JP5245978B2 - Materials for organic electronics - Google Patents

Description

  The present invention relates to an organic electronics material, an organic electronics element using the organic electronics material, an organic electroluminescence element (hereinafter sometimes referred to as an organic EL element), a display element, and a lighting device.

  Organic electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that can replace conventional inorganic semiconductors based on silicon. ing.

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

  The organic EL element has a configuration in which a thin film of an organic compound is sandwiched between a cathode and an anode. Thin film forming methods are roughly classified into vapor deposition methods and coating methods. The vapor deposition method is a method of forming a thin film on a substrate in a vacuum mainly using a low molecular compound, and commercialization has preceded.

  On the other hand, the coating method is a method of forming a thin film on a substrate using a solution such as ink jet or printing, which is highly efficient in using materials, is suitable for large area and high definition. This is an indispensable technique for EL displays.

  Although organic EL elements using either method have been energetically studied so far, low luminous efficiency, short element life, and high driving voltage are still major problems. As one means for solving this problem, multilayering of organic EL elements is progressing.

  FIG. 1 shows an example of a multilayered organic EL element. In FIG. 1, when the light emitting layer 1 is a layer responsible for light emission, the layer in contact with the anode 2 is referred to as a hole injection layer 3, and the layer in contact with the cathode 4 is referred to as an electron injection layer 5.

  Further, when a different layer exists between the light emitting layer 1 and the hole injection layer 3, it is referred to as a hole transport layer 6. Furthermore, when a different layer exists between the light emitting layer 1 and the electron injection layer 5, it is called the electron transport layer 7. In FIG. 1, 8 is a substrate.

  When film formation is performed by a vapor deposition method, multilayering can be easily achieved by performing vapor deposition while sequentially changing the compounds to be used. On the other hand, in the case of the coating method, in order to increase the number of layers, it is necessary to have a method that does not change the already formed layer when forming a new layer.

  Many organic EL devices by the coating method are formed using a polythiophene: polystyrene sulfonic acid (PEDOT: PSS) hole injection layer, which is formed using an aqueous dispersion, and an aromatic organic solvent such as toluene. The light emitting layer has a two-layer structure. In this case, since the PEDOT: PSS layer is not dissolved in toluene, a two-layer structure can be produced.

  However, when laminating using a similar solvent, the lower layer is dissolved at the time of forming the upper layer, so that it is difficult to form a multilayer in the organic EL element by the coating method. In order to cope with this problem, a technique is known in which a low molecular compound having a polymerizable substituent is applied and the solubility is changed by polymerization to form a multilayer structure (for example, Non-Patent Document 1, Patent Document 1). However, low-molecular compounds have a problem that they are easily crystallized during film formation.

  In addition, in order to solve the low luminous efficiency, short device lifetime, and high driving voltage, the organic EL device has a multilayer structure, a light emitting layer, a hole injection layer, a positive electrode, and the like. Development of materials for forming individual layers such as a hole transport layer is also actively conducted. For example, with respect to the light emitting layer, a phosphorescent light emitting material has been proposed as a material capable of raising the internal quantum yield to 100% in principle. However, studies on the hole injection layer and the hole transport layer are still insufficient, and a material suitable for improving the low luminous efficiency, the short device life, and the high driving voltage is required. .

JP 2006-279007 A

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

  As described above, in order to increase the efficiency, extend the life of the organic EL element, and reduce the driving voltage, it is desirable to make the organic layer multi-layered and to separate the functions of each layer. In order to make an organic layer into a multilayer by using a wet process, it was necessary to prevent the lower layer from being dissolved during the upper film formation. In addition, in order to increase the efficiency, extend the lifetime, and reduce the driving voltage of organic EL elements, in addition to the multilayer structure of the element, materials for forming each layer such as a hole injection layer and a hole transport layer There was a need for improvement.

In view of the above-described problems, the present invention is a material for organic electronics that can be easily multi-layered by a coating method, and can realize high efficiency, long life, and low driving voltage of an organic EL element. Is intended to provide.
It is another object of the present invention to provide an organic electronics element and an organic EL element having a light emission efficiency and a light emission lifetime superior to those of the prior art and a low driving voltage.
Furthermore, an object of the present invention is to provide an excellent display element and lighting device by using these elements.

As a result of intensive studies, the present inventors have used the first hole transport material composed of a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transportability. It has been found that the thin film can be applied stably and easily, and the solubility of the thin film is changed by the polymerization reaction, so that the dissolution of the lower layer during the upper film formation can be suppressed and the organic EL device can be multilayered. It was.
Further, the first positive hole transport material is different from the first positive hole transport material, and the second positive transport material has a work function difference of 0.5 eV or less from the first positive hole transport material. By mixing and using a hole transport material, it is found that when used in an organic electronics element, particularly an organic EL element, the driving voltage can be reduced and the luminous efficiency and the luminous lifetime can be improved, thereby completing the present invention. It came to.

That is, the present invention comprises a mixture containing a first hole transport material and a second hole transport material, and the first hole transport material comprises one or more polymerizable substituents in the molecule. And a polymer or an oligomer having a repeating unit having a hole transporting property, and a difference between a work function of the first hole transporting material and a work function of the second hole transporting material is 0.5 eV or less. The present invention relates to materials for organic electronics.
Moreover, this invention relates to the organic electronics element and organic electroluminescent element which were produced using the said material for organic electronics.
Furthermore, this invention relates to the display element and illuminating device provided with the said organic electroluminescent element.

  By using the material for organic electronics of the present invention, a thin film can be formed stably and easily, and the solubility is changed by a polymerization reaction, so that the organic thin film layer can be easily multilayered by a coating method. Moreover, since the material for organic electronics of this invention is a material excellent in hole transport property, the drive voltage of the organic EL element using this can be reduced. Therefore, the organic electronics material of the present invention is extremely useful for improving the light emission efficiency and lifetime of organic electronic elements, particularly polymer organic EL elements, lowering the driving voltage, and improving productivity. Material. By using the organic EL element of the present invention, a light emitting element and a lighting device having excellent characteristics can be obtained.

It is a schematic diagram which shows an example of the multilayered organic EL element.

  The material for organic electronics of the present invention comprises a mixture containing a first hole transport material and a second hole transport material, and the first hole transport material is capable of being polymerized in one or more molecules in the molecule. A polymer or an oligomer having a substituent and a repeating unit having a hole transporting property, and a difference in work function between the first hole transporting material and the work function of the second hole transporting material is 0.5 eV. It is characterized by the following. Hereinafter, the details of the first hole transport material will be described first.

[First hole transport material]
The first hole transport material is composed of a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transportability. Here, the “repeating unit having hole transportability” is an atomic group having the ability to transport holes, and the details thereof will be described below.

  The repeating unit having the hole transporting property is not particularly limited as long as it is a unit having the ability to transport holes, and preferably has an amine structure having an aromatic ring. General formula (1a), (2a), (3a), (4a), (5a), (6a) etc. are mentioned.

Ar _{1 to} Ar ₃₁ in the general formulas (1a), (2a), (3a), (4a), (5a), or (6a) are each independently a substituted or unsubstituted arylene group or heteroarylene group. Represents. Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic compound having a hetero atom. .

  The arylene group and heteroarylene group may be substituted or unsubstituted. Examples of the arylene group include phenylene, biphenyl-diyl, terphenyl-diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, and examples of the heteroarylene group include Pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, oxazol-diyl, oxadiazole-diyl, thiadiazole-diyl, Examples include triazole-diyl, benzoxazole-diyl, benzooxadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, and benzothiophene-diyl.

  Examples of the arylene group or heteroarylene group which may be substituted or unsubstituted are further shown in the following structural formulas (1) to (30).

Substituents R _{1 to} R _{10 in} the above general formulas (1a), (2a), (3a), (4a), (5a), or (6a), and substituents in the above structural formulas (1) to (30) Although there is no restriction | limiting in particular as R, For example, the following general formula which is -R < ¹ >, -OR < ² >, -SR < ³ >, -OCOR < ⁴ >, -COOR < ⁵ >, -SiR < ⁶ > R < ⁷ > R < ⁸ >, or (poly) ether. (A)

（ただし、Ｒ^１〜Ｒ^１１は、それぞれ独立に、水素原子、炭素数１〜２２個の直鎖、環状若しくは分岐アルキル基、又は、炭素数２〜３０個のアリール基若しくはヘテロアリール基を表し、ａ、ｂ及びｃは、１以上の整数、好ましくは１〜４の整数を表す。）
で表される置換基を挙げることができ、それぞれは同一であっても異なっていてもよい。

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more, preferably an integer of 1 to 4.
And each may be the same or different.

Examples of these substituents include the following substituents.
Examples of -R ¹ include a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, Cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group, phenyl group, naphthyl group, anthryl group, fluorenyl group, furan residue, thiophene residue, pyrrole residue, oxazole Residues, thiazole residues, imidazole residues, pyridine residues, pyrimidine residues, pyrazine residues, triazine residues, quinoline residues, quinoxaline residues can be mentioned.
Examples of —OR ² are hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group, tert-octyloxy group, phenoxy group, 4-tert-butylphenoxy group, 1- Examples thereof include a naphthyloxy group, a 2-naphthyloxy group, and a 9-anthryloxy group.
Examples of —SR ³ include a mercapto group, a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group. it can.
Examples of —OCOR ⁴ include a formyloxy group, an acetoxy group, and a benzoyloxy group.
Examples of —COOR ⁵ include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a phenoxycarbonyl group, and a naphthyloxycarbonyl group.
Examples of —SiR ⁶ R ⁷ R ⁸ include a silyl group, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and the like.
Here, R ^{1 to} R ¹¹ and R may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, and a carboxyl group. Sulfonic acid group, nitro group, aryl group, heteroaryl group and the like. These substituents may be further substituted with a halogen atom, a methyl group or the like.

Among these substituents, the above R _{1 to} R ₁₀ or R are each independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or —OR ² which is a hydrogen atom or represented by —R ^1. The hydroxyl group, alkoxy group, aryloxy group, and heteroaryloxy group represented by are preferable from the viewpoint of polymerization reactivity and heat resistance. That is, the repeating unit having a hole transporting property represented by the above general formula (1a), (2a), (3a), (4a), (5a), or (6a) is unsubstituted, alkyl group represented by R ^1, the aryl group, or has a substituent such as a heteroaryl group, a hydroxyl group represented by -OR ^2, an alkoxy group, an aryloxy group, a substituent such as heteroaryloxy group It is preferable to have.

In the general formula (1a), (2a), or (3a), an arylene group or a heteroarylene group (wherein Ar ₃ , Ar ₈ , Ar ₁₅ ) that is not directly bonded to a nitrogen atom has a solubility or From the viewpoint of chemical stability, the above structural formulas (29) and (30) having a phenylene group, a fluorene-diyl group, a phenanthrene-diyl group, or a condensed ring structure are preferred. In the structural formulas (29) and (30), l, m, and n are each independently an integer of 1 to 5, and preferably 2 to 4. In addition, when the organic electronics material of the present invention is used for a hole transport layer or a hole injection layer of an organic EL element, in order to efficiently confine electrons in the light emitting layer and improve the light emission efficiency, It is desirable that the hole injection layer has a high LUMO level. From this viewpoint, the above structural formulas (29) and (30) having a polycyclic structure are more preferable.

In the general formulas (1a) to (6a), an arylene group or a heteroarylene group (for example, Ar ₁ , Ar ₂ , Ar ₄ in (1a)) directly bonded to a nitrogen atom is used for solubility and chemistry. From the viewpoint of mechanical stability, a phenylene group or a naphthalene-diyl group is preferable.

  In addition, the polymer or oligomer used in the present invention is a copolymerization repeating unit of the above arylene group and / or heteroarylene group in addition to the repeating unit having a hole transporting property in order to adjust the solubility, heat resistance, and electrical characteristics. It may be a copolymer. When having an arylene group and / or a heteroarylene group as a copolymerization repeating unit, from the viewpoint of driving voltage and solubility, the ratio is the number of moles of the repeating unit having hole transportability: the number of moles of the arylene group and the heteroarylene group. Is preferably 1: 2 to 10: 1, more preferably 1: 1 to 5: 1.

In this case, the copolymer may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property.
In addition, the polymer or oligomer used in the present invention may have branching in the main chain and may have three or more terminals.

  The polymer or oligomer used in the present invention has one or more “polymerizable substituents”. From the viewpoint of facilitating lamination, the number is preferably 1 or more, more preferably 2 or more, and still more preferably 2 to 4. Here, the “polymerizable substituent” means a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction, and details thereof will be described below.

  Examples of the polymerizable substituent include a group having a carbon-carbon multiple bond (for example, vinyl group, acetylene group, butenyl group, acryloyl group, acryloyloxy group, acrylamide group, methacryloyl group, methacryloyloxy group, methacrylamide group, An arene group, an allyl group, a vinyloxy group, a vinylamino group, a furyl group, a pyrrole group, a thiophene group, a silole group, etc.), a group having a small ring (for example, a cyclopropyl group, a cyclobutyl group, an epoxy group) Oxetane group, diketene group, episulfide group, etc.), a lactone group, a lactam group, or a group containing a siloxane derivative.

  In addition to the above groups, combinations of groups capable of forming an ester bond or an amide bond can also be used. For example, a combination of an ester group and an amino group, an ester group and a hydroxyl group, or the like.

As the polymerizable substituent, an oxetane group, an epoxy group, a vinyl group, an acryloyloxy group, and a methacryloyloxy group are particularly preferable from the viewpoint of reactivity.
The polymerizable substituent may be introduced as a side chain of the polymer or oligomer, may be introduced at the terminal, or may be introduced at both the side chain and the terminal. Preferably, the polymerizable substituent is introduced at the end of the polymer or oligomer.

  Hereinafter, the details when the polymerizable substituent is introduced at the terminal of the polymer or oligomer will be described. A polymerizable substituent is introduced at the terminal of the polymer or oligomer, and the repeating unit having a hole transporting property is represented by the general formula (1a), (2a), (3a), (4a), (5a), or In the case of any one of (6a), examples of the polymer or oligomer include the following general formula (7a), (8a), (9a), (10a), (11a), or (12a).

〔上記一般式（７ａ）、（８ａ）、（９ａ）、（１０ａ）、（１１ａ）、又は（１２ａ）中、Ａｒ_３２〜Ａｒ_７４は、それぞれ独立に置換若しくは非置換のアリーレン基又はヘテロアリーレン基を表し、Ｅ_１〜Ｅ_１２は、それぞれ独立に、重合可能な置換基を有する基を表し、Ｒ_１１〜Ｒ_２０はそれぞれ独立に、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、ＳｉＲ^６Ｒ^７Ｒ^８、又は（ポリ）エーテルである下記一般式（Ａ）

[In the general formulas (7a), (8a), (9a), (10a), (11a), or (12a), Ar _{32 to} Ar ₇₄ are each independently a substituted or unsubstituted arylene group or heteroarylene. Represents a group, each of E _{1 to} E ₁₂ independently represents a group having a polymerizable substituent, and each of R _{11 to} R ₂₀ independently represents —R ¹ , —OR ² , —SR ³ , —OCOR; ⁴ , -COOR ⁵ , SiR ⁶ R ⁷ R ⁸ , or (poly) ether represented by the following general formula (A)

（ただし、Ｒ^１〜Ｒ^１１は、それぞれ独立に、水素原子、炭素数１〜２２個の直鎖、環状若しくは分岐アルキル基、又は、炭素数２〜３０個のアリール基若しくはヘテロアリール基を表し、ａ、ｂ及びｃは、１以上の整数、好ましくは１〜４の整数を表す。）を表し、ｎは１以上の整数を表す。〕

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more, preferably an integer of 1 to 4, and n represents an integer of 1 or more. ]

The above E _{1 to} E ₁₂ can be polymerized as described above, for example, an alkyl group, an alkoxy group, an aryl group, an arylene group, a heteroaryl group, a heteroarylene group, a group having an arylamine structure, or a group having a combination thereof. A group in which one or more substituents are bonded. Examples of these alkyl groups include -R ¹ and -OR in the substituents R _{1 to} R ₁₀ in the general formulas (1a), (2a), (3a), (4a), (5a), and (6a). The same group as ² is mentioned. As E ₁ to E _12, preferably oxetane group-containing group, for example,

等が例示される。

Etc. are exemplified.

  In the general formulas (7a), (8a), (9a), (10a), (11a), or (12a), the number average of the repeating number n is preferably 2 or more and 100 or less, and preferably 2 or more and 20 or less. Is more preferable. When n is too small, the film-forming stability is lowered, and when it is too large, the change in solubility is small even when a polymerization reaction is carried out, and lamination tends to be difficult.

  The number average molecular weight of the polymer or oligomer used in the present invention is preferably 1,000 or more and 100,000 or less, and more preferably 1,000 or more and 10,000 or less. When the molecular weight is less than 1,000, the film-forming stability is lowered, and when it exceeds 100,000, the change in solubility is small even when a polymerization reaction is carried out, and the lamination tends to be difficult. In addition, the number average molecular weight of a polymer or an oligomer is a number average molecular weight when measured in polystyrene conversion using gel permeation chromatography.

  The polydispersity of the polymer or oligomer used in the present invention is preferably greater than 1.0, more preferably 1.1 or more and 5.0 or less, and most preferably 1.2 or more and 3.0 or less. If the polydispersity is too small, aggregation tends to occur after film formation, and if it is too large, device characteristics tend to deteriorate. The polydispersity of the polymer or oligomer refers to (weight average molecular weight / number average molecular weight) when measured in terms of polystyrene using gel permeation chromatography.

[Production method]
The polymer or oligomer used in the present invention can be produced by various synthetic methods known to those skilled in the art. For example, in the case of producing a polymer or oligomer in which a monomer used for synthesis has an aromatic ring and the aromatic rings are bonded to each other, T. Yamamoto et al., Bull. Chem. Soc. Jap. 51, No. 7, p. 2091 (1978) and M. Zembayashi et al., Tet. Lett. 47, p. 4089 (1977) can be used, but Suzuki (A. Suzuki), Synthetic Communications, Vol. 11, no. 7, p. The method reported in 513 (1981) is common for the production of polymers or oligomers.

  This reaction causes a Pd-catalyzed cross-coupling reaction (usually called “Suzuki reaction”) between an aromatic boronic acid derivative and an aromatic halide, and the corresponding aromatic ring By using for the reaction which couple | bonds together, the polymer or oligomer used by this invention can be manufactured.

This reaction also requires soluble Pd compounds in the form of Pd (II) salts or Pd (0) complexes. Pd (OAc) ₂ and PdCl ₂ (dppf) complexes with 0.01 to 5 mole percent Pd (Ph ₃ P) ₄ , tertiary phosphine ligand, based on aromatic reactants, are generally preferred Pd sources.

This reaction also requires a base, with aqueous alkaline carbonate or bicarbonate being most preferred.
The reaction can also be promoted in a nonpolar solvent using a phase transfer catalyst. As the solvent, N, N-dimethylformamide, toluene, anisole, dimethoxyethane, tetrahydrofuran or the like is used.

[Second hole transport material]
In the organic electronic material of the present invention, the mixture further contains a second hole transport material, and the difference between the work functions of the first hole transport material and the second hole transport material is 0.5 eV. It is characterized by the following. Details of the second hole transport material will be described below.

  The second hole transport material has the ability to transport holes, and the work function difference between the first hole transport material and the second hole transport material (absolute value of the work function difference). However, the work function difference is more preferably 0.4 eV or less, and most preferably 0.3 eV or less. This is because if the work function difference is too large, the drive voltage tends to increase.

  The work function can be measured by irradiating ultraviolet rays onto the surface of each hole transport material having a thickness of 1 nm to 1 μm and measuring the emitted electrons. For example, it can be measured using a surface analysis device AC-1 manufactured by Riken Keiki Co., Ltd. under conditions of an irradiation light quantity of 10 to 200 nW.

  As the second hole transport material, for example, a low molecular compound, a polymer, and an oligomer can be used. From the viewpoint of the thermal stability of the thin film, a polymer or an oligomer is preferred.

The second hole transport material preferably has one or more polymerizable substituents in the molecule, and has one or more substituents identical to the polymerizable substituents of the first hole transport material. More preferably. This is because the first hole transporting material and the second hole transporting material are polymerized and tend to be laminated more easily.
As an example of the polymerizable substituent which the 2nd hole transport material has, the substituent similar to the polymerizable substituent which the 1st hole transport material has can be mentioned.

  When a low molecular compound is used as the second hole transport material, for example, a triphenylamine derivative, TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl) benzidine), α-NPB ( N, N′-diphenyl-N, N′-bis (1-naphthyl) benzidine), carbazole derivatives, CBP (4,4′-Bis (Carbazol-9-yl) -biphenyl), mCP (1,3′- Bis (Carbazol-9-yl) -benzene) and the like.

  When a polymer or oligomer is used as the second hole transport material, for example, a triphenylamine / fluorene copolymer, a triphenylamine / arylene copolymer, polyvinyl carbazole, and the like can be given.

  The second hole transporting material is preferably a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transporting properties. More preferably, it is an oligomer or polymer having one or more substituents identical to the polymerizable substituents of the first hole transporting material and having a repeating unit having a hole transporting property. This is because the thermal stability of the thin film formed by the polymerization reaction tends to be increased while improving the compatibility with the first hole transport material.

  Further, the second hole transporting material is composed of a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transporting property. It is more preferable that the repeating unit possessed is any one of the above general formulas (1a), (2a), (3a), (4a), (5a), or (6a). This is because the hole transportability tends to be high.

  In addition, the polymer or oligomer as the second hole transport material may be any one of the general formulas (7a), (8a), (9a), (10a), (11a), or (12a). Even more preferred. This is because the two hole transport materials tend to have excellent compatibility and hole transport properties by having a similar skeleton to the first hole transport material.

Further, the polymer or oligomer as the second hole transport material is the same as that of the polymer or oligomer as the first hole transport material (7a), (8a), (9a), (10a), ( It is most preferably a material represented by either 11a) or (12a) and having different substituents. In the polymer or oligomer represented by the general formula (7a), (8a), (9a), (10a), (11a), or (12a), for example, introducing a methyl group onto Ar _{32 to} Ar ₇₄ It is possible to change the work function.

[blend]
The material for organic electronics of the present invention comprises a mixture containing a first hole transport material and a second hole transport material. The mixing ratio of the first hole transport material and the second hole transport material is not particularly limited, but from the viewpoint of driving voltage, the weight ratio is the first hole transport material: second hole transport material. The material is preferably 1: 100 to 100: 1, more preferably 5:95 to 95: 5.

[Polymerization initiator]
In addition to the first hole transport material and the second hole transport material, the mixture may further contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it exhibits the ability to polymerize a polymerizable substituent by adding heat, light, microwave, radiation, electron beam, and the like. In addition, the polymerization is preferably initiated by heating, and more preferably initiated by light irradiation (hereinafter referred to as a photoinitiator).

  The photoinitiator is not particularly limited as long as it exhibits the ability to polymerize a polymerizable substituent by irradiation with light of 200 nm to 800 nm. For example, when the polymerizable substituent is an oxetane group. Is preferably an iodonium salt, a sulfonium salt, or a ferrocene derivative from the viewpoint of reactivity, and examples thereof include the following compounds, that is, the general formula (32).

  The photoinitiator may be used in combination with a photosensitizer in order to improve photosensitivity. Examples of the photosensitizer include anthracene derivatives and thioxanthone derivatives.

  Further, the blending ratio of the polymerization initiator is preferably in the range of 0.1% by weight to 10% by weight and more preferably in the range of 0.2% by weight to 8% by weight with respect to the total weight of the mixture. The range of 0.5 to 5% by weight is particularly preferable. When the blending ratio of the polymerization initiator is less than 0.1% by weight, stacking tends to be difficult, and when it exceeds 10% by weight, device characteristics tend to deteriorate.

  In addition to the polymer or oligomer, the mixture may further contain a carbon material such as carbon nanotube or fullerene in order to adjust electric characteristics.

[Method for forming thin film]
In order to form various layers used for an organic electronics element or the like by using the organic electronics material of the present invention, for example, a solution containing the organic electronics material of the present invention is, for example, an ink jet method, a casting method, or an immersion method. Coating on a desired substrate by a known method such as a printing method such as a printing method, letterpress printing, intaglio printing, offset printing, flat plate printing, letterpress reverse printing, screen printing, gravure printing, spin coating, etc. It can be carried out by advancing the polymerization reaction of the polymer or oligomer by heat treatment or the like, and changing (curing) the solubility of the coating layer. By repeating such operations, it is possible to increase the number of polymer organic electronics elements and organic EL elements.

The coating method as described above can be usually carried out in a temperature range of -20 to + 300 ° C, preferably 10 to 100 ° C, more preferably 15 to 50 ° C.
The solvent used in the above solution is not particularly limited, and examples thereof include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, anisole, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and ethyl cellosolve acetate. be able to.

  In addition, a light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a light emitting diode, or sunlight can be used for the light irradiation.

  Moreover, the said heat processing can be performed on a hotplate or in oven, and can be implemented at the temperature range of 0- + 300 degreeC, Preferably it is 20-250 degreeC, More preferably, it is 80-200 degreeC.

[Organic electronics elements, organic EL elements]
The material for organic electronics of the present invention can be used alone or in combination with other materials as a functional material for organic electronics elements.
Further, the organic electronics material of the present invention is a hole injection layer, a hole transport layer, an electron block layer, a light-emitting layer, a hole block layer, an electron transport of an organic EL element described later alone or in combination with other materials. It can be used as a layer or an electron injection layer.

Furthermore, it can be used for an organic electronics element or an organic EL element even when various additives are added.
As an additive, for example, a metal complex containing a central metal such as Ir or Pt is used for a light emitting layer of an organic EL element, and a triphenylamine derivative is used for a hole injection layer or a hole transport layer. , Electron acceptors such as tetracyanoquinodimethane, and various oxidizing agents can be used.

The organic electronics material of the present invention can be preferably used as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like of an organic EL element described later. It is more preferable to use as a hole injection layer, a hole transport layer, and a light emitting layer, and it is most preferable to use as a hole injection layer and a hole transport layer. Specifically, it is an organic electroluminescent element formed by laminating at least an anode, a hole injection layer and / or a hole transport layer, a light emitting layer and a cathode, and the hole injection layer and / or the hole transport layer. The organic electroluminescent element which is a layer formed with the material for organic electronics of this invention is mentioned.
The thickness of these layers is not particularly limited, but is preferably 10 to 100 nm, more preferably 20 to 60 nm, and still more preferably 20 to 40 nm.

  The organic electronics element and the organic EL element of the present invention may be provided with a layer containing the material for organic electronics of the present invention, and the structure thereof is not particularly limited. In addition, the general structure of organic EL includes, for example, those disclosed in US Pat. No. 4,539,507, US Pat. No. 5,151,629, etc. The organic EL element is disclosed in, for example, International Publication No. 90/13148, European Patent Publication No. 04384861, and the like.

  These usually include an electroluminescent layer (light-emitting layer) between a cathode (cathode) and an anode (anode) in which at least one of the electrodes is transparent. Further, one or more electron injection layers and / or electron transport layers are inserted between the electroluminescent layer (light emitting layer) and the cathode, one or more hole injection layers and / or hole transport layers Is inserted between the electroluminescent layer (light emitting layer) and the anode. Hereinafter, each layer will be described in detail.

[Light emitting layer]
The material used for the light emitting layer may be a low molecular compound, a polymer or an oligomer, and a dendrimer or the like can also be used. Examples of low molecular weight compounds that utilize fluorescence include perylene, coumarin, rubrene, quinacudrine, dye laser dyes (eg, rhodamine, DCM1, etc.), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ )), Stilbene, and derivatives thereof. Polymers or oligomers that utilize fluorescence include polyfluorene, polyphenylene, polyphenylene vinylene (PPV), polyvinyl carbazole (PVK), fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, and derivatives thereof. And a mixture can be suitably used.

  On the other hand, in recent years, phosphorescent organic EL devices have been actively developed in order to increase the efficiency of organic EL devices. In the phosphorescent organic EL element, not only singlet state energy but also triplet state energy can be used, and the internal quantum yield can be increased to 100% in principle. In a phosphorescent organic EL element, phosphorescence emission can be extracted by doping a host material with a metal complex phosphorescent material containing a heavy metal such as platinum or iridium as a dopant emitting phosphorescence (MA Baldo et al. , Nature, vol.395, p.151 (1998), MA Baldo et al., Applied Physics Letters, vol.75, p.4 (1999), MA Baldo et al., Nature, vol. .403, p.750 (2000), etc.).

Also in the organic EL device of the present invention, it is preferable to use a phosphorescent material for the light emitting layer from the viewpoint of high efficiency. As the phosphorescent material, a metal complex containing a central metal such as Ir or Pt can be preferably used. Specifically, as an Ir complex, for example, FIr (pic) [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate] that emits blue light and green light are emitted. Ir (ppy) ₃ [Tris (2-phenylpyridine) iridium] (see MA Baldo et al., Nature, vol. 403, p. 750 (2000), etc.) or Adachi et al. , Appl. Phys. Lett. 78no. (Btp) ₂ Ir (acac) {bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] iridium (acetyl-) Acetonate)}, Ir (piq) ₃ [tris (1-phenylisoquinoline) iridium] and the like.

Examples of the Pt complex include 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-forminplatinum (PtOEP) that emits red light.
The phosphorescent material can be a small molecule or a dendrite species, such as an iridium nucleus dendrimer. Moreover, these derivatives can also be used conveniently.

Further, in the case where a phosphorescent material is included in the light emitting layer, it is preferable that a host material is included in addition to the phosphorescent material.
The host material may be a low molecular compound or a high molecular compound, and a dendrimer or the like can also be used.

  Examples of the low molecular weight compound include CBP (4,4′-Bis (Carbazol-9-yl) -biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), CDBP (4,4′-Bis). (Carbazol-9-yl) -2,2′-dimethylbiphenyl) and the like, for example, polyvinyl carbazole, polyphenylene, polyfluorene and the like can be used, and derivatives thereof can also be used.

The light emitting layer may be formed by a vapor deposition method or a coating method.
When forming by the apply | coating method, an organic EL element can be manufactured cheaply and it is more preferable. In order to form a light emitting layer by a coating method, a solution containing a phosphorescent material and, if necessary, a host material is used, for example, an ink jet method, a casting method, a dipping method, a relief printing, an intaglio printing, an offset printing, a flat printing, a relief printing. It can be carried out by applying on a desired substrate by a known method such as a printing method such as reverse offset printing, screen printing or gravure printing, or spin coating method.

[cathode]
The cathode material is preferably a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF.

[anode]
As the anode material, metal (for example, Au) or other material having metal conductivity, for example, oxide (for example, ITO: indium oxide / tin oxide), conductive polymer (for example, polythiophene-polystyrenesulfonic acid mixture) (PEDOT: PSS)) can also be used.

[Electron transport layer, electron injection layer]
Examples of the electron transport layer and the electron injection layer include a phenanthroline derivative (for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)), a bipyridine derivative, a nitro-substituted fluorene derivative, and a diphenylquinone derivative. , Thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives (2- (4-Biphenylyl) -5 (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (II ) _(Alq 3)) and the like. Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can be used.

[substrate]
The substrate that can be used in the organic EL device of the present invention is not particularly limited to glass, plastic, and the like, but is preferably transparent and is preferably a flexible substrate. For example, glass, quartz, a light transmissive resin film and the like are preferably used. When a resin film is used, flexibility can be given to the organic EL element, which is particularly preferable.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films made of (TAC), cellulose acetate propionate (CAP) and the like.

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

  The emission color in the organic EL element of the present invention is not particularly limited, but the white light-emitting element is preferable because it can be used for various lighting devices such as home lighting, interior lighting, clocks, and liquid crystal backlights.

  As a method of forming a white light emitting element, since it is currently difficult to show white light emission with a single material, a plurality of light emitting colors can be simultaneously emitted and mixed using a plurality of light emitting materials. White luminescence is obtained. A combination of a plurality of emission colors is not particularly limited. However, a combination of three emission maximum wavelengths of blue, green, and red, a complementary color relationship such as blue and yellow, yellow green and orange is used. The thing containing two light emission maximum wavelengths is mentioned. The emission color can be controlled by adjusting the type and amount of the phosphorescent material.

  Moreover, the organic EL element of this invention can be used for display elements, such as an organic EL display and a liquid crystal display. When used in a liquid crystal display, a liquid crystal element as a display means and an organic EL element as a backlight may be combined.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these.
(Monomer Synthesis Example 1)

丸底フラスコに、３−エチル−３−ヒドロキシメチルオキセタン（５０ｍｍｏｌ）、４−ブロモベンジルブロミド（５０ｍｍｏｌ）、ｎ−ヘキサン（２００ｍＬ）、テトラブチルアンモニウムブロミド（２．５ｍｍｏｌ）及び５０重量％水酸化ナトリウム水溶液（３６ｇ）を加え、窒素下、７０℃で６時間加熱撹拌した。

In a round bottom flask, 3-ethyl-3-hydroxymethyloxetane (50 mmol), 4-bromobenzyl bromide (50 mmol), n-hexane (200 mL), tetrabutylammonium bromide (2.5 mmol) and 50 wt% sodium hydroxide An aqueous solution (36 g) was added, and the mixture was heated with stirring at 70 ° C. for 6 hours under nitrogen.

  After cooling to room temperature (25 ° C.), 200 mL of water was added, and the product was extracted with n-hexane. After the solvent was distilled off, the residue was purified by silica gel column chromatography and reduced pressure distillation to obtain 9.51 g of monomer A having a polymerizable substituent as a colorless oil. Yield 67% by weight.

1H-NMR (300 MHz, CDCl ₃ , δ ppm); 0.86 (t, J = 7.5 Hz, 3H), 1.76 (t, J = 7.5 Hz, 2H), 3.57 (s, 2H) , 4.39 (d, J = 5.7 Hz, 2H), 4.45 (d, J = 5.7 Hz, 2H), 4.51 (s, 2H), 7.22 (d, J = 8. 4Hz, 2H), 7.47 (d, J = 8.4Hz, 2H)

<Synthesis of an oligomer having a polymerizable substituent and a repeating unit having a hole transporting property>
(Oligomer synthesis example 1)

密閉可能なフッ素樹脂製容器に、２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．４ｍｍｏｌ）、４，４’−ジブロモ−４”−ｎ−ブチルトリフェニルアミン（０．３２ｍｍｏｌ）、重合可能な置換基を有するモノマーＡ（０．１６ｍｍｏｌ）、テトラキストリフェニルホスフィンパラジウム（０．００８ｍｍｏｌ）、２Ｍ炭酸カリウム水溶液（５．３ｍＬ）、Ａｌｉｑｕａｔ３３６（０．４ｍｍｏｌ）及びアニソール（４ｍＬ）を入れ、窒素雰囲気下、密閉容器中、マイクロ波を照射して９０℃、２時間加熱撹拌した。

In a sealable fluororesin container, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.4 mmol) 4,4′-dibromo-4 ″ -n-butyltriphenylamine (0.32 mmol), monomer A having a polymerizable substituent (0.16 mmol), tetrakistriphenylphosphine palladium (0.008 mmol), 2M An aqueous potassium carbonate solution (5.3 mL), Aliquat 336 (0.4 mmol) and anisole (4 mL) were added, and the mixture was heated and stirred at 90 ° C. for 2 hours in a sealed container under a nitrogen atmosphere by irradiation with microwaves.

  The reaction solution was poured into a methanol / water mixed solvent (9: 1), and the precipitated oligomer was separated by filtration. The reprecipitation was repeated twice to purify, and thus an oligomer A having a polymerizable substituent and a repeating unit having a hole transporting property was obtained. The number average molecular weight of the obtained oligomer was 4652 in terms of polystyrene, and the polydispersity was 2.0. The number average of n was 5.6.

  A toluene solution (1 wt%) of this oligomer was spin-coated on a quartz plate at 3000 rpm in nitrogen and dried at 80 ° C. for 5 minutes to obtain a thin film having a thickness of 40 nm. The work function was 5.21 eV when this thin film was measured in the atmosphere using a surface analyzer AC-1 manufactured by Riken Keiki under conditions of an irradiation light amount of 50 nW and a measurement range of 4.6 to 6.0 eV.

(Oligomer synthesis example 2)

モノマーとしてとして２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．４ｍｍｏｌ）、モノマーＢ（０．３２ｍｍｏｌ）及び重合可能な置換基を有するモノマーＡ（０．１６ｍｍｏｌ）を用い、オリゴマー合成例１と同様の方法でオリゴマーＢを合成した。得られたオリゴマーの数平均分子量はポリスチレン換算で７９７１、多分散度は２．１、ｎの数平均は１０．６であった。仕事関数は５．０５ｅＶであった。

As the monomer, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.4 mmol), monomer B (0. 32 mmol) and a monomer A (0.16 mmol) having a polymerizable substituent, and oligomer B was synthesized in the same manner as in oligomer synthesis example 1. The number average molecular weight of the obtained oligomer was 7971 in terms of polystyrene, the polydispersity was 2.1, and the number average of n was 10.6. The work function was 5.05 eV.

<Production of organic EL element: application example as hole transport layer>
Example 1
A PEDOT: PSS dispersion (Stark Vitec, AI4083 LVW142) is spin-coated at 1500 rpm on a glass substrate patterned with ITO to a width of 1.6 mm, and is heated and dried in air at 200 ° C. for 10 minutes. Thus, a hole injection layer (40 nm) was formed. The subsequent operation was performed in a dry nitrogen environment.

  Next, oligomer A (3.1 mg), oligomer B (1.3 mg) obtained above on the hole injection layer, chemical formula (38)

で表される光開始剤（０．１３ｍｇ）及びトルエン（１．２ｍＬ）を混合した塗布溶液を、３０００ｒｐｍでスピンコートした後、メタルハライドランプを用いて光照射（３Ｊ／ｃｍ^２）し、ホットプレート上で１８０℃、６０分間加熱して硬化させ、正孔輸送層（４０ｎｍ）を形成した。

A coating solution in which a photoinitiator (0.13 mg) and toluene (1.2 mL) represented by the formula (1) is mixed is spin-coated at 3000 rpm, and then irradiated with light using a metal halide lamp (3 J / cm ² ) to form a hot plate. It was heated and cured at 180 ° C. for 60 minutes to form a hole transport layer (40 nm).

Next, the obtained glass substrate was transferred into a vacuum evaporation machine, and CBP + Ir (piq) ₃ (film thickness 40 nm), BAlq (film thickness 5 nm), Alq ₃ (film thickness 30 nm), LiF (film thickness 0.5 nm), Al (film thickness 100 nm) was deposited in this order.

  After forming the electrode, the glass substrate is moved into a dry nitrogen environment without opening to the atmosphere, and the sealing glass and ITO substrate in which 0.4 mm of counterbore is added to 0.7 mm non-alkali glass are used as a photocurable epoxy resin. Sealing was performed by laminating the film, and a polymer type organic EL device having a multilayer structure was produced. Subsequent evaluation was performed in the atmosphere at room temperature (25 ° C.).

When a voltage was applied using ITO as a positive electrode and Al as a cathode of this organic EL element, red light emission was observed at about 6 V, and the current efficiency at a luminance of 5000 cd / m ² was 7.1 cd / A. The current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard Co., and the luminance was measured using a luminance meter Richard 1980B manufactured by Photo Research.

Moreover, as a lifetime characteristic, it was 120 hours when the brightness | luminance was measured with Topcon BM-7, applying a constant current, and the time for a brightness | luminance to halve from initial brightness (1000 cd / m < ² >) was measured.

(Comparative Example 1)
An organic EL device was produced in the same manner as in Example 1 except that the hole transport layer was not formed. When a voltage was applied to this organic EL element, red light emission was observed at about 6 V, the current efficiency at a luminance of 5000 cd / m ² was 5.0 cd / A, and Example 1 was 1.4 times that of Comparative Example 1. Efficiency was obtained.
Further, when the lifetime characteristics were measured, the luminance was reduced by half in 10 hours, and in Example 1, a lifetime that was 12 times longer than that in Comparative Example 1 was obtained.

<Production of organic EL element: application example as hole injection layer>
(Example 2)
On a glass substrate patterned with a width of 1.6 mm of ITO, oligomer A (0.4 mg) obtained above, oligomer B (4.0 mg), photoinitiator (chemical formula (38)) (0.13 mg) and A coating solution mixed with toluene (500 μL) was spin-coated at 3000 rpm. The subsequent operation was performed in a dry nitrogen environment.

Thereafter, light irradiation (3 J / cm ² ) was performed using a metal halide lamp and cured by heating on a hot plate at 120 ° C. for 15 minutes and at 180 ° C. for 60 minutes to form a hole injection layer (40 nm). .

  Next, a toluene solution (1.0 weight) of a mixture comprising polymer 1 (75 parts by weight), polymer 2 (20 parts by weight), and polymer 3 (5 parts by weight) represented by the following structural formula is formed on the hole injection layer. %) Was spin-coated at 3000 rpm, and heated on a hot plate at 80 ° C. for 5 minutes to form a polymer light emitting layer (film thickness 80 nm). The hole injection layer and the light emitting layer could be laminated without dissolving each other. Further, in the same manner as in Example 1, an electron transport layer, an electrode, and the like were formed and sealed.

When a voltage was applied using ITO as a positive electrode and Al as a cathode of the organic EL element, green light emission was observed at about 3V. At a luminance of 5000 cd / m ^2, the current efficiency was 8.1 cd / A, and the drive voltage was 5.2V.

Moreover, as a lifetime characteristic, when the constant current of 12 mA / cm < ² > current density was applied and the brightness | luminance half time was measured, it was 110 hours.
Furthermore, the difference (voltage increase) between the driving voltage immediately after applying the constant current and when the luminance was reduced to half was 0.2V.

<Production of organic EL element: application example as hole transport layer>
(Example 3)
An organic EL device was produced in the same manner as in Example 1 by changing the mixing ratio of the oligomer A and the oligomer B (Table 1).

(Comparative Example 2)
A PEDOT: PSS dispersion (Stark Vitec, AI4083) is spin-coated at 1500 rpm on a glass substrate patterned with a width of 1.6 mm of ITO, and is heated and dried in air at 200 ° C./10 minutes on a hot plate. Thus, a hole injection layer (40 nm) was formed. Thereafter, in the same manner as in Example 2, formation of a light emitting layer, formation of an electron transport layer, an electrode, and the like were performed, and sealing was performed to produce an organic EL element.

(Comparative Example 3 When work function difference is greater than 0.5 eV)
For the hole injection layer, a coating solution in which oligomer A (2.2 mg), 9-phenylcarbazole (2.2 mg), photoinitiator (chemical formula (38)) (0.13 mg) and toluene (500 μL) were mixed was used. Formed. Thereafter, in the same manner as in Example 2, formation of a light emitting layer, formation of an electron transport layer, an electrode, and the like were performed, and sealing was performed to produce an organic EL element. The work function of 9-phenylcarbazole was 5.80 eV, and the work function difference from oligomer A was 0.59 eV.

(Comparative Example 4 when only one kind of hole transport material is used)
The hole injection layer was formed using a coating solution in which oligomer B (4.4 mg), photoinitiator (chemical formula (38)) (0.13 mg) and toluene (500 μL) were mixed. Thereafter, in the same manner as in Example 2, formation of a light emitting layer, formation of an electron transport layer, an electrode, and the like were performed, and sealing was performed to produce an organic EL element.

  Table 1 summarizes the results of current efficiency, drive voltage, luminance half time, and voltage increase for the above Examples 1 to 3 and Comparative Examples 1 to 4.

  As shown in Table 1, the organic electronics material of the present invention was effective in improving current efficiency, lowering driving voltage, improving life characteristics, and suppressing voltage increase during driving.

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

Claims (27)

It consists of a mixture containing a first hole transport material and a second hole transport material, and the first hole transport material has one or more polymerizable substituents in the molecule and a hole transport property. repeating made units and from polymers or oligomers having, met the first organic electronic material difference in the work function of the hole transport material is less than 0.5eV work function of the second hole transport material having And
The repeating unit having a hole transporting property of the polymer or oligomer is represented by any of the following general formulas (1a), (2a), (3a), (4a), (5a), or (6a). A material for organic electronics having a structure.

[ Wherein , Ar _{1 to} Ar ₃₁ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and R _{1 to} R ₁₀ each independently represent —R ¹ , —OR ² , —SR. ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more. ] The organic electronic material according to claim 1 , wherein the polymerizable substituent of the polymer or oligomer is any one of an oxetane group, an epoxy group, a vinyl group, an acryloyloxy group, and a methacryloyloxy group. The organic electronics material according to claim 1 or 2 , wherein the polymer or oligomer has a polymerizable substituent at a terminal. The material for organic electronics according to any one of claims 1 to 3 , wherein the polymer or oligomer has a number average molecular weight of 1,000 or more and 100,000 or less. The organic electronics material according to any one of claims 1 to 4 , wherein the polydispersity of the polymer or oligomer is greater than 1.0. The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (7a).

[In the formula, Ar _{32 to} Ar ₃₇ each independently represent a substituted or unsubstituted arylene group or heteroarylene group, and E ₁ and E ₂ each independently represent a group having a polymerizable substituent. , R ₁₁ are each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (8a).

[Wherein, Ar _{38 to} Ar ₄₅ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and E ₃ and E ₄ each independently represent a group having a polymerizable substituent. , R ₁₂ and R ₁₃ are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (9a).

[In the formula, Ar _{46 to} Ar ₅₄ each independently represent a substituted or unsubstituted arylene group or heteroarylene group, and E ₅ and E ₆ each independently represent a group having a polymerizable substituent. , R ₁₄ and R ₁₅ are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (10a).

[Wherein, Ar _{55 to} Ar ₅₉ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and E ₇ and E ₈ each independently represent a group having a polymerizable substituent. , R ₁₆ are each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (11a).

[Wherein, Ar _{60 to} Ar ₆₆ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and E ₉ and E ₁₀ each independently represents a group having a polymerizable substituent. , R ₁₇ and R ₁₈ are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

[However, R ^{1 to} R ¹¹ each independently represents a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c each represents an integer of 1 or more. N represents an integer of 1 or more. ] The organic electronics material according to any one of claims 1 to 5 , wherein the polymer or oligomer has a structure represented by the following general formula (12a).

[In the formula, Ar _{67 to} Ar ₇₄ each independently represent a substituted or unsubstituted arylene group or heteroarylene group, and E ₁₁ and E ₁₂ each independently represent a group having a polymerizable substituent. , R ₁₉ and R ₂₀ are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic compound according to any one of claims 6 to 11 , wherein the number average of n in the general formulas (7a), (8a), (9a), (10a), (11a) or (12a) is 2 to 20. Materials for electronics. The organic electronics according to any one of claims 1 to 12 , wherein the second hole transport material has one or more polymerizable substituents identical to the polymerizable substituents of the first hole transport material. Materials. It said second hole transport material has one or more polymerizable substituent in the molecule, and any one of claims 1 to 13 comprising a polymer or oligomer having a repeating unit having a hole transporting property The material for organic electronics described in 1. The second hole transport material is composed of a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transportability, and has the hole transportability. repeating unit represented by the following general formula (1a), (2a), (3a), (4a), (5a), or to any one of claims 1 to 14 having a structure represented by any one of (6a) The material for organic electronics as described.

[Wherein, Ar _{1 to} Ar ₃₁ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and R _{1 to} R ₁₀ each independently represent —R ¹ , —OR ² , —SR. ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more. ] The second hole transport material comprises a polymer or oligomer having one or more polymerizable substituents in the molecule and a repeating unit having hole transportability, and the polymer or oligomer is The organic electronic device according to any one of claims 1 to 15 , which has a structure represented by any one of the general formulas (7a), (8a), (9a), (10a), (11a), and (12a). material.

[In the formula, Ar _{32 to} Ar ₇₄ each independently represents a substituted or unsubstituted arylene group or heteroarylene group, and E _{1 to} E ₁₂ each independently represents a group having a polymerizable substituent. , R _{11 to} R ₂₀ are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , or the following general formula (A)

(However, R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. , A, b and c represent an integer of 1 or more), and n represents an integer of 1 or more. ] The organic electronic material according to claim 1 , wherein the mixture further contains a polymerization initiator. Organic electronic devices manufactured using the organic electronic material according to any one of claims 1 to 17. The organic electroluminescent device manufactured using the organic electronic material according to any one of claims 1 to 17. It is an organic electroluminescent element formed by laminating at least an anode, a hole injection layer, a light emitting layer, and a cathode, and the hole injection layer uses the organic electronics material according to any one of claims 1 to 17. An organic electroluminescent element which is a formed layer. It is an organic electroluminescent element formed by laminating at least an anode, a hole transport layer, a light emitting layer, and a cathode, and the hole transport layer uses the organic electronics material according to any one of claims 1 to 17. An organic electroluminescent element which is a formed layer. The organic electroluminescence device according to any one of claims 19 to 21 , wherein the emission color is white. The organic electroluminescent element according to any one of claims 19 to 22 , wherein the organic electroluminescent element has a substrate, and the substrate is a flexible substrate. The organic electroluminescent element according to any one of claims 19 to 23 , wherein the organic electroluminescent element has a substrate, and the substrate is a resin film. Display device comprising the organic electroluminescent element according to any one of claims 19-24. Lighting apparatus comprising the organic electroluminescence element according to any one of claims 19-24. A display device comprising the lighting device according to claim 26 and a liquid crystal device as a display means.

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