JP2007308691A - Material for organic electronics, organic electronics element and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for organic electronics and thin film capable of easily forming multiple layers, and further an organic electroluminescent element and organic EL element having more excellent light-emitting efficiency and light-emitting life than those of conventional ones. <P>SOLUTION: This material for the organic electronics containing a polymeric compound expressed by general formula (1) [wherein, Ar<SB>1</SB>to Ar<SB>3</SB>are each independently an arylene, a heteroarylene or triphenylamine; Va is a functional group capable of polymerizing with epoxy or oxetane; (l), (m) are each independently ≥0 integer; and (n) is ≥1 integer], the thin film, the organic electronics element and the organic electroluminescent element produced by using the material for organic electronics are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a material for organic electronics, and a thin film, an organic electronics element and an organic electroluminescence element (hereinafter referred to as an organic EL element) using the same.

  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. ing.

  Among organic electronic elements, organic EL elements are attracting attention for use as 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 referred to as a light emitting layer 1, and 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. 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, an electron transport is described. It is described as layer 7. In FIG. 1, 8 is 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, 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, a device having a three-layer structure having a hole transport layer utilizing a photocuring reaction (see, for example, Non-Patent Document 2) and a device having a three-layer structure having a hole transport layer utilizing a crosslinking reaction of a siloxane compound ( 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 the device characteristics are not sufficient.
Y. Goto, T .; Hayashida, M .; Noto, IDW '04 Proceedings of The 11th International Display Workshop, 1343-1346 (2004) Daisuke Kumaki, Kengo Hirose, Nobuaki Koike, Satoshi Kuriyama, Shizuka Tokito, Organic EL Discussion Group (2005) 1st Regular Meeting Proceedings, P27 H. Yan, P.M. Lee, N.M. R. Armstrong, A.M. Graham, G.M. A. Evmenenko, P.M. Dutta, T.A. J. et al. Marks, J.A. Am. Chem. Soc. , 127, 3172-4183 (2005)

  In order to increase the efficiency and extend the life of organic EL elements, it is desirable to make the organic layers 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 that facilitates film formation, it is necessary to prevent the lower layer from being dissolved during the formation of the upper layer.

  An object of this invention is to provide the material for organic electronics and thin film which can be easily multilayered in view of the above-mentioned problem. Furthermore, an object of the present invention is to provide an organic electronics element and an organic EL element having light emission efficiency and light emission lifetime superior to those of the prior art.

  As a result of intensive studies, the present inventors have found that a mixture of a polymer having a functional group capable of polymerizing an epoxy group or an oxetane group and a compound having an epoxy group or an oxetane group can form a thin film stably and easily. It has been found that the solubility is changed by heating, and further that this mixture functions as a material for organic electronics, and the present invention has been completed.

  That is, the present invention is characterized by the following items <1> to <11>.

（式中、Ａｒ_１、Ａｒ_２およびＡｒ_３は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｖａはエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｎは１以上の整数を表す。） <1> An organic electronics material containing a polymer compound represented by the following general formula (1).

(Wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently an arylene group, heteroarylene group or triphenylamine derivative, Va is a functional group capable of polymerizing with an epoxy group or an oxetane group, and l and m are Each independently represents an integer of 0 or more, and n represents an integer of 1 or more.)

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、ＶｂおよびＶｃは各々独立にエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｌ＋ｍ≧１である。） <2> A material for organic electronics comprising a polymer compound represented by the following general formula (2).

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Vb and Vc are each independently a functional group capable of polymerizing with an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and l + m ≧ 1.)

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｖａ、ＶｂおよびＶｃは各々独立にエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｎは１以上の整数を表す。） <3> A material for organic electronics comprising a polymer compound represented by the following general formula (3).

(Wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Va, Vb and Vc are each independently an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and n represents an integer of 1 or more.)

  <4> The functional groups Va, Vb, and Vc in the general formulas (1), (2), and (3) are each a hydroxyl group, an amino group, a thiol group, an alkylamino group, a carboxyl group, or an imidazole group. The organic electronics material according to any one of <1> to <3> above.

（式中、Ｘは、炭素数１〜２２のアルキル基、炭素数６〜３０個の、置換又は未置換のアリール基、ヘテロアリール基、アリーレン基、ヘテロアリーレン基、トリフェニルアミン誘導体を表し、ｐは１〜８の整数を表す。）

（式中、Ｘは、炭素数１〜２２のアルキル基、炭素数６〜３０個の、置換又は未置換のアリール基、ヘテロアリール基、アリーレン基、ヘテロアリーレン基、トリフェニルアミン誘導体を表し、ｑは１〜８の整数を表す。） <5> The compound according to any one of <1> to <4>, further including a compound having an epoxy group represented by the following general formula (4) or a compound having an oxetane group represented by the following general formula (5): The material for organic electronics as described.

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; p represents an integer of 1 to 8.)

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; q represents an integer of 1 to 8.)

（式中、Ａｒ_１、Ａｒ_２およびＡｒ_３は各々独立にアリーレン基もしくはヘテロアリーレン基、トリフェニルアミン誘導体を表し、Ｚ_３は単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ_３は置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表し、ｔは１以上の整数を表す。） <6> The organic electronics material according to any one of <1> to <5>, further including a polymer represented by the following general formula (6).

(In the formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₃ represents a single bond, an oxygen atom, an ester group, or an alkylene group having 1 to 30 carbon atoms. Represents an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, E ₃ represents an optionally substituted epoxy group or oxetane group, and r and s each independently represent an integer of 0 or more. T represents an integer of 1 or more.)

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基もしくはヘテロアリーレン基、トリフェニルアミン誘導体を表し、Ｚ_４およびＺ_５は各々独立に単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ_４およびＥ_５は各々独立に置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表す。） <7> The organic electronics material according to any one of <1> to <5>, further including a compound represented by the following general formula (7).

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₄ and Z ₅ each independently represent a single bond, an oxygen atom or an ester group. Represents an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E ₄ and E ₅ each independently represents an epoxy group or an oxetane group which may be independently substituted. And r and s each independently represent an integer of 0 or more.)

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｚ_３、Ｚ_４およびＺ_５は各々独立に単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ、Ｅ_４およびＥ_５は各々独立に置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表し、ｔは１以上の整数を表す。） <8> The organic electronics material according to any one of <1> to <5>, further including a compound represented by the following general formula (8).

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Z ₃ , Z ₄ and Z ₅ are each independently a single bond. Represents an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E, E ₄ and E ₅ are each independently substituted. And represents an epoxy group or an oxetane group, and r and s each independently represent an integer of 0 or more, and t represents an integer of 1 or more.)

  <9> A thin film having a thickness of 0.5 nm to 1 mm produced using the material for organic electronics according to any one of <1> to <8>.

  <10> An organic electronics element produced using the organic electronics material according to any one of <1> to <8>.

  <11> An organic electroluminescent device produced using the organic electronics material according to any one of <1> to <8>.

  The material for organic electronics of the present invention can form a thin film stably and easily, and the solubility is changed by heating. Therefore, the organic thin film layer can be easily multi-layered. It is an extremely useful material for improving the light emission efficiency, light emission lifetime, and productivity of a polymer organic EL device.

（式中、Ａｒ_１、Ａｒ_２およびＡｒ_３は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｖａはエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｎは１以上の整数を表す。） The material for organic electronics of the present invention comprises a monomer unit represented by the following general formula (1) having a functional group capable of polymerizing an epoxy group or an oxetane group (Ar ₃ -V _a , hereinafter referred to as a polymerization promoting monomer unit). It is characterized by containing a polymer compound (hereinafter referred to as a polymerization promoting polymer) having one or more kinds of structures.

(Wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently an arylene group, heteroarylene group or triphenylamine derivative, Va is a functional group capable of polymerizing with an epoxy group or an oxetane group, and l and m are Each independently represents an integer of 0 or more, and n represents an integer of 1 or more.)

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 examples of the heteroarylene group include Pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, oxazole-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 shown in the following structural formulas (1) to (30).

The substituents R of the arylene group or heteroarylene group in the above structural formula are each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ or SiR ⁶ R ⁷ R ⁸ (where R ¹ to R ⁸ represents a hydrogen atom, a substituent selected from the group consisting of linear 1 to 22 carbon atoms, represent a cyclic or branched alkyl group or having 6 to 30 carbon atoms aryl or heteroaryl group) Each of them may be the same or different and each is a substituent bonded to a substitutable position of an arylene or heteroarylene skeleton. Among these substituents, each R is independently an unsubstituted group, that is, a hydrogen atom, or a group directly substituted by an alkyl group, aryl group, or heteroaryl group represented by -R ¹ , —OR ² , a hydroxyl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group are preferable from the viewpoints of polymerization reactivity and heat resistance. In the structural formulas (29) and (30), l, m, and n are integers from 1 to 5, and are preferably integers from 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 present invention, the triphenylamine derivative is not particularly limited as long as it has a substituted or unsubstituted triphenylamine skeleton. For example, triphenylamine, N- (4-butylphenyl)- N, N-diphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine, N, N′-bis (3 -Methylphenyl-N, N′-bis (2-naphthyl)-[1,1′-biphenyl] -4,4′-diamine, etc. In addition, the aromatic ring of these triphenylamine derivatives Examples of the substitutable group include an alkyl group having 1 to 22 carbon atoms and an alkoxy group.

When the organic electronics material of the present invention is used for a hole injection layer and a hole transport layer of an organic EL device, the copolymerization monomer unit Ar ₁ and / or Ar _{2 of the} polymerization promoting polymer is a triphenylamine derivative. The triphenylamine derivatives having the structures of the above structural formulas (29) and (30) are particularly preferable. The molar fraction of the triphenylamine derivative in the total number of monomer units is preferably 1 to 99%, more preferably 10 to 90%, and most preferably 25 to 75%. If the molar fraction of the triphenylamine derivative is less than 1%, the light emission efficiency of the organic EL device tends to decrease, and if it exceeds 99%, the solubility in an organic solvent tends to decrease, making it difficult to prepare a coating solution. There is.

  Moreover, the functional group which polymerizes the epoxy group or oxetane group contained in a polymerization promotion monomer unit can change the heat processing conditions mentioned later by changing the kind. From the viewpoint of heat treatment ease, this functional group is not particularly limited. For example, a hydroxyl group, an amino group, a thiol group, an alkylamino group, a carboxyl group, and an imidazole group are preferable, and a hydroxyl group, an amino group, and an alkylamino group. An imidazole group is more preferable, and a hydroxyl group, an amino group, and an alkylamino group are most preferable. In addition, these functional groups may be directly bonded to the polymer main chain in the polymerization promoting monomer unit, or may be bonded via an alkyl group, an alkoxy group, an aryl group, an oxyaryl group, an ester group, or the like. Good.

  The weight average molecular weight of the polymerization promoting polymer is preferably 1,000 to 1,000,000, and preferably 1,000 to 800,000. If it is less than 1,000, the film-forming ability tends to decrease, and if it exceeds 1,000,000, the solubility tends to decrease. In addition, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using gel permeation chromatography.

  In addition, each monomer unit may be included in the copolymer at random like a so-called random copolymer, and some specific monomer units may be present locally such as a lock copolymer or a graft copolymer. Any copolymer may be used. Each of the two monomer units constituting the copolymer may be a single monomer or a combination of two or more monomers.

The polymerization promoting polymer may have a polymerization promoting monomer unit in the polymer main chain or at the terminal of the polymer main chain. Moreover, you may have in both the polymer principal chain and the terminal of a polymer principal chain. Ar ₁ and Ar ₂ do not have a function of polymerizing an epoxy group or an oxetane group, but can be used as necessary as a copolymerization monomer unit in order to adjust electrical characteristics and mechanical characteristics.

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、ＶｂおよびＶｃは各々独立にエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｌ＋ｍ≧１である。） When the polymerization promoting monomer unit is present at the end of the polymer main chain, the polymerization promoting polymer is represented, for example, by the following general formula (2). Here, the polymerization promoting monomer units are Ar ₄ -V _b and Ar ₅ -V _c , which may be the same or different. Ar ₄ , Ar ₅ , Vb, and V _c are the same as Ar ₁ and V _a , respectively.

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Vb and Vc are each independently a functional group capable of polymerizing with an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and l + m ≧ 1.)

（式中、Ｚは単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、ＶはＶ_ｂまたはＶ_ｃのいずれかを表す。） Moreover, an example of a polymerization promotion monomer unit in case a polymerization promotion monomer unit exists in the terminal of a polymer principal chain is shown in following General formula (9).

(In the formula, Z represents a single bond, an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and V represents V _b or V _c. Represents one of these.)

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｖａ、ＶｂおよびＶｃは各々独立にエポキシ基又はオキセタン基と重合しうる官能基であり、ｌおよびｍは各々独立に０以上の整数を表し、ｎは１以上の整数を表す。） Moreover, when the said polymerization acceleration | stimulation monomer unit exists in a polymer principal chain and its terminal, the said polymerization acceleration | stimulation polymer is represented by following General formula (3), for example. Here, the polymerization promoting monomer units are Ar ₃ -V _a , Ar ₄ -V _b , and Ar ₅ -V _c , which may be the same or different.

(Wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Va, Vb and Vc are each independently an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and n represents an integer of 1 or more.)

（式中、Ｚは単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、ＶはＶ_ａを表す。） An example of the polymerization promoting monomer unit when the polymerization promoting monomer unit is present in the polymer main chain is shown in the following general formula 10.

(Wherein, Z is a single bond, an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, oxyarylene group, heteroarylene group, V is representative of a V _a. )

  Moreover, in the said polymerization acceleration | stimulation polymer, 0.1-99.9% is preferable, as for the molar fraction of the polymerization acceleration | stimulation monomer unit in the total number of all monomer units, 0.2-50% is more preferable, 0.5-10 % Is most preferred. If the mole fraction of the polymerization promoting monomer unit is less than 0.1%, it tends to be difficult to form a multilayer.

（式中、Ｘは、炭素数１〜２２のアルキル基、炭素数６〜３０個の、置換又は未置換のアリール基、ヘテロアリール基、アリーレン基、ヘテロアリーレン基、トリフェニルアミン誘導体を表し、ｐは１〜８の整数を表す。）

（式中、Ｘは、炭素数１〜２２のアルキル基、炭素数６〜３０個の、置換又は未置換のアリール基、ヘテロアリール基、アリーレン基、ヘテロアリーレン基、トリフェニルアミン誘導体を表し、ｑは１〜８の整数を表す。） The material for organic electronics of the present invention may further contain a compound having an epoxy group represented by the following general formula (4) or a compound having an oxetane group represented by the following general formula (5).

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; p represents an integer of 1 to 8.)

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; q represents an integer of 1 to 8.)

  The compound having an epoxy group or oxetane group used in the present invention is not particularly limited as long as it has at least one epoxy group or oxetane group as shown in the general formulas (4) and (5). Specific examples of the compound having an epoxy group include epoxy derivatives such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and alicyclic epoxy resin. Examples of the compound having an oxetane group include oxetane derivatives such as biphenylylene bisoxetane, terephthalate bisoxetane, and oxetane methacrylate.

  The number of epoxy groups or oxetane groups contained in the compound having an epoxy group or oxetane group is preferably 1 to 8, more preferably 2 to 4, and most preferably 2 to 3. . If the number of epoxy groups or oxetane groups is too small, stacking becomes difficult, and if too large, flexibility tends to decrease. Moreover, the compound which has an epoxy group or an oxetane group may use only 1 type, or may mix and use 2 or more types.

（式中、Ｚは単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅは置換されていてもよいエポキシ基もしくはオキセタン基を表す。） Moreover, when using the organic electronics material containing the compound which has the said epoxy group or oxetane group for formation of the positive hole injection layer or positive hole transport layer of an organic EL element, the said compound contains a triphenylamine derivative in a structure. It is preferable. Examples of the compound containing a triphenylamine derivative include the following general formula (11).

(In the formula, Z represents a single bond, an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group or a heteroarylene group, and E may be substituted) Represents a good epoxy or oxetane group.)

  When the polymerization promoting polymer and the compound having an epoxy group or oxetane group are mixed and used, the weight percent concentration of the polymerization promoting polymer with respect to the total weight of the organic electronics material is preferably 1 to 99%, and preferably 50 to 98. % Is more preferable, and 80 to 98% is most preferable. If the amount of the polymerization accelerating polymer is less than 1%, the electrical characteristics tend to deteriorate, and if it exceeds 99%, lamination tends to be difficult.

  Further, when the polymerization promoting polymer and the compound having the epoxy group or oxetane group are mixed and used, a polymer composed only of the copolymerization monomer unit may be mixed. When the organic electronics material of the present invention is used for a hole injection layer or a hole transport layer of an organic EL device, the polymer composed only of the copolymerization monomer unit is preferably a polymer containing a triphenylamine derivative.

（式中、Ａｒ_１、Ａｒ_２およびＡｒ_３は各々独立にアリーレン基もしくはヘテロアリーレン基、トリフェニルアミン誘導体を表し、Ｚ_３は単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ_３は置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表し、ｔは１以上の整数を表す。） Further, as a compound having an epoxy group or an oxetane group represented by the following general formula (6), the monomer unit (Ar 3 _-Z 3 _-E 3 having an epoxy group or an oxetane _group, hereinafter referred to as crosslinking monomer units ) May be used (hereinafter referred to as a crosslinkable polymer).

(In the formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₃ represents a single bond, an oxygen atom, an ester group, or an alkylene group having 1 to 30 carbon atoms. Represents an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, E ₃ represents an optionally substituted epoxy group or oxetane group, and r and s each independently represent an integer of 0 or more. T represents an integer of 1 or more.)

  The crosslinkable polymer is a polymer copolymer containing one or more types of crosslinkable monomer units, and has a crosslinkable monomer unit at the end of the polymer main chain, even if it is present in the polymer main chain. May be. Moreover, you may have in both the polymer principal chain and the terminal of a polymer principal chain. The crosslinkable monomer unit may be directly bonded to the polymer main chain, or may be bonded via an alkyl group, an alkoxy group, an aryl group, an oxyaryl group, an ester group, or the like.

  Each monomer unit of the crosslinkable polymer may be randomly contained in the copolymer like a so-called random copolymer, or some specific monomer units may be localized like a block copolymer or a graft copolymer. It may be a copolymer as it exists. Each of the two monomer units constituting the copolymer may be a single monomer or a combination of two or more monomers.

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基もしくはヘテロアリーレン基、トリフェニルアミン誘導体を表し、Ｚ_４およびＺ_５は各々独立に単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ_４およびＥ_５は各々独立に置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表す。） The crosslinkable polymer having the crosslinkable monomer unit at the end of the polymer main chain is represented by, for example, the following general formula (7). The crosslinkable monomer units are Ar ₄ -Z ₄ -E ₄ and Ar ₅ -Z ₅ -E ₅ , which may be the same or different.

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₄ and Z ₅ each independently represent a single bond, an oxygen atom or an ester group. Represents an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E ₄ and E ₅ each independently represents an epoxy group or an oxetane group which may be independently substituted. And r and s each independently represent an integer of 0 or more.)

（式中、ＺはＺ_４またはＺ_５を表し、ＥはＥ_４またはＥ_５を表す。） An example of the crosslinkable monomer unit when the crosslinkable monomer unit is present at the end of the polymer main chain is shown in the following general formula (12).

(In the formula, Z represents Z ₄ or Z ₅ , and E represents E ₄ or E _5. )

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４およびＡｒ_５は各々独立にアリーレン基、ヘテロアリーレン基またはトリフェニルアミン誘導体であり、Ｚ_３、Ｚ_４およびＺ_５は各々独立に単結合、酸素原子、エステル基、炭素数１〜３０のアルキレン基、炭素数６〜３０のアリーレン基、オキシアリーレン基、ヘテロアリーレン基を表し、Ｅ、Ｅ_４およびＥ_５は各々独立に置換されていてもよいエポキシ基もしくはオキセタン基を表し、ｒおよびｓは各々独立に０以上の整数を表し、ｔは１以上の整数を表す。） Moreover, when the said crosslinkable monomer unit exists in a polymer principal chain and its terminal, the said crosslinkable polymer is represented by following General formula (8), for example. Here, crosslinking monomer units is _{Ar 3 -Z 3 -E 3, Ar} 4 -Z 4 -E 4, Ar 5 -Z 5 -E 5, may be the same or different.

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Z ₃ , Z ₄ and Z ₅ are each independently a single bond. Represents an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E, E ₄ and E ₅ are each independently substituted. And represents an epoxy group or an oxetane group, and r and s each independently represent an integer of 0 or more, and t represents an integer of 1 or more.)

（式中、ＺはＺ_３を表し、ＥはＥ_３を表す。） An example of the crosslinkable monomer unit when the crosslinkable monomer unit is present in the polymer main chain is shown in the following general formula (13).

(In the formula, Z represents Z ₃ and E represents E _3. )

  In the crosslinkable polymer, the copolymerization monomer unit used as necessary is a monomer unit having a substituted or unsubstituted triphenylamine skeleton, an arylene and / or a heteroarylene which may be substituted or unsubstituted. A monomer unit is mentioned.

  In addition, the molar fraction of the crosslinkable monomer units in the total number of monomer units in the crosslinkable polymer is preferably 0.1 to 99.9%, more preferably 1 to 50%, and most preferably 10 to 50%. . If the molar fraction of the crosslinkable monomer unit is less than 0.1%, multilayering tends to be difficult, and if it exceeds 50%, the electrical characteristics tend to deteriorate.

  Moreover, it is preferable that the weight average molecular weights of the said crosslinkable polymer are 1000-1 million, and it is preferable that it is 5000-200000. If it is less than 1000, the film-forming ability tends to decrease, and if it exceeds 1,000,000, the solubility tends to decrease. In addition, said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using gel permeation chromatography.

  When the polymerization promoting polymer and the crosslinkable polymer are mixed and used, the weight percent concentration of the crosslinkable polymer with respect to the total weight of the organic electronics material is preferably 0.1% to 99.9%, preferably 1% to 99% is more preferable, and 10% to 90% is most preferable. If the amount of the crosslinkable polymer is too small, it is difficult to form a multilayer, and if it is too large, a long heating time tends to be required. Moreover, when mixing and using a polymerization promotion polymer and a crosslinkable polymer, the polymer which consists only of the said copolymerization monomer unit can also be mixed.

  The polymerization promoting polymer and the crosslinkable polymer in the present invention can be produced by various synthetic methods known to those skilled in the art. For example, when 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., Vol. 51). No. 7, p. 2091 (1978)) and M. Zembayashi et al. (Tet.lett., 47, 4089 (1977)) can be used. (Suzuki) et al. (Synthetic Communications, Vol. 11, No. 7, p. 513 (1981)) is generally used.

The reaction reported by Suzuki et al. Causes a Pd-catalyzed cross-coupling reaction (usually called the Suzuki reaction) between an aromatic boronic acid derivative and an aromatic halide. Various polymers that can be used in the present invention can be produced by using them for the reaction of bonding aromatic rings. This reaction also requires soluble Pd compounds in the form of Pd (II) salts or Pd (0) complexes. Aromatic reactants of 0.01 to 5 mole percent based on _{Pd (Ph 3 P) 4,} Pd and tertiary phosphine ligands (OAc) 2 complex and PdCl ₂ (dppf) complex is generally preferred Pd sources. Furthermore, this reaction also requires a base, and it is most preferable to use aqueous alkali carbonate or bicarbonate. In addition, a phase transfer catalyst can be used to promote the reaction in a nonpolar solvent. Examples of the solvent used at this time include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran.

  The thin film of the present invention is a method known to those skilled in the art for the organic electronics material of the present invention containing the polymerization promoting polymer, the compound having an epoxy group or oxetane group blended as necessary, the crosslinkable polymer, and a solvent. For example, an inkjet method, a casting method, a dipping method, letterpress printing, intaglio printing, offset printing, flat plate printing, letterpress reverse offset printing, screen printing, gravure printing, etc., coating on a substrate using a spin coating method, It can be manufactured by heat treatment. The thin film of the present invention thus obtained is, for example, alone, for example, a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, an electron injection of an organic EL element. Can be used as a layer or the like. Further, a new layer can be immediately formed thereon by performing a heat treatment after coating, and by repeating this, multilayering of organic electronics elements and organic EL elements can be easily achieved. In addition, the thickness of the thin film of the present invention may be appropriately determined according to the use and is not particularly limited. However, when used as a layer constituting an organic electronics element or an organic EL element, the thickness is in the range of 0.5 nm to 1 mm. It is desirable that

  Furthermore, even if various additives are added to the thin film, they can be used for organic electronics elements and organic EL elements. Examples of the additive include a metal complex containing a central metal such as Ir or Pt if used in a light emitting layer of an organic EL element, or a triphenylamine derivative if used in a hole injection layer or a hole transport layer. , Electron acceptors such as tetracyanoquinodimethane, and various oxidizing agents can be used.

  Moreover, the said coating method can be normally implemented in the temperature range of -20- + 300 degreeC, Preferably it is 10-100 degreeC, Most preferably, it is 15-50 degreeC. Examples of the solvent include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, anisole, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and ethyl cellosolve acetate.

  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 organic electronics element and the organic EL element of the present invention may be provided with a layer containing the organic electronics material of the present invention, and the structure thereof is not particularly limited. The general structure of organic EL is disclosed in, for example, US Pat. No. 4,539,507, US Pat. No. 5,151,629, etc., and polymer-containing organic EL elements Is disclosed in, for example, International Publication No. WO 90/13148 and European Patent Publication No. 04384861. 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. Furthermore, 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 In some cases, a layer is inserted between the electroluminescent layer (light emitting layer) and the anode.

  The cathode material is preferably a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF. As the anode, a metal (eg, Au) or other material having metal conductivity, for example, an oxide (eg, ITO: indium oxide / tin oxide) is used on a transparent substrate (eg, glass or transparent polymer). You can also

  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, and the like of an organic electronics element. Are preferably used as a hole injection layer, a hole transport layer, and a light emitting layer, more preferably used as a hole injection layer and a hole transport layer, and most preferably used as a hole transport 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.

  When the organic electronics material of the present invention is used as the hole transport layer of the organic EL element, the organic electronics material contains at least a polymerization promoting polymer and a crosslinkable polymer, and the copolymerization monomer unit in each polymer is It is preferable that the triphenylamine derivative is contained in an amount of 1 to 99%, more preferably 10 to 80%, and most preferably 40 to 50% in terms of a mole fraction in the total number of all monomer units. It can be improved.

  In addition to the above, the material for organic electronics of the present invention can also be used for organic transistors, particularly organic field effect transistors. The general structure of the organic transistor is described in “Technology improvement technique of organic transistor” (issued on November 27, 2003 by the Technical Information Association).

  The material for organic electronics of the present invention can be suitably used as an organic semiconductor layer of an organic transistor.

  In addition, after the organic transistor is manufactured, a protective layer containing an organic substance can be further applied using an inkjet method, a casting method, a dipping method, a printing method, a spin coating method, or the like.

  The material for organic electronics of the present invention can also be used for organic thin film solar cells, gas sensors, ion sensors, biosensors, pressure sensors, temperature sensors, and the like.

  The present invention is illustrated by the following examples, but the present invention is not limited thereto.

(Polymerization promoting polymer synthesis example 1)
In a round bottom flask, 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 (0.38 mmol), 3,5-dibromophenol (0.02 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10. 6 mmol), Aliquat 336 (0.4 mmol) and toluene (7 ml) were added, and the mixture was stirred at 80 ° C. for 48 hours 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 re-precipitation was repeated twice to purify, to obtain a polymerization promoting polymer A having the following structure. The molecular weight of the obtained polymer was 33,794 in terms of polystyrene.

(Polymerization promoting polymer synthesis example 2)
In a round bottom flask, 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 (0.38 mmol), 3,5-dibromoaniline (0.02 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10. 6 mmol), Aliquat 336 (0.4 mmol) and toluene (7 ml) were added, and the mixture was stirred at 80 ° C. for 48 hours 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 a polymerization promoting polymer B having the following structure was obtained. The molecular weight of the obtained polymer was 50,260 in terms of polystyrene.

(Polymerization promoting polymer synthesis example 3)
In a round bottom flask, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.41 mmol), 4,4 '-Dibromo-4''-n-butyltriphenylamine (0.4 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10.6 mmol), Aliquat 336 (0.4 mmol) and toluene ( 7 ml) and stirred at 80 ° C. for 48 hours under a nitrogen atmosphere.

4-Iodophenol (0.08 mmol) was added here, and also it stirred at 80 degreeC for 12 hours. The reaction solution was poured into a methanol / water mixed solvent (9: 1), and the precipitated polymer was filtered off. The re-precipitation was repeated twice to purify, and a polymerization promoting polymer C having the following structure was obtained. The molecular weight of the obtained polymer was 30,845 in terms of polystyrene.

(Polymerization promoting polymer synthesis example 4)
In a round bottom flask, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.41 mmol), 4,4 '-Dibromo-4''-n-butyltriphenylamine (0.4 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10.6 mmol), Aliquat 336 (0.4 mmol) and toluene ( 7 ml) and stirred at 80 ° C. for 48 hours under a nitrogen atmosphere.

To this, 2- (4-bromophenyl) ethanol (0.08 mmol) was added, and the mixture was further stirred at 80 ° C. for 12 hours. 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 a polymerization promoting polymer D having the following structure was obtained. The molecular weight of the obtained polymer was 34,506 in terms of polystyrene.

(Comparative polymer synthesis example) Synthesis of polymer consisting only of copolymerized monomer units In a round bottom flask, 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 (0.4 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M potassium carbonate An aqueous solution (10.6 mmol), Aliquat 336 (0.4 mmol) and toluene (7 ml) were added, and the mixture was stirred at 80 ° C. for 48 hours under a nitrogen atmosphere.

  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 Polymer A was obtained. The molecular weight of the obtained polymer was 60,216 in terms of polystyrene.

(Crosslinking monomer synthesis example 1)
Tetrahydrofuran (50 ml), methyltriphenylphosphonium bromide (10 mmol) and potassium-t-butoxide (10 mmol) were added to the round bottom flask and stirred for 30 minutes in a nitrogen stream.

  3,5-Dibromobenzaldehyde (10 mmol) was added thereto, and the mixture was stirred in a nitrogen stream for 5 hours. Water was added and the mixture was extracted with ether and purified by column chromatography to obtain 3,5-dibromostyrene.

  3,5-Dibromostyrene (5 mmol), chloroform (20 ml) and m-chloroperbenzoic acid (5 mmol) were added to the round bottom flask and stirred for 3 hours in a nitrogen stream. Water was added and the mixture was extracted with ether and purified by column chromatography to obtain a crosslinkable monomer A.

(Crosslinkable polymer synthesis example 1)
A round bottom flask was charged with 4,4′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4 ″ -n-butyltriphenylamine (0.4 mmol). ), 2,7-dibromo-9,9-dioctylfluorene (0.2 mmol), crosslinkable monomer A (0.2 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10.6 mmol) , Aliquat 336 (0.4 mmol) and toluene (7 ml) were added, and the mixture was stirred at 80 ° C. for 48 hours 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 and purified to obtain a crosslinkable polymer A having the following structure. The molecular weight of the obtained polymer was 13200 in terms of polystyrene.

(Crosslinking monomer synthesis example 2)
In a round bottom flask, 3-ethyl-3-hydroxymethyloxetane (1 mol) and pyridine (300 mL) were added. While cooling with ice, p-toluenesulfonic acid chloride (2 mol) was slowly added, and the mixture was further stirred at room temperature for 6 hours.

  The reaction solution was poured into 2 L of ice water, and the organic layer was separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off to give 3-ethyl-3- (p-toluenesulfonyloxymethyl) oxetane.

  4-Iodophenol (10 mmol), dimethylacetamide (10 mL) and 3-ethyl-3- (p-toluenesulfonyloxymethyl) oxetane (12 mmol) were placed in a round bottom flask. To this was added potassium hydroxide (12 mmol), and the mixture was heated with stirring at 90 ° C. for 6 hours.

  After cooling, the resulting inorganic salt was filtered off, ethyl acetate was added to the organic layer, and the mixture was washed with 1% acetic acid and water. After drying over anhydrous magnesium sulfate, the solvent was distilled off and purified by column chromatography to obtain a crosslinkable monomer B.

(Crosslinkable polymer synthesis example 2)
In a round bottom flask, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (0.41 mmol), 4,4 '-Dibromo-4''-n-butyltriphenylamine (0.4 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M aqueous potassium carbonate solution (10.6 mmol), Aliquat 336 (0.4 mmol) and toluene ( 7 ml) and stirred at 80 ° C. for 48 hours under a nitrogen atmosphere.

The crosslinkable monomer B (0.08 mmol) was added here, and also it stirred at 80 degreeC for 12 hours. 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 and purified to obtain a crosslinkable polymer B having the following structure. The molecular weight of the obtained polymer was 8300 in terms of polystyrene.

(Example of light-emitting polymer synthesis)
A round bottom flask was charged with 4,4′-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4 ″ -n-butyltriphenylamine (0.4 mmol). ), 4,4′-dibromo-triphenylamine (0.08 mmol), 4,7-dibromo-2,1,3-benzothiadiazole (0.32 mmol), tetrakistriphenylphosphine palladium (0.004 mmol), 2M An aqueous potassium carbonate solution (10.6 mmol), Aliquat 336 (0.4 mmol) and toluene (7 ml) were added, and the mixture was stirred at 80 ° C. for 48 hours 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 it to obtain a yellow light emitting polymer.

<Multilayer thin film structure fabrication example>
Example 1
Polymerization promoting polymer A (4.6 mg), bisphenol A type epoxy resin (1.4 mg), and toluene (0.68 ml) were mixed to prepare coating solution 1. The prepared coating solution 1, polymerization promoting polymer C (4.6 mg), bisphenol A type epoxy resin (1.4 mg), and toluene (0.68 ml) were mixed to prepare coating solution 2.

Next, the coating solution 1 was spin-coated at 3000 min ⁻¹ on a 27 mm × 22 mm × 0.7 mm quartz substrate and heated at 180 ° C. for 1 hour on a hot plate in a nitrogen stream. The film thickness at this time was 40 nm. Further, the coating solution 2 was spin-coated at 3000 min ⁻¹ and heated on a hot plate at 180 ° C. for 1 hour in a nitrogen stream. The final film thickness was 80 nm, and a thin film having a two-layer structure could be produced.

(Comparative Example 1)
Comparative polymer A (4.6 mg), bisphenol A type epoxy resin (1.4 mg) and toluene (0.68 ml) were mixed to prepare coating solution 3. The prepared coating solution 3 was mixed with comparative polymer A (6 mg) and toluene (0.68 ml) to prepare coating solution 4.

Next, the coating solution 3 was spin-coated at 3000 min ⁻¹ on a 27 mm × 22 mm × 0.7 mm quartz substrate, and heated at 180 ° C. for 1 hour on a hot plate in a nitrogen stream. The film thickness at this time was 40 nm. Further, the coating solution 4 was spin-coated at 3000 min ⁻¹ and heated on a hot plate at 180 ° C. for 1 hour in a nitrogen stream. The final film thickness was 40 nm, which was the same as that of the coating solution 4 alone. In Comparative Example 1, the first layer was dissolved and flowed out, and a multilayer structure could not be produced.

<Production of organic EL element>
(Example 2)
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, a coating solution 5 in which a polymerization promoting polymer A (4.4 mg), a bisphenol A type epoxy resin (0.6 mg) and toluene (1.2 ml) are mixed on the hole injection layer is spin-coated at 3000 min ^−1. Then, a hole transport layer (20 nm) was formed by heating on a hot plate at 200 ° C. for 30 minutes.

Next, a toluene solution (1.5 wt%) 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 ITO as a positive electrode and Al as a cathode of this organic EL element, yellow light emission was observed at about 5 V, and the current efficiency at a luminance of 6000 cd / m ² was 2.56 cd / A. The current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard, and the luminance was measured with SR-3 manufactured by Topcon.

In addition, as a lifetime characteristic, the luminance was measured with a Topcon BM-7 while applying a constant current of 0.5 mA, and the time when the luminance was reduced by half from the initial luminance (100 cd / m ² ) was measured. there were.

(Comparative Example 2)
An organic EL device was produced in the same manner as in Example 2 except that the hole transport layer using the coating solution 5 containing the polymerization promoting polymer A was not formed.

When a voltage was applied to this organic EL element, yellow light emission was observed at about 5 V, the current efficiency at a luminance of 6000 cd / m ² was 1.60 cd / A, and the efficiency of Example 2 was 1.6 times higher. Obtained.

  Further, when the lifetime characteristics were measured by applying a constant current of 0.5 mA, the luminance was reduced by half in 60 hours, and the lifetime of Example 2 was about 1.7 times longer.

It is the schematic of the organic EL element laminated | stacked.

Explanation of symbols

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 (11)

The material for organic electronics containing the high molecular compound represented by following General formula (1).

(Wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently an arylene group, heteroarylene group or triphenylamine derivative, Va is a functional group capable of polymerizing with an epoxy group or an oxetane group, and l and m are Each independently represents an integer of 0 or more, and n represents an integer of 1 or more.) The material for organic electronics containing the high molecular compound represented by following General formula (2).

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Vb and Vc are each independently a functional group capable of polymerizing with an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and l + m ≧ 1.) The material for organic electronics containing the high molecular compound represented by following General formula (3).

(Wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Va, Vb and Vc are each independently an epoxy group or an oxetane group. And l and m each independently represents an integer of 0 or more, and n represents an integer of 1 or more.)   The functional groups Va, Vb, and Vc in the general formulas (1), (2), and (3) are each a hydroxyl group, an amino group, a thiol group, an alkylamino group, a carboxyl group, or an imidazole group. The material for organic electronics in any one of 1-3. The material for organic electronics according to any one of claims 1 to 4, further comprising a compound having an epoxy group represented by the following general formula (4) or a compound having an oxetane group represented by the following general formula (5): .

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; p represents an integer of 1 to 8.)

(In the formula, X represents an alkyl group having 1 to 22 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a heteroaryl group, an arylene group, a heteroarylene group, or a triphenylamine derivative; q represents an integer of 1 to 8.) The organic electronics material according to any one of claims 1 to 5, further comprising a polymer represented by the following general formula (6).

(In the formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₃ represents a single bond, an oxygen atom, an ester group, or an alkylene group having 1 to 30 carbon atoms. Represents an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, E ₃ represents an optionally substituted epoxy group or oxetane group, and r and s each independently represent an integer of 0 or more. T represents an integer of 1 or more.) The organic electronics material according to any one of claims 1 to 5, further comprising a compound represented by the following general formula (7).

(In the formula, Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ each independently represent an arylene group or heteroarylene group or a triphenylamine derivative, and Z ₄ and Z ₅ each independently represent a single bond, an oxygen atom or an ester group. Represents an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E ₄ and E ₅ each independently represents an epoxy group or an oxetane group which may be independently substituted. And r and s each independently represent an integer of 0 or more.) The organic electronics material according to any one of claims 1 to 5, further comprising a compound represented by the following general formula (8).

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ are each independently an arylene group, heteroarylene group or triphenylamine derivative, and Z ₃ , Z ₄ and Z ₅ are each independently a single bond. Represents an oxygen atom, an ester group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an oxyarylene group, or a heteroarylene group, and E, E ₄ and E ₅ are each independently substituted. And represents an epoxy group or an oxetane group, and r and s each independently represent an integer of 0 or more, and t represents an integer of 1 or more.)   The thin film of thickness 0.5nm-1mm produced using the material for organic electronics in any one of Claims 1-8.   The organic electronics element produced using the organic electronics material in any one of Claims 1-8.   The organic electroluminescent element produced using the material for organic electronics in any one of Claims 1-8.

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