JP2010118653A - Organic electronics material, organic electronics element and organic electroluminescence element using the material, and display device, illumination device, display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronics material which is easily multilayered, has excitation energy larger than heretofore and adaptive to all colors, and large carrier mobility of an electron and a positive hole, to provide an organic electronics element which has excellent light emission efficiency and light emission life, and to provide an organic electroluminescence element. <P>SOLUTION: The organic electronics material contains at least a compound having at least one quaternary carbon in which all substituents are aromatic rings or heterocyclic derivatives and the substituents do not form ring structure and at least one polymerizable substituent, the organic electronics element and the organic electroluminescence element use the organic electronic material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  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.

Organic EL elements are roughly classified into two types, low molecular organic EL elements and polymer organic EL elements, depending on the materials and film forming methods used.
High-molecular organic EL elements are composed of high-molecular materials, and can be used for simple film formation such as printing and ink-jet compared to low-molecular organic EL elements that require vacuum-based film formation. Therefore, it is an indispensable element for future large-screen organic EL displays.

  Although research has been conducted energetically for both low-molecular organic EL elements and high-molecular organic EL elements, low luminous efficiency and short element lifetime are still serious problems. As one means for solving this problem, multilayering is performed in the low molecular organic EL element.

FIG. 1 shows an example of a multilayered organic EL element. In FIG. 1, the layer responsible for light emission is described as the light emitting layer 1, and the layer in contact with the anode 2 is described as the hole injection layer 3, and the layer in contact with the cathode 4 is described as the electron injection layer 5.
Furthermore, when a different layer exists between the light emitting layer 1 and the hole injection layer 3, it is described as a hole transport layer 6, and when a different layer exists between the light emitting layer 1 and the electron injection layer 5. And described as an electron transport layer 7. In FIG. 1, reference numeral 8 denotes a substrate.

Since the low molecular organic EL element is formed by vapor deposition, multilayering can be easily achieved by performing vapor deposition while sequentially changing the compounds to be used.
On the other hand, since a polymer type organic EL element is formed using a wet process such as printing or ink jetting, in order to make a multilayer, a layer already formed is not changed when a new layer is formed. A method is needed.

  In fact, most polymer type organic EL devices use a hole injection layer made of polythiophene: polystyrene sulfonic acid (PEDOT: PSS), which is formed using an aqueous dispersion, and an aromatic organic solvent such as toluene. Most devices have a two-layer structure of light emitting layers for film formation. In this case, since the PEDOT: PSS layer is not dissolved in toluene, that is, not dissolved in the dispersion for forming the light emitting layer, a two-layer structure can be produced.

  The reason why it is difficult to further increase the number of layers in the polymer organic EL element is that the lower layer dissolves when lamination is performed with a similar solvent. In order to cope with this problem, an element having a three-layer structure using compounds having greatly different solubilities has been proposed (for example, see Non-Patent Document 1).

  In addition, an element having a three-layer structure having a hole transport layer utilizing a photocuring reaction has also been reported (for example, see Non-Patent Document 2). In addition, a device having a three-layer structure having a hole transport layer utilizing a crosslinking reaction of a siloxane compound has also been reported (for example, see Non-Patent Document 3). Although these are important techniques, there are problems that materials that can be used are limited from the viewpoint of solubility, and that siloxane compounds are unstable to moisture in the air, and none of them have sufficient device characteristics.

  On the other hand, in order to increase the efficiency of organic EL elements, phosphorescent organic EL elements have been actively developed. In the phosphorescent organic EL element, not only singlet state energy but also triplet state energy can be used, and the internal quantum yield can be increased to 100% in principle. In a phosphorescent organic EL device, phosphorescence is extracted by doping a host material with a metal complex light emitting material containing a heavy metal such as platinum or iridium as a phosphorescent emitting dopant (for example, Non-Patent Document 4 and Non-Patent Document 5). And Non-Patent Document 6).

The light emission of this phosphorescent dopant has dependence on the host material.
The basic performance required for the host material includes a hole transport property and an electron transport property, and the host material has a high triplet state energy level. Generally, CBP (4,4′- Carbazole derivatives such as Bis (Carbazol-9-yl) -biphenyl) are preferably used.

  However, the energy level of the triplet state of CBP is insufficient to accommodate all colors (particularly blue). For example, in Non-Patent Document 7, the energy of the triplet state is introduced by introducing a methyl group into the biphenyl moiety of CBP. The level has been improved.

  However, as a film formation method for a low molecular compound such as CBP, a vapor deposition method is generally used. When a film is formed by direct coating, crystallization is likely to proceed, causing defects called dark spots, and heat resistance. There was a problem of low nature.

US Pat. No. 4,539,507 US Pat. No. 5,151,629 International Publication No. 90/13148 European Patent Publication No. 04384861 JP 2003-068466 A

Y. Goto, T. Hayashida, M. Noto, Idw '04 Proceedings of The 11th International Display Workshop, 1343-1346 (2004) Kengo Hirose, Daisuke Kumaki, Nobuaki Koike, Satoshi Kuriyama, Seiichiro Ikehata, Shizushi Tokito, 53rd Joint Physics Conference on Applied Physics, 26p-ZK-4 (2006) H. Yan, P. Lee, N.R. Armstrong, A. Graham, G. A. Evmenenko, P. Dutta, T. J. Marks, J. Am. Chem. Soc., 127, 3172-4183 (2005) M.A.Baldo et al., Nature, vol. 395, p. 151 (1998) M.A.Baldo et al., Applied Physics Letters, vol. 75, p. 4 (1999) M.A.Baldo et al., Nature, vol. 403, p. 750 (2000) Yoshiyuki Kaori, Noriko Ueda, Hiroshi Kita, Konica Minolta Technology Report, 2004 edition

In order to increase the efficiency and life of organic EL elements, it is desirable to divide the organic layers into layers and separate the functions of each layer. However, the organic layers can be formed using a wet process that is easy to form even in large areas. In order to increase the number of layers, it is necessary to have sufficient solubility in a solvent at the time of application, and as described above, it is necessary to prevent the lower layer from being dissolved at the time of forming the upper layer.
Further, in order to cope with all color (especially blue) light emission and to improve the reliability and efficiency of the element, it has been an important issue to increase the excitation energy of the organic layer material (material for organic electronics).

  In view of the above-described problems, an object of the present invention is to provide a material for organic electronics that is easily multi-layered and has a higher excitation energy than conventional ones.

  Moreover, this invention provides the organic electronics element and organic EL element which have the outstanding luminous efficiency and the light emission lifetime by using this organic electronics material for a light emitting layer host material, a hole injection layer, or a hole transport layer material. For the purpose.

As a result of intensive studies, the present inventors have found that a compound or mixture having one or more polymerizable substituents and containing a tetraarylmethane structure has a large excitation energy and can stably and easily form a thin film. It was found that the solubility can be changed by the polymerization reaction, and further, this compound was found useful as a material for organic electronics, and the present invention was completed.
That is, the means for solving the above problems are as follows.

(1) All the substituents are aromatic rings or heterocyclic derivatives, and at least a compound having at least one quaternary carbon that does not form a cyclic structure and at least one polymerizable substituent. A material for organic electronics, comprising:

(2) The material for organic electronics according to (1), wherein the compound includes at least one tetraarylmethane structure.

(3) The organic electronics material according to (1) or (2), wherein the compound includes a structure represented by the following general formula (1a).

〔式中、Ｒは、それぞれ独立に、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は下記一般式（２ａ）〜（４ａ）

[Wherein, R is ^{independently, -R 1, -OR 2, -SR} 3, -OCOR 4, -COOR 5, -SiR 6 R 7 R 8 or the following general formula (2a) ~ (4a)

（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基又は炭素数２〜３０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以上の整数を表す。）を表す。Ａｒは、それぞれ独立に、置換若しくは非置換のアリーレン基、ヘテロアリーレン基を表す。Ｅは、それぞれ独立に、前記Ｒと同義、又は重合可能な置換基を含む基を示す。〕

^(Wherein, R 1 ^{to R 11} represents a hydrogen atom, a linear, cyclic or branched alkyl group or an aryl group or heteroaryl group having 2 to 30 carbon atoms having 1 to 22 carbon atoms, a, b and c, Represents an integer of 1 or more. Ar independently represents a substituted or unsubstituted arylene group or heteroarylene group. E independently represents a group having the same meaning as R or a polymerizable substituent. ]

(4) The organic electronics material according to any one of (1) to (3), wherein the compound is a polymer or an oligomer.

(5) The material for organic electronics according to (4), wherein the polymer or oligomer has a number average molecular weight of 1,000 or more and 100,000 or less.

(6) The material for organic electronics according to (4) or (5), wherein the polydispersity of the polymer or oligomer is greater than 1.0.

(7) The material for organic electronics according to any one of (4) to (6), wherein the polymer or oligomer has a unit having a tetraarylmethane derivative and charge transportability.

〔式中、Ｒは、それぞれ独立に、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は一般式（２ａ）〜（４ａ） (8) The organic electronics material according to any one of (4) to (7), wherein the polymer or oligomer is represented by the following general formulas (5a) to (7a).

[In the formula, each R is independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ or general formulas (2a) to (4a).

（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基又は炭素数２〜３０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以上の整数を表す。）。Ｗは、電荷輸送性を有するユニットを表す。Ｅは、それぞれ独立に、前記Ｒと同義、又は重合可能な置換基を含む基を示す。ｎは整数を表す。〕

^(Wherein, R 1 ^{to R 11} represents a hydrogen atom, a linear, cyclic or branched alkyl group or an aryl group or heteroaryl group having 2 to 30 carbon atoms having 1 to 22 carbon atoms, a, b and c, Represents an integer of 1 or more). W represents a unit having a charge transporting property. E independently represents a group having the same meaning as R or a polymerizable substituent. n represents an integer. ]

(9) The material for organic electronics according to (8), wherein the number average of n in the general formulas (5a) to (8a) is 2 to 20.

(10) The polymerizable substituent according to any one of (1) to (9), wherein the polymerizable substituent is one selected from the group consisting of an oxetane group, an epoxy group, a vinyl group, an acrylate group, and a methacrylate group. Materials for organic electronics.

(11) The material for organic electronics according to any one of (4) to (9), wherein a polymerizable substituent in the polymer or oligomer is introduced at a terminal of the polymer or oligomer.

(12) The material for organic electronics according to any one of claims 1 to 11, further comprising an iridium complex or a platinum complex.

(13) An organic electronics element produced using the organic electronics material according to any one of (1) to (12).

(14) An organic electroluminescent device produced using the organic electronic material according to any one of (1) to (12).

(15) An organic electroluminescent device comprising at least an anode, a light emitting layer, and a cathode, wherein the light emitting layer is formed of the organic electronics material according to any one of (1) to (12). An organic electroluminescent element which is a layer.

(16) An organic electroluminescent element formed by laminating at least an anode, a hole injection layer, a light emitting layer, and an anode, wherein the hole injection layer is the organic material according to any one of (1) to (12) An organic electroluminescence device which is a layer formed of a material for electronics.

(17) An organic electroluminescence device comprising at least an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode, wherein the hole transport layer is any one of (1) to (12) An organic electroluminescent device which is a layer formed of the organic electronic material according to claim 1.

(18) The organic electroluminescent element as described in any one of (14) to (17), which emits white light.

(19) The organic electroluminescent element according to any one of (14) to (18), wherein the substrate of the organic electroluminescent element is a flexible substrate.

(20) The organic electroluminescent element according to any one of (14) to (19), wherein the substrate of the organic electroluminescent element is a resin film.

(21) A display device comprising the organic electroluminescent device according to any one of (14) to (20).

(22) An illumination device comprising the organic electroluminescence element according to any one of (14) to (20).

(23) A display device comprising the illumination device according to (22) and a liquid crystal element as display means.

  According to the present invention, a thin film can be formed stably and easily, and the solubility is changed by the polymerization reaction. Therefore, the organic thin film layer can be easily formed in a multi-layer and has a large excitation energy. In addition, it is possible to provide a material for organic electronics that is extremely useful for improving the productivity of organic electronics elements, particularly polymer type organic EL elements.

  Furthermore, since the organic electronics material has a high triplet energy level and carrier mobility, it is possible to provide an organic electronics element and an organic EL element having light emission efficiency and lifetime that are superior to those of the conventional materials.

It is a schematic cross section showing an example of a multilayered organic EL element. 2 is a ¹ H-NMR spectrum of monomer A synthesized in Monomer Synthesis Example 1. FIG. 3 is a ¹ H-NMR spectrum of monomer B synthesized in monomer synthesis example 2. FIG.

In the organic electronics material of the present invention, all substituents are aromatic rings or heterocyclic derivatives, and the substituents do not form a cyclic structure with at least one quaternary carbon and at least one polymerizable substituent. It is characterized by including the compound which has these.
Here, “substituents do not form a cyclic structure” means that the quaternary carbon is not part of an aromatic ring or heterocyclic ring, and the substituents bonded to the quaternary carbon by a single bond are It means not connected.

In the material for organic electronics of the present invention, the compound preferably includes at least one tetraarylmethane structure.
Here, in the present invention, “including at least one tetraarylmethane structure” is not particularly limited as long as it includes at least one tetraarylmethane structure in the material. Examples of the compound containing an arylmethane structure include derivatives such as tetraphenylmethane, tetrapyridylmethane, and tetrathienylmethane.

  In the organic electronics material of the present invention, more specifically, the compound preferably includes a structure represented by the following general formula (a).

〔式中、Ｒは、それぞれ独立に、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は下記一般式（２ａ）〜（４ａ）

[Wherein, R is ^{independently, -R 1, -OR 2, -SR} 3, -OCOR 4, -COOR 5, -SiR 6 R 7 R 8 or the following general formula (2a) ~ (4a)

（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基、又は炭素数２〜３０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以上の整数を表す。）を表す。Ａｒは、それぞれ独立に、置換若しくは非置換のアリーレン基、ヘテロアリーレン基を表す。Ｅは、それぞれ独立に、前記Ｒと同義、又は重合可能な置換基を含む基を示す。〕

^(Wherein, R 1 ^{to R 11} is a hydrogen atom, a straight-chain 1 to 22 carbon atoms, cyclic or branched alkyl group, or an aryl or heteroaryl group having 2 to 30 carbon atoms, a, b and c Represents an integer of 1 or more. Ar independently represents a substituted or unsubstituted arylene group or heteroarylene group. E independently represents a group having the same meaning as R or a polymerizable substituent. ]

  Here, in the present invention, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and the heteroarylene group is obtained by removing two hydrogen atoms from an aromatic compound having a hetero atom. It is an atomic group. 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 the like.

  Heteroarylene groups include, for example, pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, oxazole-diyl, oxadi Examples include azole-diyl, thiadiazole-diyl, triazole-diyl, benzoxazole-diyl, benzoxiadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, and benzothiophene-diyl. Examples of the arylene group or heteroarylene group which may be substituted or unsubstituted are shown in the following structural formulas (1) to (30).

〔式中、Ｒは、それぞれ独立に、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は前記一般式（２ａ）〜（４ａ）（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基又は炭素数２〜３０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以上の整数を表す。）を表す。〕

[In the formula, each R is independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ^8, or the general formulas (2a) to (4a) ( However, R < ¹ > -R < ¹¹ > represents a hydrogen atom, a C1-C22 linear, cyclic or branched alkyl group, or a C2-C30 aryl group or heteroaryl group, a, b, and c are 1 Represents the integer above. ]

  Here, the “group containing a polymerizable substituent” in the present invention is not particularly limited as long as it contains at least one polymerizable substituent, and examples thereof include an alkyl group, an alkoxy group, and an aryl group. And groups in which one or more polymerizable substituents are bonded to a group, heteroaryl group, arylamino group, carbazole group or the like.

  Examples of the polymerizable substituent include a group having a carbon-carbon multiple bond (for example, vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, arene group). , Allyl group, vinyl ether group, vinylamino group, furyl group, pyrrole group, thiophene group, silole group, etc.), a group having a small ring (for example, cyclopropyl group, cyclobutyl group, epoxy group, oxetane) Groups, diketene groups, episulfide groups, etc.), lactone groups, lactam groups, or groups containing siloxane derivatives.

  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, in particular, an oxetane group, an epoxy group, a vinyl group, an acrylate group, and a methacrylate group are preferable from the viewpoint of reactivity, and an oxetane group is most preferable.

  The compound according to the present invention is a polymer or oligomer from the viewpoints of solubility in a solvent for easily preparing a coating solution and film forming properties for stably forming a film by a coating method and heat resistance of the thin film. It is preferable.

  The number average molecular weight of the polymer or oligomer according to 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, making lamination 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 according to the present invention is preferably greater than 1.0, more preferably 1.1 or more and 5.0 or less, and further preferably 1.2 or more and 3.0 or less. If the polydispersity is too small, the film tends to aggregate after film formation, and if it is too large, the 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.

The polymer or oligomer according to the present invention as described above preferably has a unit having a tetraarylmethane derivative and charge transportability.
Here, in the present invention, the “unit having a charge transporting property” is an atomic group having the ability to transport holes or electrons, and the details thereof will be described below.

  The unit having the charge transporting property is not particularly limited as long as it is a monomer unit having the ability to transport holes or electrons. Particularly, the unit has an amine structure having an aromatic ring or a structure having a carbazole derivative. Preferably, there are, for example, the following general formulas (9a) to (21a).

〔式中、Ｒはそれぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は前記一般式（２ａ）〜（４ａ）（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基又は炭素数２〜３０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以上の整数を表す。）を表す。Ａｒは、それぞれ独立に、置換若しくは非置換のアリーレン基、ヘテロアリーレン基を表す。Ｘ及びＹは、それぞれ独立に、前記Ｒのうち、水素原子を１つ以上有する基から、さらに１つの水素原子を除去した基を表す。ｘは整数を表す。Ｚは、それぞれ独立に、前記Ｒのうち、水素原子を２つ以上有する基から、さらに２つの水素原子を除去した基を表す。〕

Wherein, ^-R 1 R are each ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8 or Formula (2a) ~ (4a) (where R ^{1 to} R ¹¹ represent a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group or a heteroaryl group having 2 to 30 carbon atoms, and a, b, and c are one or more. Represents an integer). Ar independently represents a substituted or unsubstituted arylene group or heteroarylene group. X and Y each independently represent a group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in the R. x represents an integer. Z independently represents a group obtained by removing two hydrogen atoms from a group having two or more hydrogen atoms in the R. ]

In the general formulas (9a), (10a), (11a), (12a), (13a), and (14a), an arylene group or heteroarylene group that is not directly bonded to a nitrogen atom (wherein Ar ₃ , Ar ₈ , Ar ₁₅ ) are preferably the above structural formulas (29) and (30) having a phenylene group, a fluorene-diyl group, a phenanthrene-diyl group, or a condensed ring structure from the viewpoints of solubility and chemical stability. .

In the structural formulas (29) and (30), l, m, and n are integers of 1 to 5, and are preferably integers of 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 (18a), (19a), (20a) and (21a), X and Y are each independently one more hydrogen from a group having one or more hydrogen atoms in the R. It represents a group from which atoms have been removed, and examples thereof include the following general formulas (31) to (35), but of course not limited thereto.

  Z in the general formula (18a) independently represents a group obtained by removing two hydrogens from a group having two or more hydrogen atoms in the R. For example, the following general formula (36) And (37) are, of course, not limited thereto.

  In addition, the polymer or oligomer according to the present invention is a copolymer having the above arylene group and heteroarylene group as a copolymer repeating unit in addition to the repeating unit having charge transportability, in order to adjust solubility, heat resistance, and electrical characteristics. It may be a polymer.

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.
Further, the polymer or oligomer according to the present invention may have branches in the main chain and may have three or more terminals.

  The polymer or oligomer according to the present invention preferably has a structure represented by the following general formulas (5a) to (8a).

〔式中、Ｒは、それぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８又は前記一般式（２ａ）〜（４ａ）（ただし、Ｒ^１〜Ｒ^１１は、水素原子、炭素数１〜２２の直鎖、環状若しくは分岐アルキル基又は炭素数２〜３０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以上の整数を表す。）を表す。Ｗは、電荷輸送性を有するユニットを表す。Ｅは、それぞれ独立に、前記Ｒと同義、又は重合可能な置換基を含む基を示す。ｎは整数を表す。〕

[In the formula, R, ^-R 1 each ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8 or Formula (2a) ~ (4a) (provided that , R ^{1 to} R ¹¹ 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, and a, b and c are 1 or more. Represents an integer). W represents a unit having a charge transporting property. E independently represents a group having the same meaning as R or a polymerizable substituent. n represents an integer. ]

  The polymer or oligomer according to the present invention has one or more “polymerizable substituents”. Here, the “polymerizable substituent” means a substituent capable of forming a bond between two or more molecules by causing a polymerization reaction, and specific examples thereof are as described above.

  The number of polymerizable substituents contained in one molecule of the polymer or oligomer is preferably an integer of 1 to 8, more preferably 1 to 4, and most preferably 2. If the number of polymerizable substituents is too large, the electrical characteristics tend to be lowered, and if too small, multilayering tends to be difficult.

  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. In particular, when introduced at the terminal, the influence on the properties of the polymer or oligomer main chain is small, which is preferable.

  As the polymer or oligomer having a polymerizable substituent introduced at the end, specifically, for example, a polymer in which E in the above general formulas (1a) to (14a) is a group having a polymerizable substituent or Examples are oligomers. E in the general formulas (1a) to (14a) is, for example, a group in which one or more polymerizable substituents described above are bonded to an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, a carbazole group, or the like. . E may be the same or different. E is preferably an oxetane-containing group, and examples thereof include the following general formula.

  In the general formulas (5a) to (8a), the number average of the repeating number n is preferably 2 or more and 100 or less, and more preferably 2 or more and 20 or less. If n is too small, the film-forming stability is lowered, and if it is too large, the change in solubility is small even when a polymerization reaction is carried out, and lamination becomes difficult.

  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 in which each monomer unit 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) wrote Synthetic Communications, Vol. 11, no. 7, p. 513 (1981) is common for polymer production.

  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 which concerns on 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 carbonates or bicarbonates 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.

  In addition to the polymer or oligomer, the organic electronics material of the present invention 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 application of heat, light, microwave, radiation, electron beam, and the like. It is preferably one that initiates polymerization by heating, and more preferably one that initiates polymerization by light irradiation (hereinafter referred to as a photoinitiator).

  The photoinitiator is not particularly limited as long as it expresses the ability to polymerize a polymerizable substituent by irradiation with light of 200 to 800 nm. For example, when the polymerizable substituent is an oxetane group. Iodonium salts, sulfonium salts, ferrocene derivatives and the like are preferable from the viewpoint of reactivity, and the following compounds are exemplified.

  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 mass or 10% by mass with respect to the total mass of the material for organic electronics, and preferably in the range of 0.2-8% by mass. More preferably, it is still more preferably in the range of 0.5 to 5% by mass. When the blending ratio of the polymerization initiator is less than 0.1% by mass, lamination tends to be difficult, and when it exceeds 10% by mass, the device characteristics tend to deteriorate.

  In addition to the polymer or oligomer, a carbon material can be further blended with the organic electronics material of the present invention in order to adjust electrical characteristics.

  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, printing on intaglio printing, intaglio printing, offset printing, lithographic printing, letterpress reverse printing, screen printing, gravure printing, and the like on a desired substrate, followed by light irradiation or 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 at a temperature range of -20 to + 300 ° C, preferably 10 to 100 ° C, particularly preferably 15 to 50 ° C. Although there is no limitation, for example, chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, anisole, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate and the like can be mentioned.

  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, Most preferably, it is 80-200 degreeC.

The material for organic electronics of the present invention can be used alone as a functional material of an organic electronics element.
Moreover, the organic electronics material of the present invention can be used alone as a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer of an organic EL element. Can do.

  As described above, the material for organic electronics of the present invention can be used as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like of an organic electronics element. Are preferably used as the hole injection layer, hole transport layer, and light emitting layer, and more preferably used as the hole transport layer and light emitting layer. 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.

<Organic EL device>
The organic EL device of the present invention is characterized by having a layer containing the organic electronic material of the present invention. The organic EL device of the present invention is not particularly limited as long as it includes a light emitting layer, a polymerized layer, an anode, a cathode, and a substrate. Other elements such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer are used. It may have a layer. 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. Examples of 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.

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) that emits blue light [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate], green light is emitted. Ir (ppy) ₃ [Factris (2-phenylpyridine) iridium] (see Non-Patent Document 3 above) or Adachi et al. , Appl. Phys. Lett. 78no. (Btp) ₂ Ir (acac) {bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C3] 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, etc. can be used as the polymer compound, 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, a metal (for example, Au) or other material having metal conductivity, for example, an oxide (for example, ITO: indium oxide / tin oxide), a conductive polymer (for example, a polythiophene-polystyrene sulfonic acid mixture (for example, PEDOT: PSS)) can also be used.

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

[substrate]
As the substrate that can be used in the organic EL device of the present invention, the kind of glass, plastic and the like is not particularly limited, and is not particularly limited as long as it is transparent, but glass, quartz, light transmissive A resin film or the like is 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.

[Luminescent color]
The emission color in the organic EL device of the present invention is not particularly limited, but the white light-emitting device 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.

<Lighting device>
The illuminating device of the present invention includes the organic EL element of the present invention described above. That is, the organic EL element of the present invention can be used as a light source of a lighting device. For example, when a white light emitting element is used, as described above, it can be used for various lighting devices such as home lighting, interior lighting, clocks, and liquid crystal backlights.

<Display element, display device>
The display element of the present invention is characterized by including the above-described organic EL element of the present invention.
For example, a color display element can be obtained by using the organic EL element of the present invention as an element corresponding to each pixel of red, green, and blue (RGB).
Image formation includes a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged and driven in each element. The former is simple in structure but has a limit on the number of vertical pixels and is used for displaying characters. The latter is used for a high-quality display because the drive voltage is low and the current is small, and a bright high-definition image is obtained.

  Further, the above-described illumination device of the present invention may be used as a backlight (white light source), and a display device using a liquid crystal element as a display unit, that is, a liquid crystal display device may be used. This configuration is a configuration in which only the backlight is replaced with the illumination device of the present invention in a known liquid crystal display device, and a known technique can be diverted to the liquid crystal element portion.

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

[Example 1]
<Synthesis of a monomer having a polymerizable substituent>
(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質量％水酸化ナトリウム水溶液（３６ｇ）を加え、窒素下、７０℃で６時間加熱攪拌した。

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% by mass 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 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. The yield was 67% by mass.

¹ H-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) .4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H). FIG. 2 shows a ¹ H-NMR spectrum of monomer A having a polymerizable substituent.

(Monomer synthesis example 2)

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（５ｍｍｏｌ）、３，５−ジブロモベンジルブロミド（５ｍｍｏｌ）、ｎ−ヘキサン（２０ｍＬ）、テトラブチルアンモニウムブロミド（０．２５ｍｍｏｌ）及び５０質量％水酸化ナトリウム水溶液（３．６ｇ）を加え、窒素下、７０℃で６時間加熱攪拌した。

In a round bottom flask, 3-ethyl-3-hydroxymethyloxetane (5 mmol), 3,5-dibromobenzyl bromide (5 mmol), n-hexane (20 mL), tetrabutylammonium bromide (0.25 mmol) and 50% by weight water An aqueous sodium oxide solution (3.6 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 extracted with toluene. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain 1.75 g of monomer B having a polymerizable substituent as a colorless solid. The yield was 96% by mass.

¹ H-NMR (300 MHz, CDCl ₃ , δ ppm); 0.88 (t, J = 7.5 Hz, 3H), 1.78 (t, J = 7.5 Hz, 2H), 3.59 (s, 2H) ), 4.40 (d, J = 5.7 Hz, 2H), 4.48 (d, J = 5.7 Hz, 2H), 4.49 (s, 2H), 7.41 (m, 2H), 7.59 (m, 1H). FIG. 3 shows a ¹ H-NMR spectrum of monomer B having a polymerizable substituent.

(Monomer Synthesis Example 3)

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（５ｍｍｏｌ）及びピリジン（１００ｍＬ）を加え、窒素下水浴で冷却しながらｐ−トルエンスルホニルクロリド（１０ｍｍｏｌ）のピリジン溶液（５０ｍＬ）をゆっくりと滴下した。

To a round bottom flask, 3-ethyl-3-hydroxymethyloxetane (5 mmol) and pyridine (100 mL) are added, and a pyridine solution (50 mL) of p-toluenesulfonyl chloride (10 mmol) is slowly added dropwise while cooling in a water bath under nitrogen. did.

  It stirred for 6 hours after completion | finish of dripping. Water (200 mL) and diethyl ether (200 mL) were added to the reaction solution for extraction. After distilling off the solvent, 0.95 g of Intermediate 1 was obtained as a pale orange oil. The yield was 70% by mass.

  Intermediate 1 (5 mmol) was dissolved in N, N-dimethylacetamide (100 mL), 4-bromophenol (4 mmol) and potassium hydroxide (5 mmol) were added, and the mixture was heated and stirred at 110 ° C. for 6 hours.

  The salt precipitated after cooling to room temperature was filtered, water (200 mL) was added, and the mixture was extracted with diethyl ether (200 mL). After distilling off the solvent, the residue was purified by distillation under reduced pressure to obtain 0.81 g of monomer C having a polymerizable substituent as a pale yellow oil. The yield was 75% by mass.

<Synthesis of monomer having tetraphenylmethane structure>
(Monomer Synthesis Example 4)

原料である４，４’−ジメチルトリフェニルメチルクロライドは、Ｊ． Ｏｒｇ． Ｃｈｅｍ．，４４， １４５４（１９７９）に従い合成した。

The raw material 4,4′-dimethyltriphenylmethyl chloride is described in J. Org. Org. Chem. , 44, 1454 (1979).

  Monomer D having a tetraphenylmethane structure was synthesized with reference to Synthesis 2002, 1157. In a round bottom flask, 4,4'-dimethyltriphenyl chloride (5 mmol) and aniline (15 mmol) were mixed and heated at 220 ° C to melt. When crystallization started, heating was stopped and the mixture was ground with stirring.

  While stirring a mixed solution of 2M hydrochloric acid (60 mL) and methanol (50 mL), the obtained powder was dispersed in the solution. The solution was heated to boiling and then cooled to room temperature and filtered. The residue was washed with water and dried, then dispersed in DMF (100 mL) while cooling with an ice bath, and concentrated sulfuric acid (10 mL) was slowly added.

Isoamyl nitrate (10 mL) was added, and the mixture was stirred at 5 to 10 ° C. for 1 hr.
Next, a 50% hypophosphorous acid solution was added, and the mixture was heated and stirred at 50 ° C. until no gas was generated. The precipitate was filtered, washed with water and ethanol, recrystallized from DMF and purified.

The obtained powder was put into a round bottom flask, carbon tetrachloride (50 mL) and FeCl ₃ (3 mmol) were added, and then bromine (10 mmol) was added dropwise. Then, after heating and refluxing overnight, the solvent was distilled off, and recrystallization was performed with THF and methanol to obtain 0.51 g of a monomer D having a tetraphenylmethane structure. The yield was 25% by mass.

<Synthesis of an oligomer having a polymerizable substituent and having a repeating unit containing a tetraphenylmethane structure>
(Oligomer synthesis example 1)

  In a sealable fluororesin container, 4,4′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4 ″ -n-butyltriphenylamine (0.4 mmol), monomer D (0.32 mmol) having a tetraphenylmethane structure, monomer A (0.16 mmol) having a polymerizable substituent, tetrakistriphenylphosphine palladium (0.008 mmol), 2M aqueous potassium carbonate solution (5.3 ml), Aliquat 336 (0.4 mmol), and toluene (4 ml) were added, and the mixture was heated and stirred at 90 ° C. for 2 hours under microwave irradiation in a sealed container under a nitrogen atmosphere.

  The reaction solution was poured into a methanol / water mixed solvent (9: 1), and the precipitated polymer was filtered off. The reprecipitation was repeated twice to purify, and thus an oligomer A having a polymerizable substituent and having a repeating unit having a tetraphenylmethane structure was obtained. The number average molecular weight of the obtained oligomer was 5782 in terms of polystyrene, and the polydispersity was 1.83.

[Comparative Example 1]
<Comparative polymer synthesis example 1>

  4,4′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4 ″ -n-butyltriphenylamine (0.4 mmol), tetraphenylmethane Oligomer synthesis example 1 using monomer D having a structure (0.32 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (5.3 ml), Aliquat 336 (0.4 mmol) and anisole (4 ml) The polymer A was synthesized in the same manner as described above to obtain a comparative polymer A having only a repeating unit having a tetraphenylmethane structure and having no polymerizable substituent. The number average molecular weight of the obtained polymer was 20,330 in terms of polystyrene.

<Comparative oligomer synthesis example 2>

  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 polymer was filtered off. Reprecipitation was repeated twice to purify, and Comparative Oligomer B having a polymerizable substituent and a repeating unit having a hole transporting property was obtained. The number average molecular weight of the obtained oligomer B was 4652 in terms of polystyrene.

<Comparison of excitation energy>
A toluene solution of oligomer A and comparative oligomer B was spin-coated at 3000 rpm on a quartz plate in nitrogen, and then heated and dried on a hot plate at 80 ° C. for 5 minutes to form a thin film having a thickness of 50 nm.
The absorption spectrum of this thin film was measured, the excitation energy of the oligomer was calculated from the absorption edge wavelength, and the results are summarized in Table 1. The absorption spectrum measurement was performed using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

  From Table 1, it can be seen that the oligomer A has a larger excitation energy than the comparative oligomer B.

[Example 2]
<Production of organic EL element>
(Example of light-emitting polymer synthesis)

  2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.4 mmol), 4,4′-dibromotriphenyl Amine (0.08 mmol), 4,7-dibromo-2,1,3-benzothiadiazole (0.32 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (5.3 ml), Aliquat 336 ( 0.4 mmol) and toluene (4 ml) were used in the same manner as in oligomer synthesis example 1 to obtain a yellow light emitting polymer.

PEDOT: PSS dispersion (Stark Vitech, CH8000 LVW233) was spin-coated at 4000 min ⁻¹ on a glass substrate patterned with ITO to a width of 1.6 mm, and 200 ° C./10 minutes in air on a hot plate. A hole injection layer (40 nm) was formed by heating and drying. Subsequent experiments were performed in a dry nitrogen environment.
Next, the oligomer A (4.4 mg) obtained above on the hole injection layer, the following chemical formula

で表される光開始剤（０．１３ｍｇ）、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) are 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, a toluene solution (1.5% by mass) of a yellow light emitting polymer is spin-coated at 3000 min ⁻¹ on the hole transport layer, and heated on a hot plate at 80 ° C. for 5 minutes to form a polymer light emitting layer (film thickness 100 nm). Formed. The hole transport layer and the light emitting layer could be laminated without dissolving each other.

Furthermore, the obtained glass substrate was moved into a vacuum evaporation machine, and electrodes were formed on the light emitting layer in the order of Ba (film thickness: 3 nm) and Al (film thickness: 100 nm).
After electrode formation, the 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 coated with a photocurable epoxy resin. Sealing was performed by using them together to produce a polymer organic EL device having a multilayer structure. Subsequent experiments were performed in the atmosphere at room temperature (25 ° C.).
When a voltage was applied using the ITO of this organic EL element as a positive electrode and Al as a cathode, yellow light emission was observed.

[Comparative Example 2]
The coating solution in which the comparative polymer A (4.4 mg) obtained above, the photoinitiator (Chemical Formula 20) (0.13 mg) and toluene (1.2 ml) were mixed as the hole transport layer material in Example 2 was used. Except for the above, a hole injection layer (40 nm) and a hole transport layer (40 nm) were formed in the same manner as in Example 1.

Subsequently, the toluene solution of the yellow light emitting polymer used in Example 2 was spin-coated at 3000 min ⁻¹ and heated on a hot plate at 80 ° C. for 5 minutes to form a polymer light emitting layer (film thickness 100 nm). When the total film thickness was measured, it was 140 nm. That is, in Comparative Example 2, the hole transport layer was dissolved and a multilayer structure could not be produced.

[Example 3]
A coating solution in which the oligomer A (4.4 mg), the photoinitiator (Chemical Formula 20) (0.13 mg) and toluene (500 μl) obtained above were mixed on a glass substrate patterned with ITO in a width of 1.6 mm was prepared. Spin-coated at 3000 min ⁻¹ . Subsequent experiments were performed in a dry nitrogen environment.

Next, light irradiation (3 J / cm ² ) was performed using a metal halide lamp, followed by heating and curing on a hot plate at 120 ° C. for 15 minutes and at 180 ° C. for 60 minutes to form a hole injection layer (50 nm).

Next, a toluene solution (1...) Of a mixture of polymer 1 (75 parts by mass), polymer 2 (20 parts by mass) and polymer 3 (5 parts by mass) represented by the following structural formula is formed on the hole injection layer. 0 mass%) was spin-coated at 3000 min ⁻¹ 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, Ba / Al electrodes were formed and sealed in the same manner as in Example 1.
When voltage was applied with the ITO of this organic EL element as the positive electrode and Al as the cathode, green light emission was observed.

[Comparative Example 3]
Except for using a coating solution in which a comparative polymer (4.4 mg), a photoinitiator (Chemical Formula 20) (0.13 mg) and toluene (500 μl) were mixed as the hole injection layer material, the same procedure as in Example 2 was performed. When an organic EL element was produced and a voltage was applied to the organic EL element, uniform light emission was not obtained. That is, in Comparative Example 3, the hole injection layer was dissolved and mixed with the light emitting layer.

<Production of white organic EL element and lighting device>
[Example 4]
In the same manner as in Example 2, a hole injection layer (40 nm) was formed using PEDOT: PSS dispersion, and a hole transport layer was formed using oligomer A and a photoinitiator (same as Example 2).

Next, in nitrogen, CDBP (15 mg), FIr (pic) (0.9 mg), Ir (ppy) 3 (0.9 mg), (btp) 2Ir (acac) (1.2 mg), dichlorobenzene (0. 5 mL) was spin-coated at 3000 rpm and then dried at 80 ° C. for 5 minutes to form a light emitting layer (40 nm). Furthermore, BAlq (bis (2-methyl-8-hydroxyquinolinate) (4-biphenyloxolate) aluminum) (10 nm), Alq ₃ (30 nm), LiF (film thickness 0.5 nm), Al (film thickness 100 nm) ) Were deposited in this order and sealed to produce an organic EL element and a lighting device.

  When voltage was applied to the white organic EL element and the lighting device, uniform white light emission was observed.

[Comparative Example 4]
A white organic EL element and a lighting device were produced in the same manner as in Example 4 except that the hole transport layer was formed of Comparative Oligomer B and a photoinitiator (same as in Example 2).

  When voltage was applied to the white organic EL element and the lighting device, white light emission was observed, but the light emission lifetime was 1/3 that of Example 4.

  From the comparison between Example 4 and Comparative Example 4 above, it can be seen that the white organic EL element and the lighting device can be stably driven by using the organic electronic material in the present invention.

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

Claims (23)

  All the substituents are aromatic rings or heterocyclic derivatives, and at least include a compound having at least one quaternary carbon in which the substituents do not form a cyclic structure and at least one polymerizable substituent. A characteristic material for organic electronics.   The organic electronics material according to claim 1, wherein the compound contains at least one tetraarylmethane structure. The organic electronics material according to claim 1 or 2, wherein the compound includes a structure represented by the following general formula (1a).

[Wherein, R is ^{independently, -R 1, -OR 2, -SR} 3, -OCOR 4, -COOR 5, -SiR 6 R 7 R 8 or the following general formula (2a) ~ (4a)

^(Wherein, R 1 ^{to R 11} represents a hydrogen atom, a linear, cyclic or branched alkyl group or an aryl group or heteroaryl group having 2 to 30 carbon atoms having 1 to 22 carbon atoms, a, b and c, Represents an integer of 1 or more. Ar independently represents a substituted or unsubstituted arylene group or heteroarylene group. E independently represents a group having the same meaning as R or a polymerizable substituent. ]   The organic electronic material according to claim 1, wherein the compound is a polymer or an oligomer.   The organic electronics material according to claim 4, wherein the number average molecular weight of the polymer or oligomer is 1,000 or more and 100,000 or less.   The organic electronics material according to claim 4 or 5, wherein the polydispersity of the polymer or oligomer is greater than 1.0.   The organic electronics material according to any one of claims 4 to 6, wherein the polymer or oligomer has a unit having charge transportability with a tetraarylmethane derivative. The organic electronics material according to any one of claims 4 to 7, wherein the polymer or oligomer is represented by the following general formulas (5a) to (8a).

[In the formula, each R is independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ or general formulas (2a) to (4a).

^(Wherein, R 1 ^{to R 11} represents a hydrogen atom, a linear, cyclic or branched alkyl group or an aryl group or heteroaryl group having 2 to 30 carbon atoms having 1 to 22 carbon atoms, a, b and c, Represents an integer of 1 or more). W represents a unit having a charge transporting property. E independently represents a group having the same meaning as R or a polymerizable substituent. n represents an integer. ]   The organic electronics material according to claim 8, wherein the number average of n in the general formulas (5a) to (8a) is 2 to 20.   10. The organic electronics according to claim 1, wherein the polymerizable substituent is one selected from the group consisting of an oxetane group, an epoxy group, a vinyl group, an acrylate group, and a methacrylate group. material.   The material for organic electronics according to any one of claims 4 to 9, wherein a polymerizable substituent in the polymer or oligomer is introduced at a terminal of the polymer or oligomer.   Furthermore, the material for organic electronics of any one of Claims 1-11 containing an iridium complex or a platinum complex.   The organic electronics element produced using the organic electronics material of any one of Claims 1-12.   The organic electroluminescent element produced using the organic electronics material of any one of Claims 1-12.   An organic electroluminescence device comprising at least an anode, a light emitting layer, and a cathode, wherein the light emitting layer is a layer formed of the organic electronics material according to any one of claims 1 to 12. Electroluminescence element.   It is an organic electroluminescent element formed by laminating at least an anode, a hole injection layer, a light emitting layer, and an anode, and the hole injection layer is made of the organic electronics material according to any one of claims 1 to 12. An organic electroluminescent element which is a formed layer.   It is an organic electroluminescent element formed by laminating | stacking an anode, a positive hole injection layer, a positive hole transport layer, a light emitting layer, and a cathode at least, Comprising: The said positive hole transport layer is any one of Claims 1-12. An organic electroluminescent element which is a layer formed of an organic electronic material.   The organic electroluminescent element according to claim 14, which emits white light.   The organic electroluminescent element according to any one of claims 14 to 18, wherein the substrate of the organic electroluminescent element is a flexible substrate.   The organic electroluminescent element according to any one of claims 14 to 19, wherein a substrate of the organic electroluminescent element is a resin film.   A display element comprising the organic electroluminescent element according to claim 14.   An illuminating device comprising the organic electroluminescent element according to any one of claims 14 to 20.   23. A display device comprising: the lighting device according to claim 22; and a liquid crystal element as display means.

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