting property.

Specific examples of the branch starting point structural unit, that is, structural units (1b) to (11b) are listed below. The structural units (2b) to (4b) are structural units corresponding to an aromatic amine structure, and the structural units (5b) to (8b) correspond to structural units having a carbazole structure.

<Structural unit (1b)~(11b)>

In the formula, W represents a trivalent linking group, and examples thereof include a group remaining after removing one hydrogen atom from 2 to 30 carbon atoms of the aryl group or the heteroaryl group.

Ar each independently represents a divalent linking group, and for example, independently represents an exoaryl group or a heteroaryl group having 2 to 30 carbon atoms. Ar is preferably an aryl group, more preferably a phenyl group.

Y represents a divalent linking group and is not particularly limited. For example, in the above E (excluding a group having a substituent capable of undergoing polymerization) The group in which one or more hydrogen atoms are further removed after leaving one hydrogen atom or the group shown in the above-mentioned linking group (C).

Z represents any one of a carbon atom, a germanium atom or a phosphorus atom.

The structural units (1b) to (11b) may have a substituent, and the substituent may, for example, be the same group as the above E.

(end structure)

At least one end of the charge transporting polymer or oligomer has a condensed polycyclic aromatic hydrocarbon moiety. The charge transporting polymer or oligomer may have only one kind or have two or more condensed polycyclic aromatic hydrocarbon sites. By including a condensed polycyclic aromatic hydrocarbon moiety at the terminal end, it is considered that the electron transportability of the charge transporting polymer or oligomer can be improved, that is, the stability of electrons can be improved, and as a result, it can be used as an organic electronic material. high performance.

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 a benzene ring. Each ring has more than two atoms in common with the other rings. In addition, the "condensed polycyclic aromatic hydrocarbon moiety" means an atomic group remaining after removing one hydrogen atom from a condensed polycyclic aromatic hydrocarbon. The condensed polycyclic aromatic hydrocarbon contained in the condensed polycyclic aromatic hydrocarbon moiety may be substituted or unsubstituted, and in a preferred embodiment, may be unsubstituted.

Examples of the condensed polycyclic aromatic hydrocarbon moiety include a site in which a benzene ring is linearly connected (for example, a ruthenium site), and a site in which a benzene ring is connected in a non-linear shape (for example, a phenanthrene moiety). In addition, condensed polycyclic aromatic Examples of the hydrocarbon moiety include a site where the benzene ring is directly bonded (for example, a ruthenium site), and a site where the benzene ring is bonded via another cyclic hydrocarbon (for example, a fluoranthene site).

The number of benzene rings contained in the condensed ring of the condensed polycyclic aromatic hydrocarbon moiety is preferably 8 or less, more preferably from the viewpoint of solubility in a solvent when synthesizing a polymer or an oligomer. 7 or less, further preferably 6 or less. Moreover, from the viewpoint of obtaining excellent life characteristics, it is preferably six or less, and for example, it can be five or less. The number of benzene rings is three or more from the viewpoint of obtaining excellent life characteristics. For example, when a charge transporting polymer or oligomer is used in the hole transporting layer, it is preferably four or more.

The substituent which the condensed polycyclic aromatic hydrocarbon may have may be, for example, a linear, cyclic or branched alkyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 15). Preferably, the carbon number is 1 to 10); a linear, cyclic or branched alkoxy group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 15, more preferably a carbon number of 1 to 10). ; phenyl, etc. 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 condensed polycyclic aromatic hydrocarbon is derived from ruthenium (3), fused tetraphenyl (4), fused pentabenzene (5), phenanthrene (3), 1,2-benzophenanthrene (4) ), triphenylene (4), tetrafen (4), ruthenium (4), ruthenium (5), penfen (5), ruthenium (5), pentrasene (5), hexaspene (6), seven Spiroene (7), hydrazine (7), fluoranthene (3), acephenanthrylene (3), aceanthrene (3), vinegar (aceanthrylene) (3), pyridene (4), tetraphenylene (4), cholanthrene (4), dibenzopyrene (5), benzopyrene (5), Rubicene (5), hexaphene (6), hexabenzene (6), trinaphthylene (7), heptaphene (7), thick heptabenzene (7) Selected from the group consisting of pyranthrene (8) and ovale (10). In the above, the number in parentheses indicates the number of benzene rings contained in the condensed polycyclic aromatic hydrocarbon. From the viewpoint of improving properties, the condensed polycyclic aromatic hydrocarbon preferably contains ruthenium, fused tetraphenyl, fused pentabenzene, phenanthrene, 1,2-benzophenanthrene, triphenylene, tetraphene, anthracene, At least one of the group consisting of ruthenium, penfen, hydrazine, pentra-nene, hexacro-nene, hepta- olefin, and fluorene. Although not particularly limited, when the condensed polycyclic aromatic hydrocarbon contains rhodium, phenanthrene, fused tetraphenyl, tetraphene, 1,2-benzophenanthrene, triphenylene, anthracene, pentacene, penfen, and hydrazine When one of the selected groups is selected, it is more preferable because it is easy to obtain excellent durability. The condensed polycyclic aromatic hydrocarbon is particularly preferably one selected from the group consisting of ruthenium, triphenylene, anthracene and fused pentabenzene.

The condensed polycyclic aromatic hydrocarbon moiety may, for example, be the following structure (1c).

<Structure (1c)>

In the formula, Ar ¹ represents a condensed polycyclic aromatic hydrocarbon group having 3 to 8, preferably 3 to 6 benzene rings. Ar ¹ is unsubstituted or has a substituent. The substituent may, for example, be a substituted or unsubstituted linear, cyclic or branched alkyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 15, more preferably carbon). a linear or cyclic alkoxy group substituted or unsubstituted (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 15, more preferably a carbon number) 1~10); substituted or unsubstituted phenyl group. In one embodiment, Ar ¹ may be unsubstituted.

Preferred examples of the condensed polycyclic aromatic hydrocarbon moiety, that is, structures (c1) to (c17) are listed below.

The structural unit having a terminal having a condensed polycyclic aromatic hydrocarbon moiety may, for example, be the following structural unit (1c). The structural unit at the end is a monovalent structural unit.

<Structural unit (1c)>

In the formula, Ar ¹ is as described above. Ar represents an exoaryl or heteroaryl group having 2 to 30 carbon atoms, and n represents 0 or 1. Ar is, for example, a phenyl group.

In the embodiment, the charge transporting polymer or oligomer may have a portion other than the condensed polycyclic aromatic hydrocarbon moiety at the terminal (hereinafter also referred to as "other end portion"). The charge transporting polymer or oligomer may have only one or two or more other terminal sites. The other end portions are not particularly limited. For example, the structural unit represented by any one of the above (1a) to (84a) (the portion where E is bonded to the terminal bond bond) or has an aromatic hydrocarbon structure or an aromatic compound structure. Part. The site having an aromatic hydrocarbon structure or an aromatic compound structure may, for example, be a structure (1d) shown below. The structure (1d) is a structure having a structure different from that of the condensed polycyclic aromatic hydrocarbon. In other words, the structure (1d) is a structure excluding a portion having a condensed polycyclic aromatic hydrocarbon.

<Structure (1d)>

In the formula, Ar ² represents an aryl group or a heteroaryl group having 2 to 30 carbon atoms. From the viewpoint of easily introducing a substituent which can be polymerized to the terminal, Ar ^{2 is,} for example, an aryl group, preferably a phenyl group. Ar ² may have a substituent, and as the substituent, for example, the same group as the above E may be mentioned. When it has a substituent, it is preferably a substituted or unsubstituted linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or a group having a substituent which can be polymerized.

The structural unit having the end of the other end portion may, for example, be the following structural unit (1d).

<Structural unit (1d)>

In the formula, Ar ² is as described above. Ar represents an exoaryl or heteroaryl group having 2 to 30 carbon atoms, and n represents 0 or 1. Ar is, for example, a phenyl group.

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

The ratio at all the ends can be determined by the feed ratio (mole ratio) of the monomer corresponding to the structural unit at the end, which is used when synthesizing the charge transporting polymer or oligomer. monomer.

When the charge transporting polymer or oligomer has other terminal sites, the ratio of the other terminal sites on all the ends is based on the total number of terminals, preferably 75, from the viewpoint of improving the characteristics of the organic electronic component. % or less, more preferably 70% or less, further preferably 65% or less. The lower limit is not particularly limited, and may be, for example, 5% or more in consideration of introduction of a substituent which can be polymerized as described later, and introduction of a substituent or the like for improving film formability and wettability.

(polymerizable substituent)

The substituent which can be polymerized (also referred to as "polymerizable substituent") means a substituent which can form a bond between two or more molecules by a polymerization reaction. By the polymerization reaction, a cured product of the charge transporting compound can be obtained, and the solubility of the charge transporting compound in the solvent changes, and the laminated structure can be easily formed.

The position at which the charge transporting polymer or oligomer has a substituent capable of being polymerized is not particularly limited. It suffices that a bond can be formed between two or more molecules by generating a polymerization reaction. The charge transporting polymer or oligomer may have a substituent capable of being polymerized at a terminal structural unit, or a polymerizable substituent at a structural unit other than the terminal, or a structural unit other than the terminal and a terminal at the terminal. Both of the units have substituents that can be polymerized. It is preferred that at least the structural unit at the end has a substituent which can be polymerized.

Examples of the substituent which can be polymerized include a group having a carbon-carbon multiple bond; a group having a cyclic structure (having an aromatic heterocyclic ring) Except for the structure; a group having an aromatic heterocyclic structure; a group containing a siloxane derivative; a combination of a group capable of forming an ester bond or a guanamine 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; specifically, for example, an acryloyl group, an acryloxy group, or a propylene group; Amidino, methacryloyl, methacryloxy, methacrylamido, vinyloxy, vinylamine, styryl, etc; allyl, butenyl, vinyl (where The alkenyl group such as the above-exemplified group; an alkynyl group such as an ethynyl 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 group structure, a lactone group (a group having a cyclic ester structure), and an indole amine group (having a ring). The base of the guanamine structure), etc.; specifically, for example, a cyclopropyl group, a cyclobutyl group, a 1,2-dihydrobenzocyclobutenyl group, an epoxy group (epoxyethyl group), an epoxy group An oxetanyl, a diketene group, an epithiol group, an α-lactone group, a β-lactone group, an α-indolyl group, a β-indolyl group, and the like.

Examples of the group having an aromatic heterocyclic structure include a furyl group, a pyrrolyl group, a thienyl group, and a silole group.

The combination of a group capable of forming an ester bond or a guanamine bond may, for example, be a combination of a carboxyl group and a hydroxyl group, or a combination of a carboxyl group and an amine group.

The number of substituents capable of undergoing polymerization per molecule of the charge transporting polymer or oligomer is preferably two or more, and more preferably three or more, from the viewpoint of excellent curability. Charge transporting polymer The number of substituents which can be polymerized, from the viewpoint of the stability of the oligomer, is preferably 1,000 or less, more preferably 500 or less.

The charge transporting polymer or oligomer may have "a substituent which can be polymerized" as "a group having a substituent capable of undergoing polymerization". From the viewpoint of increasing the degree of freedom of the substituent which can be polymerized and easily causing a polymerization reaction, it is preferred to have a substituent group capable of undergoing polymerization, a substituent having an alkyl group and a polymerizable group, and the like. The alkyl group is bonded. Examples of the alkylene group include a linear alkyl group such as a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. The carbon number of the alkyl group is preferably from 1 to 8.

From the viewpoint of improving the affinity with a hydrophilic electrode such as indium tin oxide (ITO), a substituent having a substituent capable of being polymerized, having a hydrophilic portion, and a polymerizable substituent is preferable. Hydrophilic site bonding. Examples of the hydrophilic moiety include an oxygen-extended alkyl structure such as an oxymethylene structure or an oxygen-extended ethyl structure; a linear chain such as a polyoxymethylene structure or a polyoxyalkylene structure; Hydrophilic part. The carbon number of the hydrophilic portion is preferably from 1 to 8.

Further, from the viewpoint of easily modulating the charge transporting polymer or oligomer, a group having a substituent capable of undergoing polymerization, an alkyl group or a hydrophilic portion and a polymerizable substituent and/or having a transport The junction between the radicals of the charge capacity may include an ether bond, an ester bond, or the like.

The substituent groups (A) to (N) are exemplified below as specific examples of the substituent having a substituent which can be polymerized. In the present embodiment, the example of the "substituent having a substituent capable of undergoing polymerization" also includes "a substituent which can be polymerized" itself.

<Substituent group (A)~(N)>

Substituent group (A)

Substituent group (B)

Substituent group (C)

Substituent group (D)

Substituent group (E)

Substituent group (F)

Substituent group (G)

Substituent group (H)

Substituent group (I)

Substituent group (J)

Substituent group (K)

Substituent group (L)

Substituent group (M)

Substituent group (N)

The charge transporting polymer or oligomer preferably has a substituent capable of undergoing polymerization at the end of the molecular chain. In this case, the charge transporting polymer or oligomer may have a structural unit as a terminal structural unit, and the structural unit has a polymerizable substituent. in particular, For example, the structural unit (1d) having any one of the groups shown in the above substituent groups (A) to (N) may be mentioned.

When the charge transporting polymer or oligomer has a structural unit as a structural unit of the terminal (the structural unit has a polymerizable substituent), from the viewpoint of the hardenability of the charge transporting polymer or oligomer, all The proportion of the structural unit at the end is preferably 5% or more, more preferably 10% or more, further preferably 15% or more, based on the total number of ends. Further, from the viewpoint of improving the characteristics of the organic electronic component, the ratio of the structural unit at all the ends is preferably 75% or less, more preferably 70% or less, based on the total number of ends, and further preferably Less than 65%.

The charge transporting polymer or oligomer may be a homopolymer having one structural unit or a copolymer having two or more structural units. When the charge transporting polymer or oligomer is a copolymer, the copolymer may be an alternating copolymer, a block copolymer, or a graft copolymer, and may also be a copolymer having a structure interposed therebetween. For example, a random copolymer having a block property.

a charge transporting polymer or oligomer having at least a divalent structural unit having a charge transporting property, and a monovalent structural unit having a condensed polycyclic aromatic hydrocarbon moiety, and Further having a branching starting structural unit and/or a monovalent structural unit, the monovalent structural unit having other terminal sites.

From the viewpoint of obtaining sufficient charge transportability, a charge transporting divalent structure in a charge transporting polymer or oligomer The ratio of the total number of units (e.g., structural units (1a) to (84a)) to the total number of structural units is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more. Further, from the viewpoint of obtaining high charge injectability and charge transportability, the ratio of the total number of divalent structural units (for example, structural units (1a) to (84a)) having charge transportability is preferably higher. Moreover, from the viewpoint of improving the durability while imparting charge transportability, it is preferably 95% or less, more preferably 90% or less, still more preferably 85% or less.

The "ratio of the structural unit" can be determined by the ratio of the feed amount (mol ratio) of the monomer corresponding to each structural unit, which is a single used when synthesizing the charge transporting polymer or oligomer. body.

When the charge transporting polymer or oligomer has a branching starting point structural unit, from the viewpoint of sufficiently covering the unevenness of the anode, in the charge transporting polymer or oligomer, the branching starting point structural unit (for example, a structure) The ratio of the total number of the units (1b) to (11b)) to the total number of structural units is preferably 1% or more, more preferably 5% or more, still more preferably 10% or more. Further, from the viewpoint of satisfactorily synthesizing a charge transporting polymer or oligomer, the ratio of the total number of branching starting point structural units (for example, structural units (1b) to (11b)) is preferably 50% or less, and more preferably Preferably, it is 40% or less, and further preferably 30% or less.

From the viewpoint of improving the characteristics of the organic electronic component, the total number of structural units (for example, structural unit (1c)) having a condensed polycyclic aromatic hydrocarbon moiety in the charge transporting polymer or oligomer is relative to all structural units The ratio of the number is preferably 5% or more, more preferably 10%. Further, it is further preferably 15% or more. Further, from the viewpoint of preventing a decrease in hole transportability, the ratio of the total number of structural units (for example, structural unit (1c)) having a condensed polycyclic aromatic hydrocarbon moiety is preferably 95% or less, more preferably 90. % or less, further preferably 85% or less.

When the charge transporting polymer or oligomer has a structural unit (the structural unit has other terminal sites), it has a charge transporting polymer or oligomer from the viewpoint of improving solubility, film forming property, and the like. The ratio of the total number of structural units (e.g., structural unit (1d)) at the other end portions to the total number of structural units is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more. Further, from the viewpoint of preventing a decrease in hole transportability, the ratio of the total number of structural units (for example, structural unit (1d)) having other end portions is preferably 95% or less, more preferably 90% or less, further Jia is 85% or less.

The charge transporting polymer or oligomer is preferably a compound which has a structural unit having an aromatic amine structure and/or has a carbazole from the viewpoint of having high hole injectability, hole transportability, and the like. The structural unit of the structure serves as the main structural unit (main skeleton). Further, from the viewpoint of easy multilayering, the charge transporting polymer or oligomer is preferably a compound having at least two or more substituents which can be polymerized. From the viewpoint of having excellent curability, the substituent which can be polymerized 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 transport property. Further, from the viewpoint of maintaining good solubility in a solvent and easily modulating the composition, it is preferably 1,000,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less. The number average molecular weight refers to a number average molecular weight converted by standard polystyrene 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 transport property. Further, from the viewpoint of maintaining good solubility in a solvent and easily modulating the composition, it is preferably 1,000,000 or less, more preferably 700,000 or less, still more preferably 400,000 or less. The weight average molecular weight means a weight average molecular weight converted by standard polystyrene by gel permeation chromatography (GPC).

(Production method)

The charge transporting polymer or oligomer can be produced by various synthesis methods, and is not particularly limited. A condensed polycyclic aromatic hydrocarbon moiety can be introduced into a conventional charge transporting polymer or oligomer. The synthesis method may, for example, be a method using the following conventional coupling reaction: Suzuki coupling, root-shore coupling, head coupling, Stille coupling, Buchwald-Hartwig coupling, and the like. Suzuki coupling uses a Pd catalyst between the aromatic boronic acid derivative and the aromatic halide to create a cross-coupling reaction. If coupled by Suzuki Further, it is possible to easily produce a charge transporting polymer or oligomer by bonding desired aromatic rings to each other.

In the coupling reaction, for example, a Pd(0) compound, a Pd(II) compound, a Ni compound or the like is used as a catalyst. In addition, it is also possible to use a catalytic species which is produced by using stilbene (diphenylmethyleneacetone) dipalladium (0), palladium acetate (II) or the like as a precursor and coordinating with a phosphine. Base mixing.

When a charge transporting polymer or oligomer is synthesized, a monomer corresponding to the above-described divalent structural unit, trivalent structural unit, and monovalent structural unit can be used. As the monomer, the following can be exemplified.

<Monomer A>

R-A-R

<Monomer B>

<monomer C>

R-C

<Monomer D>

R-D

In the formula, A represents a divalent structural unit, C represents a structural unit having a terminal of a "condensed polycyclic aromatic hydrocarbon moiety", D represents a structural unit having an end of "other terminal moiety", and B represents a trivalent or A tetravalent structural unit. R represents a functional group capable of forming a bond with each other, and preferably each independently represents any one selected from the group consisting of a boric acid group, a boric acid ester group, and a halogen group.

From the viewpoint of exhibiting high charge transportability, the content of the charge transporting polymer or oligomer in the organic electronic material is preferably 50% by mass or more, more preferably 55 mass, based on the total mass of the organic electronic material. More preferably, it is 60% by mass or more. The upper limit of the content of the charge-transporting polymer or the oligomer is not particularly limited, and may be 100% by mass, and may be 99.5% by mass or less in consideration of the fact that the organic electronic material contains the additive described later.

[additive]

In the present embodiment, the organic electronic material contains at least a charge transporting polymer or an oligomer. The organic electronic material may contain, in addition to the charge transporting polymer or oligomer, various additives known as additives for organic electronic materials in the technical field of the present invention. For example, the organic material may further include an electron-accepting compound capable of generating an electron acceptor for a charge transporting polymer or oligomer in order to adjust charge transportability; and capable of generating electrons for a charge transporting polymer or oligomer An electron donating compound which acts as a donor; a radical polymerization initiator which acts as a polymerization initiator for a charge transporting polymer or oligomer, a cationic polymerization initiator, and the like. When the organic electronic material contains a hole transporting polymer or oligomer and further contains an electron accepting compound, it is preferable from the viewpoint of easily obtaining excellent hole transportability.

(electron accepting compound)

As the electron accepting compound, specifically, any of an inorganic substance and an organic substance can be used. For example, the electron-accepting compound described in Japanese Laid-Open Patent Publication No. 2003-233162, and the Japanese Patent Publication No. Hei. No. 2006-23310, and the like. Super Brønsted acid compounds and derivatives. Further, for example, a phosphonium salt containing at least one selected from the group consisting of cations and at least one selected from the following anions can be used. When the charge transporting polymer or oligomer has a substituent capable of being polymerized, a phosphonium salt can be preferably used 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 salt ion, imidazolium salt ion, pyrrolidinium salt ion, and quinolinium salt ion. , imidium ion, aminium ion, oxonium ion, pyrylium ion, chromenium ion , xanthylium ion, strontium ion, strontium ion, tropylium ion, cation with transition metal, etc., preferably carbene ion, ammonium ion, benzene Ammonium ion, amine sulfonium salt ion, strontium ion, strontium ion, cycloheptatrienium salt ion, and the like. From the viewpoint of coexisting charge transporting property and storage stability, an ammonium ion, an anisidine salt, a cerium ion, a cerium ion or the like is more preferable, and a cerium ion is more preferable.

(anion)

The anion may, for example, be a halogen ion such as F ^- , Cl ^- , Br ^- or I ^- ; OH ^- ; ClO ₄ ^- ; FSO ₃ ^- , ClSO ₃ ^- , CH ₃ SO ₃ ^- , C ₆ H ₅ SO ₃ ^- , CF ₃ SO ₃ ^- and other sulfonic acid ions; HSO ₄ ^- , SO ₄ ^2- and other sulfate ions; HCO ₃ ^- , CO ₃ ^2- and other carbonate ions; H ₂ PO ₄ ^- , HPO ₄ ^2- , PO ₄ ^3- phosphate phosphates; PF ₆ ^- , PF ₅ OH ^- and other fluorophosphate ions; [(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] - and the like fluorophosphate ions such as _{fluoroalkyl; (CF 3 SO 2) 3} C -, (CF 3 SO 2) 2 N - methyl and other fluoroalkyl sulfonic acyl anion (fluoroalkanesulfonyl Methion ion) and fluorocarbon sulfonium iodide ion; BF ₄ ^- , B (C ₆ F ₅ ) ₄ ^- , B (C ₆ H ₄ CF ₃ ) ₄ ^- and other boric acid ions; SbF ₆ ^- , SbF ₅ OH ^- isoflurane ion; AsF ₆ ^- , AsF ₅ OH ^- and other fluorine arsenate ions; AlCl ₄ ^- , BiF ₆ ^- and the like. Among them, preferred are: PF ₆ ^- , PF ₅ OH ^- and the like fluorophosphate ions; [(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 ] ^- isofluoroalkylfluorophosphate ion; (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₂ N ^- isofluranesulfonylmethyl anion and halothane sulfonate醯imino ion; BF ₄ ^- , B (C ₆ F ₅ ) ₄ ^- , B (C ₆ H ₄ CF ₃ ) ₄ ^- and other boric acid ions; SbF ₆ ^- , SbF ₅ OH ^- and other fluoroantimonic acid ions Etc., more preferably boric acid ions.

As the electron accepting compound, it is preferred to use an onium salt having an anion having an electrophilic substituent. Specific examples of the compound include the following compounds.

When the electron-accepting compound is used, the content thereof is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the organic electronic material. It is preferably 0.5% by mass or more. In addition, from the viewpoint of maintaining good film formability, the content thereof is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less based on the total mass of the organic electronic material.

<Ink composition>

In the embodiment of the present invention, the ink composition contains the organic electronic material and the solvent of the above embodiment. The solvent can use a solvent capable of forming a coating layer using an organic electronic material. It is preferred to use a solvent capable of dissolving the organic electronic material. The organic layer can be easily formed by a simple method such as a coating method by using an ink composition.

[solvent]

The solvent may, for example, be water or an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol; alkanes such as pentane, hexane, and octane; and cyclic alkanes such as cyclohexane; benzene, toluene, xylene, and mesitylene; An aromatic hydrocarbon such as tetrahydronaphthalene or diphenylmethane; an aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate; 2-Dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3- An aromatic ether such as dimethylanisole or 2,4-dimethylanisole; an aliphatic ester such as ethyl acetate, n-butyl acetate, ethyl lactate or n-butyl lactate; phenyl acetate; Aromatic esters such as phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; N,N-dimethylformamide, N,N-dimethyl A guanamine-based solvent such as guanamine; dimethyl hydrazine, tetrahydrofuran, acetone, chloroform, dichloromethane, 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 the oligomer to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably It is an amount of 0.5% by mass or more. Further, the content of the solvent is the following: the ratio of the charge transporting polymer or the oligomer to the solvent is preferably 10% by mass or less, more preferably The amount of 5% by mass or less is more preferably 3% by mass or less.

(other additives)

The ink composition may further contain other various additives. Specific examples of the various additives include, for example, a polymerization inhibitor, a stabilizer, a thickener, a gelling agent, a flame retardant, an antioxidant, an anti-reducing agent, an oxidizing agent, a reducing agent, a surface modifying agent, an emulsifier, and a defoaming agent. Agent, dispersant, surfactant, and the like.

<organic layer>

In the embodiment of the present invention, the organic layer is formed using the organic electronic material or the ink composition of the above embodiment. The organic layer is a layer containing an organic electronic material. The organic electronic material is contained in the organic layer in the form of an organic electronic material itself; a form of a derivative derived from an organic electronic material such as a polymer, a reactant, a decomposition product, or the like. When the ink composition is used, the organic layer can be favorably formed by a coating method. The method of coating the ink composition may, for example, spin coating method; casting method; dipping method; letterpress printing, relief printing, offset printing, lithography, letterpress offset printing, screen printing, gravure printing, etc. A conventional method such as a printing method such as an inkjet method. Further, when the organic layer is formed by a coating method, after the ink composition is applied, the resulting coating layer can be dried by a hot plate or an oven to remove the solvent.

When the charge transporting polymer or oligomer has a substituent capable of being polymerized, since the coating layer can be hardened by polymerization, it is easy to further add an organic layer by a coating method to obtain a plurality of layers. Chemical. The charge transporting polymer or oligomer starts to be polymerized, and generally, a method such as illumination or heating is used. Although it is not particularly limited, it is preferably a method of heating from the viewpoint of a simple process.

When using the method of illuminating, it is possible to use: a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a light-emitting diode, and sunlight. light source. The wavelength of the light to be irradiated is, for example, 200 to 800 nm.

When heating, a heating device such as a heating plate or an oven can be used. The heating temperature and the heating time can be adjusted within a range in which the polymerization reaction can be sufficiently performed. Although not particularly limited, the heating temperature is preferably 300 ° C or lower, more preferably 250 ° C or lower, further preferably 200 ° C or lower. By setting the temperature range as described above, it is possible to apply various substrates. Further, from the viewpoint of accelerating the polymerization rate of the coating layer, the heating temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher, further preferably 60 ° C or higher. From the viewpoint of improving productivity, the heating time is preferably 2 hours or shorter, more preferably 1 hour or shorter, further preferably 30 minutes or shorter. Further, from the viewpoint of allowing the polymerization to proceed completely, the heating time is preferably 1 minute or longer, more preferably 3 minutes or longer, and still more preferably 5 minutes or longer.

The thickness of the organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and still more preferably 3 nm or more from the viewpoint of improving the efficiency of transporting the holes. Further, from the viewpoint of lowering the electric resistance of the organic layer, the thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, further preferably 100 nm or less.

<organic electronic components>

An organic electronic device according to an embodiment of the present invention includes at least the organic layer of the above embodiment. The organic electronic component may, for example, be an organic electroluminescence (organic EL) device, an organic thin film solar cell, an organic light-emitting transistor or the like. The organic electronic component preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

<Organic EL element>

A specific embodiment of the organic EL device will be described as an example of an organic electronic component. An organic EL device according to an embodiment of the present invention has an organic layer formed using an organic electronic material. The organic EL device usually has a substrate, at least a pair of anodes and cathodes, and a light-emitting layer, and may have other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer, as needed. An embodiment of the organic EL device has an organic layer as a light-emitting layer and other functional layers. A preferred embodiment of the organic EL device 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 device. Fig. 1 is a view showing the structure of an organic EL element having a plurality of organic layers composed of a light-emitting layer 1 and a plurality of other functional layers. In the figure, reference numeral 2 denotes an anode, reference numeral 3 denotes a hole injection layer, reference numeral 4 denotes a cathode, and reference numeral 5 denotes an electron injection layer. Further, reference numeral 6 denotes a hole transport layer, reference numeral 7 denotes an electron transport layer, and reference numeral 8 denotes a substrate. Each layer will be described in detail below.

(lighting layer)

The material used for the light-emitting layer may be a low molecular compound or a polymer or an oligomer, and a dendrimer or the like can also be used. Examples of the low molecular weight compound that emits fluorescence include hydrazine, coumarin, rubrene, quinacridone, and pigment laser pigments (for example, rhodamine, DCM1 (4- (dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran,4-(dicyanomethylidene)-2-methyl-6-(4-dimethylaminostyryl)- 4H-pyran), aluminum complex (for example, tris(8-hydroxyquinolinato)aluminum (III) (Alq3)), stilbene, derivatives thereof, etc. . Fluorescent polymers or oligomers can be preferably utilized: polyfluorene, polyphenylene, poly(styrene) (PPV), poly(vinylcarbazole) (PVK), fluorene-benzothiazepine An azole copolymer, a ruthenium-triphenylamine copolymer, such derivatives, and mixtures thereof.

On the other hand, in recent years, in order to increase the efficiency of organic EL devices, phosphorescent organic EL devices have been actively developed. The phosphorescent organic EL device can utilize not only the singlet energy but also the triplet energy, and theoretically can increase the internal quantum yield up to 100%. In a phosphorescent organic EL device, a metal complex phosphorescent material is doped into a host material to extract phosphorescent light as a phosphorescent dopant, and the metal complex phosphorescent material contains heavy metals such as platinum and rhodium (see MA). Baldo et al., Nature, vol. 395, p. 151 (1998), MABaldo et al., Applied Pyhsics Letters, vol. 75, p. 4 (1999), M. A. Baldo et al., Nature, vol. 403, p. 750 (2000)).

In the organic EL device of 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, the Ir complex may, for example, be a blue-emitting FIr(pic) [bis[(4,6-difluorophenyl)pyridine-N,C ² ]pyridinecarboxylic acid ruthenium (bis ((4) ,6-difluorophenyl)pyridinato-N,C ² )picolinatoiridium)(III)], Ir(ppy) ₃ for green luminescence [face ginseng (2-phenylpyridine) hydrazine (refer to the aforementioned MABaldo et al., Nature, Vol.403, p.750(2000)), or (btp) ₂ Ir(acac){bis[2-(2'-benzo[4,5-α]thienyl)pyridine-N, which is red-emitting, C ³ 〕 (acetamidine) 铱 ( (see Adachi et al., Appl. Phys. Lett., 78 no. 11, 2001, 1622), Ir(piq) ₃ [paran (1-phenylisoquinoline) ) 铱] and so on.

As the Pt complex, for example, 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum (2,3,7,8, which is red-emitting) is used. 12,13,17,18-octaethyl-21H, 23H-porphin platinum, PtOEP) and the like. The phosphorescent material can use a low molecular compound or a dendrite species, such as a rhodium core dendrimer. In addition, such derivatives can also be preferably used.

Further, when the phosphor layer contains a phosphorescent material, it preferably contains a host material in addition to the phosphorescent material. As the host material, a low molecular compound or a high molecular compound can be used, and a dendrimer or the like can also be used.

As the low molecular compound, for example, α-NPD (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine), CBP (4,4'-bis(carbazole-) can be used. 9-yl)biphenyl), mCP (1,3-bis(9-carbazolyl)benzene), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethyl Biphenyl) and so on. As the polymer compound, for example, poly(vinylcarbazole), polyphenylene, polyfluorene or the like can be used. In addition, such derivatives can also be used.

The light-emitting layer can be formed by a vapor deposition method or can be formed by a coating method.

When formed by a coating method, an organic EL element can be manufactured inexpensively, and is preferable. When the light-emitting layer is formed by a coating method, it can be carried out by applying a solution to a desired substrate by a conventional method, the solution comprising a phosphorescent material and a host material as needed. Examples of the coating method include a spin coating method; a casting method; a dipping method; a plate printing method such as letterpress printing, die printing, offset printing, lithography, letterpress offset printing, screen printing, and gravure printing; A printing method such as an inkjet method or the like.

(cathode)

As the cathode material, for example, a metal or a metal such as Li, Ca, Mg, Al, In, Cs, Ba, Mg/Ag, LiF, or CsF is preferable. gold. The form of formation of the cathode is not particularly limited, and can be carried out by a conventional method.

(anode)

As the anode, a metal (for example, Au) or another material having a metal conductivity can be used. Other materials include, for example, an oxide (for example, ITO: indium oxide/tin oxide) and a conductive polymer (for example, polythiophene-polystyrenesulfonic acid mixture (PEDOT: PSS)). The form of formation of the anode is not particularly limited, and can be carried out by a conventional method.

(other functional layers)

The organic EL element preferably has at least one layer selected from the group consisting of a light-emitting layer as a functional layer: a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. . In the embodiment, it is preferable to include at least one of a hole injection layer and a hole transport layer. A representative functional layer will be described below.

(hole injection layer, hole transport layer)

The organic EL element preferably has an organic layer as at least one of a hole injection layer and a hole transport layer, and the organic layer is formed using the organic electronic material of the above embodiment. In one embodiment, the organic EL element preferably has an organic layer as a hole transporting layer, and the organic layer is formed using the organic electronic material of the above embodiment. In this embodiment, the hole transport layer can be easily formed by an ink composition containing an organic electronic material. When the organic EL element further has a hole injection layer, the hole injection layer is not particularly limited, and the technical field to which the present invention pertains can be used. The well-known materials are formed. It is also possible to use the organic electronic material of the above embodiment in the hole injection layer.

In another embodiment, the organic EL device preferably has an organic layer as a hole injection layer, and the organic layer is formed using the organic electronic material of the above embodiment. In this embodiment, the hole injection layer can be easily formed by an ink composition containing an organic electronic material. When the organic EL element further has a hole transport layer, the hole transport layer is not particularly limited and can be formed using materials well known in the art to which the present invention pertains. The organic electronic material of the above embodiment can also be used in the hole transport layer.

In one embodiment, the layer of the hole injection layer/hole transport layer can be easily formed by coating the ink composition to form a coating layer, and then hardening the coating layer to form a hole injection layer, and then forming the hole injection layer. After the ink composition is applied onto the hole injection layer to form a coating layer, it is dried or hardened.

(electron transport layer, electron injection layer)

The manner in which the electron transport layer and the electron injection layer are formed can be carried out in accordance with methods well known in the art to which the present invention pertains. Materials which can be used in forming the electron transport layer and/or the electron injecting layer include, for example, a phenanthroline derivative (for example, 2,9-dimethyl-4,7-diphenyl-1,10-morpholine (BCP)). a bipyridine derivative, a nitro-substituted anthracene derivative, a diphenylphenylhydrazine derivative, a thiopyran dioxide derivative; a heterocyclic tetracarboxylic anhydride such as naphthalene or naphthoquinone; a carbodiimide; a mercapto methane derivative, a quinodimethane and an anthrone derivative, an oxadiazole derivative (for example, 2-(4-biphenyl)-5-(4-tri-butylphenyl-1,3, 4-oxadiazole) (PBD)), benzimidazole derivative (1,3,5-paran (1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi)), aluminum complex (e.g., VIII (8-hydroxyquinoline) aluminum (III) (Alq ₃ ), bis(2-methyl-8-quinoline)-4-phenylphenol aluminum (III) (BAlq)), and the like. Further, the following thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom in the above oxadiazole derivative; quinoxaline which is known as an electrophilic group can also be used. a cyclic quinoxaline derivative or the like.

(substrate)

The substrate that can be used for the organic EL device is not particularly limited, and may be a substrate such as glass or a resin film. In one embodiment, it is preferable to use a flexible substrate known as a flexible substrate in the technical field of the present invention. An example of the flexible substrate is, for example, a substrate comprising at least one selected from the group consisting of a film glass, an aluminum foil, and a resin film. Further, the substrate is preferably transparent. From such a viewpoint, for example, a glass substrate, a quartz substrate, a substrate containing a light-transmitting resin film, or the like is preferable. In particular, when a light-transmissive resin film is used as the substrate, it is particularly preferable because it is excellent in transparency, and it is easy to impart flexibility to the organic EL element.

The resin film may, for example, be a film composed of polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyether oxime (PES), or polyether oxime. Imine, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimine, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) Wait.

When a resin film is used, an inorganic substance such as cerium oxide or tantalum nitride may be applied to the resin film in order to suppress penetration of water vapor, oxygen, or the like. Further, the resin film may be used singly or in combination of plural kinds and used in a plurality of layers.

(seal)

The organic EL element can be sealed by extending the life in order to reduce the influence of external gas. Further, as a material used for sealing, glass, epoxy resin, acrylic resin, plastic film such as PET or PEN, inorganic materials such as cerium oxide and tantalum nitride, and the like can be used.

The method of sealing is not particularly limited, and the following method can be used, for example, a method of directly forming on an organic EL element by vacuum deposition, sputtering, a coating method, or the like; or glass or by an adhesive; A method in which a plastic film is bonded to an organic EL element.

(light color)

The luminescent color of the organic EL element is not particularly limited, and the white light-emitting element is preferably used for various lighting devices such as home lighting, interior lighting, clocks, or liquid crystal backlights.

Regarding white light-emitting elements, it is currently difficult to display white light by a single material. Therefore, white light emission is currently obtained by using a plurality of kinds of luminescent materials to simultaneously emit and combine colors of a plurality of luminescent colors. The combination of the plurality of luminescent colors is not particularly limited, and examples thereof include a combination of illuminating maximum wavelengths including three colors of blue, green, and red, and illuminating poles of two colors of blue, yellow, yellow-green, and orange. A combination of large wavelengths. Further, the control of the luminescent color can be performed by adjusting the type and amount of the phosphor material.

<display element, lighting device, display device>

In the embodiment of the present invention, the light-emitting element includes the organic EL element of the above embodiment. For example, the above-described organic EL element is used as an element corresponding to each pixel of red, green, and blue (RGB), that is, a color display element can be obtained. The pixel formation method includes a simple matrix type in which each of the organic EL elements arranged in the panel is directly driven using electrodes arranged in a matrix shape, and an active matrix type in which a thin film transistor is disposed on each element and drive. Although the structure of the simple matrix type is simple, since the number of vertical pixels has a limit, it is preferably used for displaying characters and the like. Since the active matrix type has a low driving voltage and a small current, and can obtain a bright high-definition image, it can be preferably used as a high-grade display.

Further, an illuminating device according to an embodiment of the present invention includes the organic EL element of the above embodiment. Further, the display device according to the embodiment of the present invention includes the illumination device and a liquid crystal element as a display means. A display device can be produced which uses the illumination device as a backlight (white light source) and uses a liquid crystal element as a display means, that is, a liquid crystal display device. In such a configuration, in the conventional liquid crystal display device, only the backlight is replaced by the illumination device, and the liquid crystal element portion can be transferred to a conventional technique.

[Examples]

Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the following examples.

<Pd Catalyst Modulation>

In a hand-held working chamber in a nitrogen atmosphere, ginseng (diphenylmethyleneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature, and after adding anisole (15 mL), stirring was carried out. 30 minutes. Similarly, ginseng (tertiary butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, and after adding anisole (5 mL), it was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to prepare a catalyst. All solvents were degassed by bubbling with nitrogen for 30 minutes or more before use.

<Synthesis of Charge Transporting Polymer 1>

The following monomer A1 (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 further added thereto. Pd catalyst solution (7.5 mL). After stirring for 30 minutes, a 10% aqueous solution of tetraethylammonium hydroxide (20 mL) was added. All solvents were degassed by bubbling with nitrogen for 30 minutes or more before use. The mixture was heated to reflux for 2 hours. All operations up to this point were carried out in a stream of nitrogen.

After completion of the reaction, the organic layer was washed with water, and then the organic layer was poured into methanol-water (9:1). The resulting precipitate was recovered by suction filtration and washed with methanol-water (9:1). After the resulting precipitate was dissolved in toluene, it was reprecipitated from methanol. The obtained precipitate was recovered by suction filtration, dissolved in toluene, and a metal adsorbent ("Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer" manufactured by Strem Chemicals Co., Ltd., 200 mg with respect to the polymer 100 mg was added thereto. After that, stir for one night. After the completion of the stirring, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was concentrated using a rotary evaporator. After the concentrate was dissolved in toluene, it was reprecipitated from methanol-acetone (8:3). The precipitate formed was recovered by suction filtration and washed with methanol-acetone (8:3). The resulting precipitate was vacuum dried to obtain a charge transporting polymer 1.

The obtained charge transporting polymer 1 had a number average molecular weight of 7,800 and a weight average molecular weight of 31,000. The charge transporting polymer 1 has a structural unit (1a) (derived from the monomer A1), a structural unit (2b) (derived from the monomer B1), and a structural unit (1d) having a glycidyl group (derived from a monomer) D1), and the ratio of each structural unit is 45.5%, 18.2%, and 36.4%.

The number average molecular weight and the weight average molecular weight were measured by using GPC (in terms of polystyrene) using tetrahydrofuran (THF) as a solution. The measurement conditions are as follows.

Liquid feeding pump: L-6050 Hitachi High-Technologies Co., Ltd.

UV-Vis Detector: L-3000 Hitachi High-Technologies Co., Ltd.

Pipe column: Gelpack ^(R) GL-A160S/GL-A150S Hitachi Chemical Co., Ltd.

Lysate: THF (for HPLC, no stabilizer) and Guangchun Pharmaceutical Industry Co., Ltd.

Flow rate: 1mL/min

Column temperature: room temperature

Molecular Weight Standard Material: Standard Polystyrene

<Synthesis of Charge Transporting Polymer 2>

The above-mentioned monomer A1 (5.0 mmol), the following monomer B2 (2.0 mmol), the above-mentioned monomer D1 (1.0 mmol), the following monomer D2 (3.0 mmol), and anisole were placed in a three-necked round bottom flask. (20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 2 is carried out. The obtained 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 has a structural unit (1a) (derived from the monomer A1), a structural unit (6b) (derived from the monomer B2), and a structural unit (1d) having a glycidyl group (derived from the monomer D1) And a structural unit (1d) having an alkyl group (derived from the monomer D2), and the ratio of each structural unit is 45.5%, 18.2%, 9.1%, and 27.3%.

<Synthesis of Charge Transporting Polymer 3>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the following monomer C1 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the charge transporting polymer 3 is synthesized. The obtained charge transporting polymer 3 had a number average molecular weight of 8,800 and a weight average molecular weight of 25,700. Charge transporting polymer 3 has structural unit (1a) (derived from Monomer A1), structural unit (6b) (derived from monomer B2), structural unit (1c) (derived from monomer C1), and structural unit (1d) having epoxy propyl group (derived from monomer D1) And, the ratio of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 4>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the following monomer C2 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 4 is carried out. The obtained charge transporting polymer 4 had a number average molecular weight of 6,600 and a weight average molecular weight of 30,000. The charge transporting polymer 4 has a structural unit (1a) (derived from the monomer A1), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C2), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 5>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the following monomer C3 (3.0 mmol), the aforementioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, the synthesis of the charge transporting polymer 5 is carried out in the same manner as the synthesis of the charge transporting polymer 1. The obtained charge transporting polymer 5 had a number average molecular weight of 7,400 and a weight average molecular weight of 26,200. The charge transporting polymer 5 has a structural unit (1a) (derived from the monomer A1), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C3), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 6>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B1 (2.0 mmol), the above-mentioned monomer C1 (3.0 mmol), the aforementioned monomer D1 (1.0 mmol), and anisole (20 mL) were placed in a three-necked round bottom flask. Further, the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 6 is carried out. The obtained 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 has a structural unit (1a) (derived from the monomer A1), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C1), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 7>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B1 (2.0 mmol), the above-mentioned monomer C2 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole (20 mL) were placed in a three-necked round bottom flask. Further, the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 7 is carried out. The obtained 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 has a structural unit (1a) (derived from the monomer A1), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C2), and an epoxy group. Propyl structural unit (1d) (from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 8>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B1 (2.0 mmol), the above-mentioned monomer C3 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole (20 mL) were placed in a three-necked round bottom flask. Further, the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 8 is carried out. The obtained 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 has a structural unit (1a) (derived from the monomer A1), a structural unit (2b) (derived from the monomer B1), a structural unit (1c) (derived from the monomer C3), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 9>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B1 (2.0 mmol), the following monomer D3 (3.0 mmol), the aforementioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, in the same manner as the synthesis of the charge transporting polymer 1, the synthesis of the charge transporting polymer 9 is carried out. The obtained charge transporting polymer 9 had a number average molecular weight of 30,900 and a weight average molecular weight of 123,000. The charge transporting polymer 9 has a structural unit (1a) (source) From monomer A1), structural unit (6b) (derived from monomer B2), structural unit (1d) (derived from monomer D3), and structural unit (1d) having epoxy propyl group (derived from monomer D1) And, the ratio of each structural unit is 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 10>

The following monomer A2 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the above-mentioned monomer D2 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, the synthesis of the charge transporting polymer 10 is carried out in the same manner as the synthesis of the charge transporting polymer 1. The resulting charge transporting polymer 10 had a number average molecular weight of 17,500 and a weight average molecular weight of 54,800. The charge transporting polymer 10 has the following structural unit: a structural unit having a fluorene structure (derived from the monomer A2), a structural unit (6b) (derived from the monomer B2), and a structural unit having an alkyl group (1d) (source) From monomer D2), and structural unit (1d) having a propylene group (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 11>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the following monomer C4 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, the synthesis of the charge transporting polymer 11 is carried out in the same manner as the synthesis of the charge transporting polymer 1. The obtained charge transporting polymer 11 had a number average molecular weight of 24,800 and a weight average molecular weight of 62,000. The charge transporting polymer 11 has a structural unit (1a) (derived from the monomer A1), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C4), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 12>

The above-mentioned monomer A1 (5.0 mmol), the above-mentioned monomer B2 (2.0 mmol), the following monomer C5 (3.0 mmol), the above-mentioned monomer D1 (1.0 mmol), and anisole were added to a three-necked round bottom flask ( 20 mL), the prepared Pd catalyst solution (7.5 mL) was further added. Then, the synthesis of the charge transporting polymer 12 is carried out in the same manner as the synthesis of the charge transporting polymer 1. The resulting charge transporting polymer 12 had a number average molecular weight of 29,000 and a weight average molecular weight of 58,800. The charge transporting polymer 12 has a structural unit (1a) (derived from the monomer A1), a structural unit (6b) (derived from the monomer B2), a structural unit (1c) (derived from the monomer C5), and an epoxy group. The structural unit (1d) of propyl (derived from monomer D1), and the ratio of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Production of Organic EL Element>

[Example 1]

The charge transporting polymer 1 (10.0 mg), the following electron-accepting compound 1 (0.5 mg), and toluene (2.3 mL) were mixed in a nitrogen atmosphere to prepare an ink composition. The ink composition was spin-coated on a glass substrate having a pattern of 3,000 min ^-1 and patterned into a 1.6 mm wide glass substrate, and then heated on a hot plate at 220 ° C for 10 minutes to be hardened to form a hole injection layer. (25nm).

Then, charge transporting polymer 3 (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 formed as described above at a number of revolutions of 3,000 min ^-1 , and then heated on a hot plate at 200 ° C for 10 minutes to be hardened to form a hole transport layer (40 nm). ). The hole transport layer can be formed without dissolving the hole injection layer.

The substrate obtained above was transferred to a vacuum evaporation machine, and CBP:Ir(ppy) ₃ (94:6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (stepwise) were sequentially deposited by vapor deposition. After forming a film of 0.8 nm) and Al (100 nm), a sealing treatment was performed to prepare an organic EL device.

[Embodiment 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 step of forming the hole transporting layer.

[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 step of forming the hole transporting layer.

[Example 4]

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 11 in the step of forming the hole transporting layer.

[Example 5]

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 12 in the step of forming the hole transporting layer.

[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 step of forming the hole transporting layer.

[Comparative 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 9 in the step of forming the hole transporting layer.

[Comparative 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 10 in the step of forming the hole transporting layer.

The layer configuration of the organic EL elements obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is shown in Table 1.

When a voltage was applied to the organic EL elements obtained in Examples 1 to 5 and Comparative Examples 1 to 3, green light emission was confirmed. Determination of the emission luminance of each element 1,000cd / m ² of the light emission efficiency and brightness at the beginning of 5,000cd / m ² of the emission lifetime (luminance half-life). The measurement results are shown in Table 2.

As shown in Table 2, an organic electronic material which is an embodiment of the present invention is used in the hole transport layer, that is, an element having high luminous efficiency, excellent driving stability, and long life can be obtained.

[Embodiment 6]

The charge transporting polymer 6 (10.0 mg), the above electron-accepting compound 1 (0.5 mg), and toluene (2.3 mL) were mixed in a nitrogen atmosphere to prepare an ink composition. The ink composition was spin-coated on a glass substrate having a pattern of 3,000 min ^-1 and patterned into a 1.6 mm wide glass substrate, and then heated on a hot plate at 220 ° C for 10 minutes to be hardened to form a hole injection layer. (25nm).

Then, charge transporting polymer 2 (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 formed as described above at a number of revolutions of 3,000 min ^-1 , and then heated on a hot plate at 200 ° C for 10 minutes to be hardened to form a hole transport layer (40 nm). ). The hole transport layer can be formed without dissolving the hole injection layer.

The substrate obtained above was transferred to a vacuum evaporation machine, and CBP:Ir(ppy) ₃ (94:6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (stepwise) were sequentially deposited by vapor deposition. After forming a film of 0.8 nm) and Al (100 nm), a sealing treatment was performed to prepare an organic EL device.

[Embodiment 7]

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

[Embodiment 8]

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

The layer constitution of the organic EL elements obtained in Examples 6 to 8 and Comparative Example 1 is shown in Table 3.

When a voltage was applied to the organic EL elements obtained in Examples 6 to 8 and Comparative Example 1, green light emission was confirmed. Determination of the emission luminance of each element 1,000cd / m ² of the light emission efficiency and brightness at the beginning of 5,000cd / m ² of the emission lifetime (luminance half-life). The measurement results are shown in Table 4.

As shown in Table 4, an organic electronic material which is an embodiment of the present invention is used for the hole injection layer, that is, an element having high luminous efficiency, excellent driving stability, and long life can be obtained.

<Production of White Organic EL Element (Lighting Device)>

[Embodiment 9]

The charge transporting polymer 1 (10.0 mg), the above electron-accepting compound 1 (0.5 mg), and toluene (2.3 mL) were mixed in a nitrogen atmosphere to prepare an ink composition. The ink composition was spin-coated on a glass substrate having a pattern of 3,000 min ^-1 and patterned into a 1.6 mm wide glass substrate, and then heated on a hot plate at 220 ° C for 10 minutes to be hardened to form a hole injection layer. (25nm).

Then, 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 formed as described above at a number of revolutions of 3,000 min ^-1 , and then heated on a hot plate at 200 ° C for 10 minutes to be hardened to form a hole transport layer (40 nm). ). The hole transport layer can be formed without dissolving the hole injection layer.

Then, under nitrogen, CDBP (15.0 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 number of revolutions of 3,000 min ^-1 , and then dried on a hot plate at 80 ° C for 5 minutes to dry to form a light-emitting layer (40 nm). The light-emitting layer can be formed without dissolving the hole transport layer.

The glass substrate was transferred to a vacuum vapor deposition machine, and BAlq (10 nm), TPBi (30 nm), LiF (0.5 nm), and Al (100 nm) were sequentially formed by a vapor deposition method. Then, a sealing treatment was performed to prepare a white organic EL element. The white organic EL element can be used as a lighting device.

[Comparative Example 4]

A white organic EL device was produced in the same manner as in Example 9 except that the charge transporting polymer 4 was changed to the charge transporting polymer 2. The light-emitting layer can be formed without dissolving the hole transport layer. The white organic EL element can be used as a lighting device.

A voltage was applied to the white organic EL device obtained in Example 9 and Comparative Example 4 to measure the light-emitting lifetime (brightness half-life) at an initial luminance of 1,000 cd/m ² . When the luminescence lifetime of Example 9 was set to 1, Comparative Example 4 was 0.72. Further, when the voltage at the time of the light emission luminance of Example 9 was 1,000 cd/m ² , the comparative example 4 was 1.12.

The white organic EL element of Example 9 exhibited excellent luminescence lifetime and driving voltage.

The effects of the embodiments of the present invention have been described above using the embodiments. In addition to the charge transporting polymer used in the examples, It is also possible to obtain an organic EL element having a long life by using the charge transporting polymer described above, and exhibiting an excellent effect.

Claims (15)

An organic electronic material containing a charge transporting polymer or oligomer having a condensed polycyclic aromatic hydrocarbon moiety at at least one terminal of the charge transporting polymer or oligomer, the condensed polycyclic aromatic The hydrocarbon moiety has three or more benzene rings. 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 organic electronic material according to any one of claims 1 to 3, wherein the condensed polycyclic aromatic hydrocarbon moiety comprises a ruthenium moiety, a thick tetraphenyl moiety, a condensed pentabenzene moiety, a phenanthrene moiety, and 1, a group consisting of a 2-benzophenanthrene moiety, a triphenylene moiety, a tetraphene moiety, an anthraquinone moiety, a quinone moiety, a penfen moiety, a quinone site, a pentamole moiety, a hexaspene moiety, a heptapeptide site, and a quinone moiety At least one of the selected ones. The organic electronic material according to any one of claims 1 to 4, wherein the condensed polycyclic aromatic hydrocarbon moiety comprises a condensed polycyclic aromatic hydrocarbon moiety, and the condensed polycyclic aromatic hydrocarbon moiety has 3~ 8 benzene rings. The organic electronic material according to any one of claims 1 to 5 The above-mentioned charge transporting polymer or oligomer further has a substituent capable of undergoing polymerization. An ink composition comprising the organic electronic material according to any one of claims 1 to 6, and a solvent. An organic layer formed using the organic electronic material according to any one of claims 1 to 6 or the ink composition described in claim 7. An organic electronic component having at least one organic layer as claimed in claim 8. An organic electroluminescent device having at least one organic layer as claimed in claim 8. The organic electroluminescent device according to claim 10, further comprising a flexible substrate. The organic electroluminescent device according to claim 10, further comprising a resin film substrate. A display element comprising the organic electroluminescent device according to any one of claims 10 to 12. A lighting device comprising the organic electroluminescent device according to any one of claims 10 to 12. A display device comprising the illumination device according to claim 14 and a liquid crystal element as a display means.