JP6123288B2 - Composition with variable solubility, hole transport material composition, and organic electronic device using the same - Google Patents

Description

  Embodiments of the present invention relate to a composition with varying solubility, a hole transport material composition, and an ink composition. In addition, another embodiment of the present invention relates to an organic layer using a composition in which solubility changes, a hole transport material composition, or an ink composition, and a method for forming the organic layer. Moreover, other embodiment of this invention is related with the organic electronics element which has an organic layer, an organic electroluminescent element (henceforth an organic EL element), and an organic photoelectric conversion element. Furthermore, other embodiment of this invention is related with the display element using an organic EL element, and an illuminating device.

  An organic electronics element is an element that performs an electrical operation using an organic substance. Organic electronic devices are expected to exhibit features such as energy saving, low cost, and high flexibility, and are attracting attention as technologies that replace conventional inorganic semiconductors mainly composed of silicon.

  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 or 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 organic material used. As the organic material, a low molecular material is used in the low molecular organic EL element, and a high molecular material is used in the high molecular organic EL element. Compared with a low-molecular-type organic EL element in which film formation is mainly performed in a vacuum system, a polymer-type organic EL element can be easily formed by printing or ink-jet. Therefore, the polymer organic EL element is expected as an indispensable element for future large-screen organic EL displays.

  Although low molecular organic EL elements and polymer organic EL elements have been intensively studied so far, improvement of element characteristics such as light emission efficiency and element lifetime is still a problem. As one means for solving this problem, the organic layers constituting the organic EL element are multilayered.

  In a low molecular weight organic EL element, since film formation is generally performed by a vapor deposition method, multilayering can be easily achieved by sequentially changing compounds used for vapor deposition. On the other hand, in the polymer type organic EL element, it is difficult to increase the number of layers. The reason is that, in the polymer type organic EL element, film formation is performed by a wet process such as printing or ink jetting, so that the lower layer formed earlier is dissolved when the upper layer is formed. In order to make a polymer organic EL element multi-layered, a method is desired in which when the upper layer is formed, the already formed lower layer does not change.

  In order to realize multilayering, studies have been made using compounds having greatly different solubilities. As a typical example, a film was formed using a hole injection layer made of polythiophene: polystyrene sulfonic acid (PEDOT: PSS) formed using an aqueous dispersion and an aromatic organic solvent such as toluene. An element having a two-layer structure with a light emitting layer can be given. In this case, since the hole injection layer made of PEDOT: PSS is not dissolved in the aromatic organic solvent, a two-layer structure can be produced.

  However, in this element, it is difficult to remove water, and water causes the characteristics of the organic EL element to deteriorate. In addition, since the drying is performed at a high temperature and / or for a long time to remove water, it is difficult to produce an organic EL element using a resin base material. Also, there are significant limitations to the process such as the need for reduced pressure conditions for water removal.

  As another method for realizing multi-layering, studies using the reaction of compounds have been made (for example, see Non-Patent Document 1, Patent Document 1, or Patent Document 2). These documents disclose a multilayering method by reacting a polymerizable substituent introduced into a compound. For example, multilayering using a polymerization reaction such as a silyl group, a styryl group, an oxetane group, or an acrylic group, or multilayering using a dimerization such as a trifluorovinyl ether group or a benzocyclobutene group.

Japanese Patent Laid-Open No. 2004-199935 International Publication No. 2005/053056

Carlos A. Zuniga, Stephen Barlow, and Seth R. Marder, "Approaches to Solution-Processed Multilayer Organic Light-Emitting Diodes Based on Cross-Linking", Chem. Mater., 2011, 23 (3), pp 658-681

  However, in the above method, when producing an organic EL device, those polymerizable substituents must be introduced into the compound used for forming the organic layer.

  An effective method for multilayering is required for all organic electronic devices in which two adjacent organic layers are formed by coating. For example, two adjacent organic layers (for example, a buffer layer and a photoelectric conversion layer) are formed by coating. The formed organic photoelectric conversion element is also desired.

  Therefore, an object of the embodiment of the present invention is to provide a composition, a hole transporting material composition, and an ink composition that enable multilayering of an organic layer by a coating method. Another object of another embodiment of the present invention is to provide an organic layer that can be multilayered by a coating method, and a method for forming the organic layer. Another object of the present invention is to provide an organic electronics element, an organic EL element, and an organic photoelectric conversion element having an organic layer formed by a coating method. Furthermore, another embodiment of the present invention aims to provide a display element and an illumination device using an organic EL element having an organic layer formed by a coating method.

  As a result of intensive investigations, the present inventors have found that a thin film formed using a composition having a unit having a hole transporting property and containing a polymer or oligomer having a pyrrolyl group and a solvent is subjected to heat and / or It has been found that the solubility of the thin film in the solvent is changed by adding light, and the present invention has been completed.

That is, the embodiment of the present invention contains a polymer or oligomer (A) having a unit having hole transporting property and having a pyrrolyl group which may have a substituent, and a solvent (B). , Heat, light, or a composition whose solubility is changed by applying both heat and light, and also relates to a hole transport material composition and an ink composition containing the composition.
In another embodiment of the present invention, an organic layer (I) formed by applying a composition having a variable solubility, a hole transport material composition, or an ink composition; A method of changing the solubility, comprising the step of applying heat, light, or both heat and light to the organic layer (I); and heat, light, or heat and light to the organic layer (I) It relates to the organic layer (II) obtained by adding both.
Moreover, other embodiment of this invention is related with the organic electronics element which has organic layer (II), an organic electroluminescent element, and an organic photoelectric conversion element.
Furthermore, other embodiment of this invention is related with the display element and illuminating device which used the organic electroluminescent element.

An example of the above embodiment is shown below.
As an example of the composition whose solubility is changed, a composition further containing an initiator (C); the unit having hole transportability is selected from the group consisting of a unit containing an aromatic amine structure and a unit containing a carbazole structure A composition comprising at least one unit selected from the group consisting of a polymer or an oligomer (A) represented by formula (Ia), a structure represented by formula (Ib), and formula (Ic) A composition having at least one structure selected from the group consisting of: a composition having a pyrrolyl group at the terminal of the polymer or oligomer (A); the polymer or oligomer (A) has a branched structure; And a polymer or oligomer having three or more terminals and having a pyrrolyl group at three or more of all terminals; the polymer or oligomer (A) is represented by the following formula (IIa): A composition having at least one structure selected from the group consisting of a structure represented by the structure represented by formula (IIIc): a composition in which the initiator (C) is an oxidizing agent; an initiator (C), The composition which is an onium salt; Or the composition whose weight average molecular weights of a polymer or an oligomer (A) are 1,000-1,000,000 are mentioned.
Examples of the organic electronics element include an element having at least two electrodes and an organic layer (II) positioned between the electrodes; examples of the organic electroluminescence element include an anode, an organic layer ( II), an element having a light emitting layer, and a cathode; and examples of the organic photoelectric conversion element include an anode, an organic layer (II), a photoelectric conversion layer, and an element having a cathode.

  According to the embodiment of the present invention, it is possible to provide a composition, a hole transporting material composition, and an ink composition that enable a multilayered organic layer by a coating method. Moreover, according to other embodiment of this invention, the formation method of the organic layer which can be multilayered by the apply | coating method, and an organic layer can be provided. Moreover, according to other embodiment of this invention, the organic electronics element, organic EL element, and organic photoelectric conversion element which have the organic layer formed into a film by the apply | coating method can be provided. Furthermore, according to other embodiment of this invention, the display element and illuminating device using the organic EL element which has the organic layer formed into a film by the apply | coating method can be provided.

Embodiments of the present invention will be described below.
[Composition with varying solubility]
The composition with varying solubility according to an embodiment of the present invention includes a polymer or oligomer (A) having a unit having hole transporting property and having a pyrrolyl group which may have a substituent, and a solvent It is a composition that contains (B) and whose solubility is changed by applying heat, light, or both heat and light. Here, the “pyrrolyl group” refers to a monovalent substituent derived from pyrrole. If necessary, the composition whose solubility is changed may contain an initiator (C). Moreover, even if the composition from which a solubility changes contains 1 type of polymer or an oligomer (A), a solvent (B), or an initiator (C), respectively, and may contain 2 or more types, respectively. Good.

[Polymer or oligomer (A)]
The unit having a hole transporting property is not limited as long as it has an ability to transport holes, and examples thereof include a unit including an aromatic amine structure, a unit including a carbazole structure, and a unit including a thiophene structure. A unit containing an aromatic amine structure and a unit containing a carbazole structure are preferred. The polymer or oligomer (A) may have two or more of these units. The polymer or oligomer (A) may have a branched structure in the molecule and may have three or more terminals. The branched structure refers to a structure in which a polymer or oligomer chain has a branched portion and units constituting the polymer or oligomer chain are directed in three or more directions from the branched portion. The polymer or oligomer (A) having a branched structure and having three or more terminals is composed of a main chain and a side chain.

  Formulas (1a) to (93a), which are examples of units having hole transportability, are listed below. The units represented by the formulas (85a) to (93a) have a branched portion.

<Formulas (1a) to (84a)>

In formulas (1a) to (84a), each E independently represents —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , and the following formula (a): ) To (c)

(Wherein 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, a, b and c represents an integer greater than or equal to 1. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, which may have a substituent. And an atomic group obtained by removing one hydrogen atom from an aromatic compound having a hetero atom, which may have a substituent. Examples of the substituent here include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, and a hydroxyl group. Group, hydroxyalkyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imino group, amide group (-(NH) -COR), Examples thereof include an imide group (—N (COR) ₂ ), a carboxyl group, a substituted carboxyl group, a cyano group, and a monovalent heterocyclic group. Moreover, a, b, and c preferably represent an integer of 1 to 4.

  In the above, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-nonyl group. N-decyl group, n-undecyl group, n-dodecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, cycloheptyl Group, cyclooctyl group and the like. Examples of the aryl group include phenyl, biphenyl-yl, terphenyl-yl, naphthalen-yl, anthracenyl, tetracene-yl, fluorenyl, phenanthrene-yl and the like. Examples of the heteroaryl group include pyridyl-yl, pyrazin-yl, quinolin-yl, isoquinolin-yl, acridine-yl, phenanthroline-yl, furan-yl, pyrrol-yl, thiophen-yl, carbazol-yl, oxazole- Yl, oxadiazol-yl, thiadiazol-yl, triazol-yl, benzoxazol-yl, benzooxadiazol-yl, benzothiadiazol-yl, benzotriazol-yl, benzothiophene-yl and the like. In the following, examples similar to these can be used as the alkyl group, aryl group, and heteroaryl group.

  Ar independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms, or represents an aryl group or heteroaryl group having 2 to 30 carbon atoms. The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and may have a substituent. The heteroarylene group is a group of two hydrogen atoms from an aromatic compound having a hetero atom. It is an atomic group excluding and may have a substituent. The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and may have a substituent. The heteroaryl group is a hydrogen atom from an aromatic compound having a hetero atom. It is an atomic group excluding one, and may have a substituent. Examples of the substituent here include the same groups as those described above for E.

  Examples of the arylene group include phenylene, biphenyl-diyl, terphenyl-diyl, naphthalene-diyl, anthracene-diyl, tetracene-diyl, fluorene-diyl, phenanthrene-diyl, and the like. Examples of the heteroarylene group include pyridine-diyl, pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl, phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl, carbazole-diyl, oxazole- Examples include diyl, oxadiazole-diyl, thiadiazole-diyl, triazole-diyl, benzoxazole-diyl, benzooxadiazole-diyl, benzothiadiazole-diyl, benzotriazole-diyl, and benzothiophene-diyl. In the following, examples similar to these can be used as the arylene group (arenediyl group) and the heteroarylene group (heteroarenediyl group).

  X and Z are each independently a divalent linking group, and there is no particular limitation. However, a group in which one hydrogen atom is further removed from a group having one or more hydrogen atoms in E, or the following linking group: The groups exemplified in the group (A) are preferred. x represents an integer of 0-2. Y is a trivalent linking group, and is not particularly limited. However, a group obtained by further removing two hydrogen atoms from a group having two or more hydrogen atoms in E is preferable.

<Linking group group (A)>

  In the formula, each R independently represents a hydrogen atom, an optionally substituted linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an optionally substituted carbon atom. Represents 2 to 30 aryl groups or heteroaryl groups. Ar represents a trivalent or tetravalent linking group, and is preferably an atomic group obtained by further removing one or two hydrogen atoms from an arylene group or heteroarylene group having 2 to 30 carbon atoms.

<Formulas (85a) to (93a)>

  In the formulas (85a) to (93a), each Ar independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. Y represents a divalent linking group. The units represented by formulas (85a) to (93a) may have a substituent, and examples of the substituent include the same groups as E in formulas (1a) to (84a).

  Y in the formulas (89a) and (93a) is preferably a divalent linking group represented by the following formula.

  In the formula, each R independently represents a hydrogen atom, an optionally substituted linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an optionally substituted carbon atom. Represents 2 to 30 aryl groups or heteroaryl groups.

  Examples of the formulas (85a) and (86a) include the following formulas (85a-1) and (86a-1). In the following, only examples of the formulas (85a) and (86a) are shown, but as an example of the formulas (87a) to (89a) and (91a) to (93a), Ar similarly has a substituent. Examples of the unit may be a benzene ring.

  In formula (85a-1) or (86a-1), R each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. Examples of the monovalent organic group represented by R include 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. May have a group bonded through an ether bond.

  The polymer or oligomer (A) may be a copolymer having two or more units constituting a polymer or oligomer chain. The copolymer may be an alternating, random, block or graft copolymer, or a copolymer having an intermediate structure thereof, for example, a random copolymer having a block property.

  The polymer or oligomer (A) is represented by the above-mentioned arylene group or heteroarylene group, or the following formulas (1) to (32), in addition to the above units, in order to adjust the solubility, heat resistance, or electrical characteristics. A copolymer having a structure as a copolymer unit may be used. The units represented by the formulas (30) to (32) have a branch portion.

<Formulas (1) to (28)>

  In formulas (1) to (28), examples of R include the same groups as E in formulas (1a) to (84a).

<Formula (29)>

In formula (29), R ¹ and R ² are each independently selected from the group consisting of hydrogen and substituents consisting of C, H and / or X (where X is a heteroatom), Ar ¹ and Ar ² is independently a group selected from the group consisting of a divalent aromatic ring consisting of C and H, and a divalent aromatic ring consisting of C, H and X (X is a heteroatom). is there. Note that R ¹ and R ² are not simultaneously hydrogen. C is a carbon atom and H is a hydrogen atom. Examples of X include O (oxygen atom), N (nitrogen atom), S (sulfur atom), Si (silicon atom), halogen atom, and the like.

R ¹ and R ² have a substituent composed of C, H and / or X, an aliphatic substituent composed of C and H, an aromatic substituent composed of C and H, an aromatic composed of C, H and X Substituents, substituents composed of C, H and / or X (including aliphatic substituents) other than these can be mentioned. The divalent aromatic ring composed of C and H in Ar ¹ and Ar ² is a divalent aromatic such as a single ring or a condensed ring formed by condensing two or more, preferably 2 to 5 rings. Group hydrocarbon ring. Examples of the divalent aromatic ring composed of C, H and X (X is a heteroatom) include a heteromonocyclic ring or a condensed ring formed by condensing 2 or more, preferably 2 to 5 rings. A bivalent heteroaromatic ring is mentioned. The groups Ar ¹ and Ar ² may have a substituent.

Specific examples of R ¹ and R ² include the same groups as E in formulas (1a) to (84a). Specific examples of Ar ¹ and Ar ² include the same groups as Ar in formulas (1a) to (84a).

<Formulas (30) to (32)>

  In formulas (30) to (32), W represents a trivalent linking group, and is preferably an atomic group obtained by further removing one hydrogen atom from an arylene group or heteroarylene group having 2 to 30 carbon atoms. . Ar independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms, and Z represents any of a carbon atom, a silicon atom, or a phosphorus atom. The units represented by formulas (30) to (32) may have a substituent, and examples of the substituent include the same groups as E in formulas (1a) to (84a).

  The polymer or oligomer (A) has a pyrrolyl group which may have a substituent. The polymer or oligomer (A) may have a pyrrolyl group as a substituent of a unit constituting the main chain or side chain, and may have a terminal of the main chain or side chain. The units constituting the main chain or the side chain are, for example, units represented by the above formulas (1a) to (93a) and formulas (1) to (32).

  Examples of the pyrrolyl group which may have a substituent include a 1-pyrrolyl group, a 2-pyrrolyl group and a 3-pyrrolyl group which may have a substituent. The pyrrolyl group is represented by any of the following formulas (Ia) to (Ic), for example.

（式（Ｉａ）〜（Ｉｃ）中のＲ^１〜Ｒ^４は、それぞれ独立に、水素原子又はアルキル基を表し、Ｒ^２〜Ｒ^４の少なくとも１つは水素原子である。）
アルキル基としては、例えば、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基が挙げられ、直鎖アルキル基が好ましい。炭素数はより好ましくは１〜１０個である。

(R ^{1 to} R ^{4 in} formulas (Ia) to (Ic) each independently represent a hydrogen atom or an alkyl group, and at least one of R ^{2 to} R ⁴ is a hydrogen atom.)
As an alkyl group, a C1-C22 linear, cyclic or branched alkyl group is mentioned, for example, A linear alkyl group is preferable. The number of carbon atoms is more preferably 1-10.

  Examples of the polymer or oligomer (A) having a pyrrolyl group include polymers or oligomers having a structure represented by the following formulas (IIa) to (IIIc).

（式（IIａ）〜（IIｃ）中のＲ^１〜Ｒ^４は、それぞれ独立に、水素原子又はアルキル基を表し、Ｒ^２〜Ｒ^４の少なくとも１つは水素原子であり、Ａｒ^ａは、アレーンジイル基又はヘテロアレーンジイル基を表す。）

(R ^{1 to} R ^{4 in} formulas (IIa) to (IIc) each independently represent a hydrogen atom or an alkyl group, at least one of R ^{2 to} R ⁴ is a hydrogen atom, and Ar ^a is an arenediyl Represents a group or a heteroarenediyl group.)

（式（IIIａ）〜（IIIｃ）中のＲ^１〜Ｒ^４は、それぞれ独立に、水素原子又はアルキル基を表し、Ｒ^２〜Ｒ^４の少なくとも１つ以上は水素原子であり、Ａｒ^ｂは、アレーントリイル基又はヘテロアレーントリイル基を表す。）

(R ^{1 to} R ^{4 in} formulas (IIIa) to (IIIc) each independently represent a hydrogen atom or an alkyl group, at least one of R ^{2 to} R ⁴ is a hydrogen atom, and Ar ^b is Represents an arenetriyl group or a heteroarenetriyl group.)

Here, Ar ^a represents, for example, an arenediyl group having 2 to 30 carbon atoms or a heteroarenediyl group. An arenediyl group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, which may have a substituent, and a heteroarenediyl group is two hydrogen atoms from an aromatic compound having a heteroatom. It is an atomic group excluding and may have a substituent. Examples of the substituent include the same groups as E in formulas (1a) to (84a).

Ar ^b represents, for example, an arenetriyl group having 2 to 30 carbon atoms or a heteroarenetriyl group. An arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon and may have a substituent. A heteroarenetriyl group is a hydrogen atom from an aromatic compound having a heteroatom. An atomic group excluding three atoms, which may have a substituent. Examples of the substituent include the same groups as E in formulas (1a) to (84a).

  Examples of the arene-triyl group include benzene-triyl, biphenyl-triyl, terphenyl-triyl, naphthalene-triyl, anthracene-triyl, tetracene-triyl, fluorene-triyl, phenanthrene-triyl, and the like. Examples of the heteroarene triyl group include pyridine-triyl, pyrazine-triyl, quinoline-triyl, isoquinoline-triyl, acridine-triyl, phenanthroline-triyl, furan-triyl, pyrrole-triyl, thiophene-triyl, carbazole-triyl, Examples include oxazole-triyl, oxadiazole-triyl, thiadiazole-triyl, triazole-triyl, benzoxazole-triyl, benzooxadiazole-triyl, benzothiadiazole-triyl, benzotriazole-triyl, benzothiophene-triyl, and the like.

Ar ^a and Ar ^b are specifically Ar in the formulas (1a) to (93a), a carbazole structure, a thiophene structure; a benzene ring in the formulas (85a-1) and (86a-1); ) To (28) Arylene group, heteroarylene group; Ar ¹ and Ar ^{2 in} formula (29); W in formula (30); fluorene structure in formula (31); Ar in formula (32) Etc.

Specific structures included in the polymer or oligomer (A) are listed below. In formula, n is an integer of 1-22, Preferably it is an integer of 1-10.
<Pyrrolyl group (A)>

<Pyrrolyl group (B)>

  Among these, the following structures are preferable from the viewpoint of increasing the change in solubility, reducing the influence on the energy level of the hole transport site, and improving productivity.

When it has a pyrrolyl group as a substituent, for example, the polymer or oligomer (A) may contain a unit having a pyrrolyl group. As the unit having a pyrrolyl group, specifically, a unit represented by the formulas (1a) to (14a) in which any one or more of monovalent Ar is a pyrrolyl group; any one or more of E is pyrrolyl A unit represented by formulas (15a) to (84a) as a group; a unit represented by formulas (1a) to (93a) in which Ar has a pyrrolyl group; a formula in which any one or more of R is a pyrrolyl group Units represented by (1) to (28); Ar ¹ and / or Ar ² represented by formula (29) having a pyrrolyl group; represented by formulas (30) to (32) having a pyrrolyl group Units.

  An example of a preferable polymer or oligomer (A) has a unit represented by any one of formulas (85a) to (93a) and formulas (30) to (32), and constitutes a main chain or a side chain. The unit has a pyrrolyl group represented by the formula (Ia), (Ib) or (Ic) as a substituent. The polymer or oligomer (A) having a pyrrolyl group represented by the formula (Ia), (Ib) or (Ic) as a substituent is, for example, a monomer corresponding to the above pyrrolyl group group (B) as a monomer used for synthesis. Can be obtained.

  In the case of having a pyrrolyl group at the terminal, the terminal may be the terminal of the main chain or the terminal of the side chain, or may be the terminal of both the main chain and the side chain. Moreover, the polymer or oligomer (A) may have a pyrrolyl group at all of the terminals, or may have a part of all the terminals. Specifically, when the polymer or oligomer (A) has two ends and a pyrrolyl group at the two ends, the polymer or oligomer (A) has three or more ends, and the three or more In the case of having a pyrrolyl group at three or more of the ends of

  The polymer or oligomer (A) preferably has a pyrrolyl group at the end, more preferably only at the end, from the viewpoints of improving characteristics and increasing the change in solubility of the composition. preferable.

  Further, the polymer or oligomer (A) preferably has a pyrrolyl group at all of the terminals from the viewpoint of increasing the solubility change of the composition, and has three or more terminals, all of them. It is more preferable to have a pyrrolyl group. The fact that the polymer or oligomer (A) has three or more terminals, that is, that it has a branched structure, can increase the weight average molecular weight, increase the glass transition temperature, and improve the heat resistance. It is also preferable from the viewpoint of contributing.

  An example of a preferable polymer or oligomer (A) has a unit represented by any one of formulas (85a) to (93a) and formulas (30) to (32), and is terminated with formula (Ia), ( It has a pyrrolyl group represented by Ib) or (Ic). The polymer or oligomer (A) having a pyrrolyl group represented by the formula (Ia), (Ib) or (Ic) at the terminal is, for example, a monomer corresponding to the pyrrolyl group group (A) as a monomer used for synthesis. It can be obtained by using.

  The weight average molecular weight of the polymer or oligomer (A) is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of suppressing crystallization and obtaining good film forming properties. More preferably, it is 1,000 or more. Further, the weight average molecular weight of the polymer or oligomer (A) is 1,000,000 or less from the viewpoint that the solubility in a solvent is improved and a composition containing a solvent described later can be easily produced. It is preferably 900,000 or less, more preferably 800,000 or less. The “weight average molecular weight” refers to a weight average molecular weight in terms of standard polystyrene as determined by gel permeation chromatography (GPC).

  More specifically, the weight average molecular weight of the polymer or oligomer (A) is preferably 1,000 to 1,000,000. More preferably, it is 2,000-900,000, More preferably, it is 3,000-800,000.

  The average value of the number of units of the units of the polymer or oligomer (A) is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more from the viewpoint of obtaining good film-forming stability. Further, the average value of the number of units is preferably 1,000 or less, more preferably 500 or less, and even more preferably 200 or less, from the viewpoint that the solubility of the composition changes sufficiently and the organic layer can be easily laminated. The “average value of the number of units” can be determined from the weight average molecular weight of the polymer or oligomer (A), the molecular weight of each unit, and the ratio of each unit in the polymer or oligomer (A). In addition, the “unit ratio” can be determined from the charged amount ratio (molar ratio) of monomers corresponding to each unit used to synthesize the polymer or oligomer (A).

  More specifically, the average value of the number of units of the polymer or oligomer (A) is preferably 2 to 1,000, more preferably 5 to 500, and still more preferably 10 to 200.

  Further, the ratio of the units represented by the formulas (1a) to (93a) with respect to all units in the polymer or oligomer (A) is preferably 10% or more from the viewpoint of obtaining excellent hole transportability, and 25% The above is more preferable, and 50% or more is more preferable. Further, the proportion of the units represented by the formulas (1a) to (93a) can be 100%, or 95% or less when considering the introduction of a pyrrolyl group at the terminal. Preferably, 90% or less is more preferable, and 80% or less is more preferable.

  More specifically, the ratio of the units represented by the formulas (1a) to (93a) to all units in the polymer or oligomer (A) is preferably 10 to 95%, more preferably 25 to 90%, -80% is more preferable.

  When the polymer or oligomer (A) has a branched structure, the ratio of the units represented by the formulas (85a) to (93a) and the formulas (30) to (32) with respect to all units in the polymer or oligomer (A) is: From the viewpoint of increasing the number of terminals and increasing the change in solubility, it is preferably 1% or more, more preferably 3% or more, and even more preferably 10% or more. Moreover, the ratio of the units represented by formulas (85a) to (93a) and formulas (30) to (32) is from the viewpoint of preventing poor synthesis due to gelation during the synthesis of the polymer or oligomer (A). 50% or less is preferable, 30% or less is more preferable, and 25% or less is more preferable.

  More specifically, the ratio of the units represented by any one of formulas (85a) to (93a) and formulas (30) to (32) with respect to all units in the polymer or oligomer (A) is 1 to 50%. Is preferable, 3 to 30% is more preferable, and 10 to 25% is more preferable.

  From the viewpoint of increasing the change in solubility of the composition, the ratio of pyrrolyl groups to all units in the polymer or oligomer (A) is preferably 1% or more, more preferably 3% or more, and even more preferably 10% or more. The proportion of the pyrrolyl group is preferably 80% or less, more preferably 60% or less, and even more preferably 40% or less from the viewpoint of reducing the influence on the energy level of the hole transporting site. The “proportion of pyrrolyl group” herein is the proportion of units having a structure represented by the formula (Ia) or (Ib), and is preferably represented by the pyrrolyl group group (A) or (B). It is the ratio of the unit which has a structure to be formed, More preferably, it is the ratio of the unit which has a structure represented by the pyrrolyl group group (A).

  More specifically, the ratio of pyrrolyl groups to all units in the polymer or oligomer (A) is preferably 1 to 80%, more preferably 3 to 60%, and even more preferably 10 to 40%.

  The polymer or oligomer (A) can be produced by various synthetic methods known to those skilled in the art. For example, in the case of producing a polymer or oligomer (A) in which each monomer unit used for the synthesis of the polymer or oligomer (A) has an aromatic ring and the aromatic rings are bonded to each other, T. Yamamoto Bull. Chem. Soc. Jpn., 51, 7, 2091 (1978), M. Zembayashi et al., Tet. Lett., 47, 4089 (1977), and Suzuki (A Suzuki) Synthetic Communications, Vol.11, No.7, p.513 (1981) can be used. In particular, the process described in A. Suzuki is common for the production of polymers or oligomers (A). As each monomer unit, a monomer unit corresponding to the unit exemplified above and a monomer unit corresponding to the pyrrolyl group exemplified above can be used.

  The method described in A. Suzuki is a cross-coupling reaction (usually called “Suzuki reaction”) using a Pd catalyst between an aromatic boronic acid derivative and an aromatic halide. ). A polymer or an oligomer (A) can be produced by using desired aromatic rings in a bonding reaction.

In the Suzuki reaction, a Pd (II) salt or a soluble Pd compound in the form of a Pd (0) complex is generally used as the Pd catalyst. For example, 0.01-5 mol% Pd (Ph ₃ P) ₄ , Pd (OAc) ₂ complex with a tertiary phosphine ligand, Pd ₂ (dba) ₃ complex and PdCl ₂ (dppf) based on aromatic reactants Complexes are the preferred Pd source.

  In this reaction, a base is also generally used, and the base is preferably an aqueous alkali carbonate or bicarbonate, or a hydroxide of tetraalkylammonium. 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.

[Solvent (B)]
The composition whose solubility varies includes a solvent. As the solvent, a solvent capable of forming a coating layer using the composition can be used, and preferably a solvent capable of dissolving the polymer or oligomer (A) and the initiator (C) used as necessary. Can be used.

  Examples of the solvent include water; alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin and diphenylmethane. Aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3- Aromatic ethers such as methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, and lactate n Aliphatic esters such as butyl; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like. Aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers are preferred.

  The content of the solvent in the composition can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the polymer or oligomer (A) to the solvent is 0.1% by weight or more, more preferably 0.2% by weight or more, and 0.5% by weight. The amount which becomes above is more preferable. The solvent content is preferably such that the ratio of the polymer or oligomer (A) to the solvent is 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less. preferable.

  More specifically, the content of the solvent in the composition is preferably such that the ratio of the polymer or oligomer (A) to the solvent is 0.1 to 10% by weight, and is 0.2 to 5% by weight. The amount is more preferably 0.5 to 3% by weight.

[Initiator (C)]
Initiator (C) may be used to change the solubility of the composition. As the initiator (C), a substance that can act as an oxidizing agent in the composition can be used. The use of a substance that can act as an oxidizing agent for the polymer or oligomer (A) is preferable from the viewpoint of improving hole transportability. As the initiator (C), an onium salt composed of a cation and an anion is preferable from the viewpoint of a change in the solubility of the composition, and details thereof will be described below. From the viewpoint of increasing the amount of change in solubility of the composition, it is preferable to use the initiator (C).

[Cation]
Examples of the cation include H ⁺ , carbenium ion, ammonium ion, anilinium ion, pyridinium ion, imidazolium ion, pyrrolidinium ion, quinolinium ion, imonium ion, aminium ion, oxonium ion, and pyrylium ion. , Chromenilium, xanthylium ion, iodonium ion, sulfonium ion, phosphonium ion, tropylium ion, cation with transition metal, etc., carbenium ion, ammonium ion, anilinium ion, aminium ion, iodonium ion, sulfonium ion Tropylium ion is preferred. Ammonium ion, anilinium ion, iodonium ion, and sulfonium ion are more preferable from the viewpoint of compatibility between the solubility change characteristics of the composition and storage stability.

[Anion]
Examples of the anion include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ and C ₆ H ₅ SO ₃ ^−. , Sulfonate ions such as CF ₃ SO ₃ ^— , sulfate ions such as HSO ₄ ⁻ , SO ₄ ²⁻ ; carbonate ions such as HCO ₃ ⁻ , CO ₃ ²⁻ ; H ₂ PO ₄ ⁻ , HPO ₄ ^{2. -,} phosphate ion such as _{^{PO 4 3-; PF 6 -,}} PF 5 OH - fluorophosphate ions such _{as; [(CF 3 CF 2)} 3 PF 3] -, [(CF 3 CF 2 CF 2 ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF _{3 ^{] -, [((CF 3}} ) CFCF _{2) 2} PF _4] ^- a fluorinated alkyl fluorophosphate ions such ^{_{as; (CF 3 SO 2) 3}} C -, (CF 3 SO 2) 2 N - fluoroalkanes methide such as, imide ion such; BF _{^{4 -, B (C 6 F}} 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such _{^{as; SbF 6 -, SbF 5 OH}} - fluoro antimonate ion such as; AsF ₆ ^- , _AsF 5 OH ^- fluoroarsenate periodate ions such as; AlCl ₄ ^-, BiF ₆ ^-, and the like. From the viewpoint of the property of changing the solubility of the composition when used in combination with the aforementioned cation, fluorophosphate ions such as PF ₆ ⁻ and PF ₅ OH ⁻ ; [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) Fluorinated alkyl fluorophosphate ions such as ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^— ; (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO _{2) 2} N ^- fluoroalkanes methide such as, imide ion _{^{such; BF 4 -, B (C}} 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such as; SbF ₆ ^-, SbF OH ^- preferably fluoro antimonate ion such as, inter alia borate ions are particularly preferred.

  More specifically, one selected from ammonium ion, anilinium ion, iodonium ion, and sulfonium ion, and fluorophosphate ions, fluorinated alkylfluorophosphate ions, fluoroalkanesulfonylmethide, imide ions And an initiator comprising one selected from borate ions and fluoroantimonate ions. Specific examples of the anion and cation contained in this preferred initiator are not limited to the above, and known anions and cations can be used.

  Even when the composition does not contain an initiator, the solubility of the composition can be changed by light irradiation and / or heating. When the composition contains an initiator, the solubility change tends to increase. Further, the solubility can be changed by low temperature and short time heating. From the viewpoint of facilitating lamination by coating, the composition preferably contains an initiator (C).

  When the composition contains the initiator (C), the content is 0.1% relative to the weight of the polymer or oligomer (A) from the viewpoint of changing the solubility of the composition and facilitating lamination. It is preferably at least wt%, more preferably at least 0.2 wt%, and even more preferably at least 0.5 wt%. In addition, the content of the initiator (C) is preferably 30% by weight or less from the viewpoint of preventing deterioration of device characteristics due to a substance derived from the initiator (C) remaining in the organic layer. More preferably, it is less than or equal to 20% by weight and even more preferably less than or equal to 20% by weight. Examples of the substance derived from the initiator (C) include the initiator (C) itself, a decomposition product of the initiator (C), and a reaction product.

  More specifically, the content of the initiator (C) is preferably in the range of 0.1 to 30% by weight, preferably 0.2 to 25% by weight, based on the weight of the polymer or oligomer (A). The range is more preferable, and the range of 0.5 to 20% by weight is particularly preferable.

  The solubility of the composition can be changed by light irradiation and / or heating, so that lamination by coating with the same kind of solvent is possible. For light irradiation, for example, light having a wavelength of 200 to 800 nm can be used. Moreover, it is preferable that heating temperature is 60-300 degreeC, It is more preferable that it is 80-250 degreeC, It is further more preferable that it is 100-220 degreeC. The heating time is preferably 10 seconds to 2 hours, more preferably 1 minute to 1 hour, and even more preferably 1 to 10 minutes.

  Although the mechanism for changing the solubility of the composition is not clear, in one example of the mechanism, pyrrolyl groups form bonds with each other, for example, pyrrolyl groups form covalent bonds with the action of light and / or heat and an initiator. It is estimated that the solubility of the composition changes. The polymer or oligomer (A) may have a group that forms a bond such as a carbon-carbon double bond group or a group having a small ring, but in addition to the pyrrolyl group, from the viewpoint of improving device characteristics. May not have a group for forming a bond. Since the composition changes in solubility, as an embodiment, the composition can be used as a curable resin composition.

  In order to increase the number of organic layers, it is preferable that the degree of change in the solubility of the composition in the solvent is larger. “The solubility of the composition changes” can be confirmed by whether or not the solubility of the organic layer formed using the composition in the solvent changes before and after the application of light and / or heat. Specifically, first, an organic layer (1) is formed by a coating method using a composition containing a polymer or oligomer (A) and, if necessary, an initiator (C) and a solvent (1). After passing through an arbitrary drying step, light and / or heat is applied to the organic layer (1) to obtain the organic layer (2). Subsequently, the organic layer (2) is brought into contact with the solvent (2) to obtain the organic layer (3). It can be said that the greater the thickness of the organic layer (3) obtained, the greater the degree of change in solubility of the composition. That is, it is preferable that the ratio of the thickness of the organic layer (3) to the thickness of the organic layer (2) (that is, the residual ratio of the organic layer) is large. Specifically, the residual ratio is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more. The residual rate can be obtained from the ratio of the measured thickness values of the organic layer (2) and the organic layer (3) or the ratio of the measured absorbance values of the organic layer (2) and the organic layer (3).

  At this time, the thickness of the organic layer (2) may be in the same range as the thickness of the organic layer which is an embodiment of the present invention described later. The solvent (2) may be the same solvent as the solvent (1), or when the solvent (1) is a mixed solvent, the solvent having the largest weight ratio contained in the solvent (1) or toluene. it can. In the solvent (1), the solvent having the largest weight ratio contained in the solvent (1), or the confirmation using toluene, it is preferable that the film thickness of the organic layer (3) is not less than the above. Confirmation using the solvent having the largest weight ratio contained in the solvent (1) or toluene is simple, and confirmation using toluene is particularly easy.

  Since the composition whose solubility is changed contains a polymer or oligomer (A) having a unit having a hole transport property as described above, it is used for forming an organic electronic element such as an organic EL element or an organic photoelectric conversion element. It can preferably be used as a hole transport material composition to be used.

[Hole transport material composition]
Moreover, embodiment of this invention is related with the positive hole transport material composition containing the said composition.
The hole transport material composition only needs to contain a polymer or oligomer (A) and, if necessary, an initiator (C), and generally a solvent (B) capable of dissolving or dispersing them. Examples of the solvent are as described above. The hole transport material composition may further contain a low molecular compound, a substance that can act as a dopant, and the like.

[Ink composition]
An embodiment of the present invention also relates to an ink composition containing the composition.
The ink composition only needs to contain a polymer or oligomer (A) and, if necessary, an initiator (C), and generally a solvent (B) capable of dissolving or dispersing them. Examples of the solvent are as described above. The ink composition further includes other additives such as polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, anti-reducing agents, oxidizing agents, reducing agents, surface modifiers, An emulsifier, an antifoaming agent, a dispersant, a surfactant and the like may be included.

[Organic layer]
In addition, in the embodiment of the present invention, the organic layers (I) and (II) (hereinafter referred to as the organic layer (I) and the organic layer (I)) formed from the composition, the hole transporting material composition, or the ink composition, in which the solubility is changed. / Or the organic layer (II) may be simply referred to as “organic layer”). The organic layer (I) can be formed by applying these compositions.

  As a coating method, for example, an ink jet method, a casting method, a dipping method, a relief printing, an intaglio printing, an offset printing, a planographic printing, a printing plate reverse printing, a printing method such as a screen printing, a gravure printing, a known method such as a spin coating method, etc. The method is mentioned. Application | coating 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. Moreover, after application | coating, the obtained organic layer (I) is normally dried with a hotplate or oven at the temperature range of + 30- + 300 degreeC, Preferably it is 60-250 degreeC, Most preferably, it is 80-220 degreeC, May be removed. The drying time is usually 10 seconds to 2 hours, preferably 1 minute to 1 hour, particularly preferably 1 to 10 minutes.

  By adding heat, light, or both heat and light to the organic layer (I) formed by coating, an organic layer (II) having a different solubility from that before the addition can be obtained. Conditions for applying light and / or heat (light irradiation and / or heating conditions) are as described above. Since the organic layer (II) has low solubility in a solvent, another organic layer can be easily formed on the organic layer (II) using a coating solution. The solvent contained in the coating solution when forming another organic layer is not limited to the above-mentioned solvent (2).

  For light irradiation, 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, and heating is performed on a hot plate or in an oven. Can be done within.

  The thickness of the organic layer can be appropriately set depending on the application. For example, the thickness can be 5 nm to 10 μm. In particular, when an organic layer is used for a hole injection layer and / or a hole transport layer of an organic EL device, the thickness of the organic layer changes in solubility from the viewpoint of relaxing the surface roughness of the anode and reducing short circuit. Before and after the treatment, 5 nm or more is preferable, 10 nm or more is more preferable, and 20 nm or more is more preferable. The thickness of the organic layer is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less from the viewpoint of reducing the driving voltage of the organic EL element. Specifically, 5-500 nm is preferable, 10-200 nm is more preferable, and 20-100 nm is further more preferable.

[Organic electronics elements, display elements, lighting equipment]
Moreover, embodiment of this invention is related with organic electronics elements, such as the organic EL element which has the above-mentioned organic layer, and an organic photoelectric conversion element. Organic electronic devices have at least two electrodes and an organic layer located between the electrodes.
Furthermore, the embodiment of the present invention relates to a display element and an illumination device using an organic EL element.

[Organic EL device]
The organic EL element of the embodiment of the present invention includes the organic layer. The organic EL element usually includes a light emitting layer, an anode, a cathode, and a substrate, and may have other layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. . The organic EL element has at least the above-described organic layer. For example, the organic layer can be used as a light emitting layer and other layers, and preferably used as a hole injection layer and / or a hole transport layer. be able to. Therefore, an example of the organic EL element has an anode, an organic layer as a hole injection layer and / or a hole transport layer, a light emitting layer, and a cathode in this order, and further includes an arbitrary layer between these layers. You may do it. Hereinafter, each layer will be described in detail.

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

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

Also in the organic EL element which is the embodiment of the present invention, a phosphorescent material can be used for the light emitting layer from the viewpoint of high efficiency. As the phosphorescent material, a metal complex containing a central metal such as Ir or Pt can be preferably used. Specifically, as an Ir complex, for example, FIr (pic) [iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate] that emits blue light and green light are emitted. Ir (ppy) ₃ [Factris (2-phenylpyridine) iridium] (see MA Baldo et al., Nature, vol. 403, p. 750 (2000)), or emits red light (btp) ₂ Ir ( acac) {Bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] iridium (acetyl-acetonate)} (Adachi et al., Appl. Phys. Lett., 78 no 11, 2001, 1622), Ir (piq) ₃ [tris (1-phenylisoquinoline) iridium] and the like. Examples of the Pt complex include 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-forminplatinum (PtOEP) that emits red light. The phosphorescent material may be a low molecular weight compound 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, a polymer or an oligomer, and a dendrimer 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), αNPD (4,4′-Bis [(1-naphthyl) phenylamino] -1,1′-biphenyl) and the like can be used. As the polymer or oligomer, for example, polyvinyl carbazole, polyphenylene, polyfluorene or the like can be used, and derivatives thereof can also be used.

The light emitting layer may be formed by a vapor deposition method or a coating method.
When forming by the apply | coating method, an organic EL element can be manufactured cheaply and it is more preferable. The light emitting layer can be formed by applying a solution containing a phosphorescent material and, if necessary, a host material on a desired substrate by a known application method. Examples of the coating method include an inkjet method, a casting method, a dipping method, a relief printing, an intaglio printing, an offset printing, a planographic printing, a relief printing reverse offset printing, a screen printing, a gravure printing, and a 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 (eg, Au) or other material having metal conductivity can be used. Examples of the other material include an oxide (for example, ITO: indium oxide / tin oxide) and a conductive polymer (for example, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[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. Thiopyran dioxide derivatives, condensed ring tetracarboxylic anhydrides such as naphthalene and perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives (eg 2- (4-Biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD)), aluminum complexes (eg, Tris (8-hydroxyquinolinato) aluminum (III) (Alq ₃ ), Bis (2-methyl-8 -quninolinato) -4-phenylphenolate aluminum (III) (BAlq)). 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 for the organic EL element, the kind of glass, plastic, or the like is not particularly limited. Further, a transparent substrate is preferable, and glass, quartz, a light transmissive resin film, and the like are preferably used. When a resin film is used, flexibility can be imparted to the organic EL element (that is, a flexible substrate), 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. (TAC), the film which consists of cellulose acetate propionate (CAP) etc. is mentioned.

  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.

[Sealing]
The organic EL element which is an embodiment of the present invention may be sealed by the same method as the photoelectric conversion element described later in order to extend the life by reducing the influence of outside air.

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

  As 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, but a combination of three emission maximum wavelengths of blue, green, and red, and complementary colors such as blue and yellow, yellow green and orange are used. And those containing the two emission maximum wavelengths. The emission color can be controlled by adjusting the type and amount of the phosphorescent material.

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

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element as stated above. Furthermore, the display apparatus which is embodiment of this invention is provided with the illuminating device and the liquid crystal element as a display means. The illumination device 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 a backlight is replaced with the illumination device in a known liquid crystal display device, and a known technique can be diverted to the liquid crystal element portion.

[Organic photoelectric conversion element]
The organic photoelectric conversion element includes an organic solar cell and an organic photosensor, and usually includes a photoelectric conversion layer, an electrode, and a substrate. Furthermore, in order to improve the conversion efficiency or the stability in the air, one or more other layers such as a buffer layer and an electron transport layer may be included. The organic photoelectric conversion element has at least the above-described organic layer, and the organic layer can be used as a photoelectric conversion layer and a buffer layer, and is preferably used as a buffer layer. Therefore, the example of the organic photoelectric conversion element includes an anode, an organic layer as a buffer layer, a photoelectric conversion layer, and a cathode in this order, and may further include an arbitrary layer between these layers. The configuration of the organic photoelectric conversion element is described below.

[Photoelectric conversion layer]
Any material can be used for the photoelectric conversion layer as long as it absorbs light to cause charge separation and generate electromotive force. In particular, from the viewpoint of conversion efficiency, a mixture obtained by blending a p-type organic semiconductor and an n-type organic semiconductor is preferable.

  Examples of p-type organic semiconductors include polymers or oligomers such as oligothiophene, polyalkylthiophene, poly (3-hexylthiophene) (P3HT), polyphenylene vinylene (PPV); porphyrin, phthalocyanine, copper phthalocyanine; and derivatives thereof. It can be used suitably.

Examples of n-type organic semiconductors include CN-poly (phenylene-vinylene) (CN-PPV), MEH-CN-PPV, and -CF ₃ substituted polymers such as -CN group or -CF ₃ group-containing polymer or oligomer. Polymers or oligomers such as poly (fluorene) derivatives and fluorene-benzothiadiazole copolymers; fullerene (C ₆₀ ), [6,6] -Phenyl-C ₆₁ -butyric acid methyl ester (PCBM), [6,6] -Phenyl-C ₇₁ -butyric acid methyl ester (PCBM), naphthalenetetracarboxylic acid anhydride (NTCDA), perylenetetracarboxylic acid anhydride (PTCDA), naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid diimide, quinacdrine; A derivative etc. can be used conveniently.

  The method for forming the photoelectric conversion layer is not particularly limited, and may be formed by a vapor deposition method or a coating method. When forming by the apply | coating method, an organic photoelectric conversion element can be manufactured cheaply and it is more preferable. As a method of forming by a coating method, the method described in the method of forming a light emitting layer can be used.

[Other layers]
Moreover, the organic photoelectric conversion element has the above-described buffer layer in addition to the photoelectric conversion layer, and may further have a layer such as an electron transport layer. As the buffer layer, the above-described organic layer can be used, and as the electron transport layer, LiF, TiOx, ZnOx, or the like is generally used.

[electrode]
Any material can be used for the electrode as long as it has conductivity. Examples of the electrode include platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, lithium fluoride and other metals or alloys or salts thereof; indium oxide, tin oxide, etc. Metal oxides or alloys thereof (ITO); conductive polymers such as polyaniline, polypyrrole, polythiophene and polyacetylene; acids such as hydrochloric acid, sulfuric acid and sulfonic acid; Lewis acids such as FeCl ₃ ; halogen atoms such as iodine; sodium; The conductive polymer to which a dopant such as a metal atom such as potassium is added; a conductive composite material in which conductive particles such as metal particles, carbon black, fullerene, and carbon nanotubes are dispersed in a matrix such as a polymer binder. . Moreover, you may use combining these.

  Further, at least a pair (two) of electrodes are provided, but at least one of them is a transparent electrode. Examples of the transparent electrode include oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO); metal thin films; and conductive polymers such as PEDOT: PSS.

  The electrode has a function of collecting holes and electrons generated in the photoelectric conversion layer, and an electrode material suitable for collecting holes and electrons is preferably used in pairs. Examples of the electrode material suitable for collecting holes include materials having a high work function such as Au and ITO. On the other hand, examples of the electrode material suitable for collecting electrons include a material having a low work function such as Al.

  The method for forming the electrode is not particularly limited, and for example, vacuum deposition, sputtering, coating method, or the like can be used.

[substrate]
As the substrate, any material can be used as long as it can support each layer. Examples of the substrate include inorganic materials such as glass; polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyimide (PI), polyetherimide (PEI), and cycloolefin polymer (COP). , Organic materials such as polyphenylene sulfide (PPS), nylon, polystyrene, polyethylene, polypropylene, polyvinyl alcohol, fluorine resin, vinyl chloride, cellulose, polyvinylidene chloride, aramid, polyurethane, polycarbonate, polyarylate, polynorbornene, polylactic acid; insulation For example, composite materials such as metals such as stainless steel, titanium, and aluminum whose surfaces are coated or laminated in order to impart properties. Further, a substrate on which an inorganic material such as silicon oxide or silicon nitride is stacked may be used for providing gas barrier properties.

  In particular, a film made of an organic material such as PET, PEN, PES, PI, PEI, COP, or PPS is preferable because it can impart transparency and flexibility.

[Sealing]
The organic photoelectric conversion element according to the embodiment of the present invention may be sealed in order to reduce the influence of outside air and extend the life. As a material used for sealing, glass, epoxy resin, acrylic resin, plastic films such as PET and PEN, inorganic materials such as silicon oxide and silicon nitride, and the like can be used.

  The sealing method is not particularly limited. For example, a method of directly forming on an organic photoelectric conversion element by vacuum deposition, sputtering, coating method, or the like, a method of attaching glass or plastic film to the organic photoelectric conversion element with an adhesive Etc. can be used.

  EXAMPLES Hereinafter, although an Example demonstrates embodiment of this invention, this invention is not restrict | limited to these Examples.

<Polymer synthesis>
(Preparation of Pd catalyst)
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature, anisole (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tri-tert-butylphosphine (129.6 mg, 640 μmol) was weighed in a sample tube, anisole (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to form a catalyst. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes.

(Synthesis Example 1)
(Synthesis of Monomer 1 (1- (4′-Bromophenyl) pyrrole))

To a 100 mL eggplant flask, 7.91 g (46.0 mmol) of 4-bromoaniline was taken, and 22.5 mL of acetic acid was added and stirred. 6.12 g (46.3 mmol) of 2,5-dimethoxytetrahydrofuran was taken in a syringe and dropped into the eggplant flask over about 1 minute. The reaction solution was heated in an oil bath at about 90 ° C. and refluxed for 1 hour. After stopping the heating, acetic acid was distilled off under reduced pressure. The reaction solution was further dried with a vacuum pump, and the residue was dissolved in toluene and purified by a silica gel column (hexane / ethyl acetate = 10/1). The purified product was dried with an evaporator and a vacuum pump to obtain 9.25 g (41.7 mmol) of a brown solid (yield 91%).
1H-NMR (CDCl3) [δ = 7.52 (d, 2H), 7.24 (d, 2H), 7.03 (t, 2H), 6.34 (t, 2H)]

(Synthesis of polymer A having a pyrrole ring at the end)

  To a three-necked round bottom flask, monomer 2 (1.0 mmol), monomer 3 (2.5 mmol), monomer 1 (2.0 mmol), and anisole (20 ml) were added, and the prepared Pd catalyst solution (1.0 mL) was further added. added. After the mixture was stirred for 30 minutes, 10% aqueous tetraethylammonium hydroxide (12 mL) was added. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes. This mixture was heated to reflux for 2 hours. All the operations so far were performed under a nitrogen stream.

  After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The resulting precipitate was collected by suction filtration, dissolved in toluene, and added with triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer (Strem Chemicals, 200 mg per 100 mg of polymer, hereinafter referred to as “metal adsorbent”). , Stirred overnight. After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The resulting precipitate was vacuum dried to obtain polymer A having pyrrole at the end. The molecular weight was measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent. The weight average molecular weight was 57,000, and the yield was 38%. Polymer A has units of formula (87a) (corresponding to monomer 2), formula (1a) (corresponding to monomer 3), and pyrrolyl group (A) (corresponding to monomer 1). The percentages of were 18.2%, 45.5%, and 36.4%. Moreover, the average value of the number of units of Formula (87a), Formula (1a), and pyrrolyl group (A) was 45, 112, and 89, respectively.

The measurement conditions for the weight average molecular weight are as follows.
Liquid feed pump: L-6050 Hitachi High-Technologies Corporation
UV-Vis detector: L-3000 Hitachi High-Technologies column: Gelpack ^(R) GL-A160S / GL-A150S Hitachi Chemical Co., Ltd.
Eluent: THF (manufactured by Wako Pure Chemical Industries, HPLC, without stabilizer)
Flow rate: 1 mL / min
Column temperature: Room temperature Molecular weight Standard: Standard polystyrene

(Synthesis Example 2)
(Synthesis of monomer 2 (1- (2 ′, 5′-dibromophenyl) pyrrole))

To a 100 mL eggplant flask, 11.54 g (46.0 mmol) of 2,5-dibromoaniline was added, and 22.5 mL of acetic acid was added and stirred. 6.12 g (46.3 mmol) of 2,5-dimethoxytetrahydrofuran was taken in a syringe and dropped into the eggplant flask over about 1 minute. The reaction solution was heated in an oil bath at about 90 ° C. and refluxed for 1 hour. After stopping the heating, acetic acid was distilled off under reduced pressure. Furthermore, the reaction liquid was dried with a vacuum pump to obtain 13.39 g (44.5 mmol) of a brown liquid (yield 97%).
1H-NMR (CDCl3) [δ = 7.53 (d, 1H), 7.48 (d, 1H), 7.34 (dd, 1H), 6.86 (t, 2H), 6.33 (t, 2H)]

(Synthesis of polymer B having a pyrrole ring as a substituent of the polymer chain)

  Polymer B was obtained in the same manner as in Synthesis Example 1 except that the monomer was changed to monomer 4 (2.5 mmol) and monomer 5 (2.5 mmol). The weight average molecular weight was 13,000, and the yield was 53%. The polymer B has units of the formula (1a) (corresponding to the monomer 5) and the pyrrolyl group (B) (corresponding to the monomer 4), and the ratio of each unit is 50%, The average value of both was 26.

<Preparation of ink composition>
Example 1
Polymers A and B obtained above were each dissolved in toluene (polymer 4.5 mg / 465 μL), and an ethyl acetate solution of initiators 1 to 6 (50 μL, initiator concentration 10 μg / 1 μL) was added, respectively. Produced. Further, the polymers A and B obtained above were dissolved in toluene (polymer 4.5 mg / 465 μL), and an ink composition was prepared without adding an initiator. All ink compositions were obtained as uniform solutions. In addition, in an ink composition containing an initiator, an ink composition using an initiator having an iodonium ion or a sulfonium ion as a cation was particularly excellent in storage stability.

<Preparation of solvent-resistant thin film (organic layer)>
(Residual film rate evaluation)
The ink composition prepared in Example 1 was spin-coated at 3000 min ⁻¹ on a quartz glass plate having a size of 22 mm × 29 mm × thickness 1 mm at room temperature (25 ° C.) to form a thin film (1). Thereafter, the thin film (1) was cured by heating at 180 ° C. or 200 ° C. for 10 minutes on a hot plate to form a thin film (2) (50 nm). The film thickness was measured using a stylus type step / surface shape measuring device XP-2 manufactured by Tech Science Co., Ltd. The thin film (2) is grasped with tweezers together with the quartz glass plate, immersed in a 200 mL beaker filled with toluene (25 ° C.), rinsed by vibrating 10 times in the thickness direction of the substrate for 10 seconds, and the thin film (3) Got. From the ratio of the absorbance of the thin film before and after rinsing, the remaining ratio (remaining film ratio) of the thin film (3) was determined. The results are summarized in Table 1.

Absorbance measurement conditions are as follows.
The absorbance was measured using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). About the thin film, the light absorbency in the maximum absorption in 300-420 nm was calculated | required.

  As is clear from Table 1, the thin film (organic layer) obtained using the ink composition according to the embodiment of the present invention showed an excellent remaining film ratio. A thin film (organic layer) obtained from a composition with varying solubility has solvent resistance even when the polymer contained in the composition does not contain a general polymerizable substituent such as a styryl group or an oxetane group. Had. By using a composition whose solubility varies, it is possible to make a multilayer by a coating method of an organic electronics element. Moreover, the solvent resistance could be provided to the thin film by heating at a lower temperature by adding an initiator to the composition. The composition preferably has a solubility that changes at lower temperatures.

<Production of organic EL element>
(Example 2: Organic EL characteristics)
Polymer A obtained above was dissolved in toluene (polymer 4.5 mg / 465 μL), and an ethyl acetate solution of initiator 1 (50 μL, initiator concentration 10 μg / 1 μL) was added to prepare an ink composition. This ink composition was spin coated at 3000 min ⁻¹ on a glass substrate patterned with ITO to a width of 1.6 mm to form a thin film. The thin film was cured by heating at 180 ° C. for 10 minutes on a hot plate to form a hole injection layer (film thickness 50 nm).

Next, a toluene solution (1.0%) of a mixture of polymer 1 (75% by weight), polymer 2 (20% by weight) and polymer 3 (5% by weight) represented by the following structural formula is formed on the hole injection layer. % By weight) was spin-coated at 3000 min ⁻¹ to form a thin film. The thin film was heated on a hot plate at 80 ° C. for 5 minutes to form a polymer light emitting layer (film thickness 80 nm). The polymer light-emitting layer could be laminated without dissolving the hole injection layer.

  Furthermore, the obtained glass substrate was transferred into a vacuum vapor deposition machine, and electrodes were formed on the polymer light emitting layer in the order of Ba (film thickness: 3 nm) and Al (film thickness: 100 nm).

  After the electrode formation, the glass substrate was moved into a dry nitrogen environment without opening to the atmosphere. Sealing is performed by laminating a sealing glass and a glass substrate in which 0.4mm depth of counterbore is added to a non-alkali glass with a thickness of 0.7mm using a photo-curable epoxy resin. A molecular organic EL device was produced. Subsequent evaluation was performed in the atmosphere at room temperature (25 ° C.).

When a voltage was applied using ITO as an anode and Al as a cathode of the organic EL element, green light emission was observed at about 3V. At a luminance of 5000 cd / m ^2, the current efficiency was 10.1 cd / A, and the drive voltage was 5.3V. The current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard Co., and the luminance was measured using a luminance meter Pritchard 1980B manufactured by Photo Research.

<Production of charge transportability evaluation element>
(Example 3)
On a glass substrate patterned with a width of 1.6 mm of ITO, a mixed solution of polymer A (100 mg), initiator 5 (3.0 mg), and anisole (1.91 mL) was spin-coated at 3000 min ⁻¹ to form a thin film. Formed. The thin film was heated on a hot plate at 180 ° C. for 10 minutes to produce a charge transport layer (film thickness: 125 nm). Next, the obtained glass substrate was transferred into a vacuum evaporation machine, and Al (film thickness 100 nm) was evaporated on the charge transport layer.

  After depositing Al, the glass substrate was moved into a dry nitrogen environment without opening to the atmosphere. Sealing is performed by laminating a sealing glass with a 0.4mm depth of counterbore into a 0.7mm-thick alkali-free glass and a glass substrate using a photo-curable epoxy resin, and evaluation of charge transportability An element was produced.

  Similarly, a charge transportability evaluation element was produced using a mixed solution of polymer A (100 mg), initiator 6 (3.0 mg), and anisole (1.91 mL).

(Comparative Example 1)

三口丸底フラスコに、モノマー２（２．０ｍｍｏｌ）、モノマー３（５．０ｍｍｏｌ）、モノマー４（４．０ｍｍｏｌ）、及びアニソール（２０ｍＬ）を加え、さらに調製したＰｄ触媒溶液（７．５ｍＬ）を加えた。混合物を３０分撹拌した後、１０％テトラエチルアンモニウム水酸化物水溶液（２０ｍＬ）を加えた。すべての溶媒は３０分以上窒素バブルにより脱気した後、使用した。この混合物を２時間加熱・還流した。ここまでの全ての操作は窒素気流下で行った。

To a three-necked round bottom flask, monomer 2 (2.0 mmol), monomer 3 (5.0 mmol), monomer 4 (4.0 mmol), and anisole (20 mL) were added, and the prepared Pd catalyst solution (7.5 mL) was further added. added. After the mixture was stirred for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added. All solvents were used after degassing with nitrogen bubble for more than 30 minutes. This mixture was heated to reflux for 2 hours. All the operations so far were performed under a nitrogen stream.

  After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was collected by suction filtration, dissolved in toluene, a metal adsorbent (200 mg relative to 100 mg of polymer) was added, and the mixture was stirred overnight. After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The resulting precipitate was vacuum-dried to obtain polymer 4. The weight average molecular weight of the obtained polymer 4 was 31,000.

  As in Example 3, a mixed solution of polymer 4 (100 mg), initiator 5 (3.0 mg), and anisole (1.91 mL), polymer 4 (100 mg), initiator 6 (3.0 mg), and anisole A charge transportability evaluation element was produced using a mixed solution of (1.91 mL).

A voltage was applied to these charge transportability evaluation elements using ITO as an anode and Al as a cathode, and the change in current when the voltage was applied was measured. Table 2 shows the voltage required for 10 mA / cm ² energization.

  As is clear from Table 2, the charge transportability evaluation element of Example 3 had higher charge transportability than the charge transportability evaluation element of Comparative Example 1, and was able to pass the same current at a low voltage. Further, when an initiator having borate ions as anions was used, the charge transportability evaluation element showed particularly high charge transportability.

<Production of organic EL element>
(Example 4: Organic EL reliability)
A coating solution in which polymer 4 (10 mg) obtained above, initiator 1 (0.5 mg), and toluene (1000 μL) were mixed was prepared. This coating solution was spin-coated at 3000 min ⁻¹ on a glass substrate on which ITO was patterned to a width of 1.6 mm to form a thin film. The thin film was cured by heating on a hot plate at 180 ° C. for 10 minutes to form a hole injection layer (film thickness 30 nm).

Next, on the hole injection layer, a coating solution in which polymer A (10 mg) and toluene (1000 μL) were mixed was spin-coated at 3000 min ⁻¹ to form a thin film. The thin film was cured by heating at 200 ° C. for 10 minutes on a hot plate to form a hole transport layer (film thickness 30 nm).

The obtained glass substrate was transferred into a vacuum deposition machine, and (CBP + Ir (ppy) ₃ (100: 6, film thickness 30 nm), BAlq (film thickness 10 nm), Alq ₃ (film thickness 30 nm), LiF (film thickness 0. 8 nm) and Al (thickness 150 nm) were deposited in this order.

  After the electrode formation, the glass substrate was moved into a dry nitrogen environment without opening to the atmosphere. Sealing is performed by laminating a sealing glass with a 0.4mm depth of counterbore into a non-alkali glass with a thickness of 0.7mm and a glass substrate using a photo-curable epoxy resin. An element was produced. Subsequent experiments were performed in the atmosphere at room temperature (25 ° C.).

When a voltage was applied to this organic EL element using ITO as an anode and Al as a cathode, green light emission was observed at 4.6V. The current efficiency at a luminance of 1000 cd / m ² was 18 cd / A.

In addition, as a lifetime characteristic, the luminance was measured with Topcon BM-7 while applying a constant current, and the time for the luminance to be halved from the initial luminance (3000 cd / m ² ) was measured and found to be 200 hours.

(Comparative Example 2: Organic EL reliability)
An organic EL device was produced in the same manner as in Example 4 except that the polymer used for the hole transport layer was changed from polymer A (10 mg) to polymer 4. When evaluated in the same manner as in Example 4, green light emission was observed at 4.5 V, and the current efficiency at a luminance of 1000 cd / m ² was 18 cd / A. The time for the luminance to halve from the initial luminance (3000 cd / m ² ) was 10 hours.

  A polymerizable substituent such as a styryl group or an oxetane group is a substituent that does not bear a function such as charge transport, charge recombination, or light emission, and a composition containing a polymer or oligomer into which such a polymerizable substituent is introduced. In the organic layer formed by using, functional sites such as charge transport, charge recombination, and light emission are relatively diluted, and there is a possibility that the characteristics of the organic electronics element are deteriorated. By using the composition that changes the solubility according to the embodiment of the present invention, the driving voltage of the organic electronics element can be reduced, and the light emission efficiency, the power efficiency, or the lifetime can be increased.

Claims (20)

Containing a polymer or oligomer (A) having a unit having a hole transporting property and having a pyrrolyl group optionally having a substituent, and a solvent (B);
The polymer or oligomer (A) has the pyrrolyl group at its end;
A composition whose solubility is changed by applying heat, light, or both heat and light.   Containing a polymer or oligomer (A) having a unit having a hole transporting property and having a pyrrolyl group optionally having a substituent, and a solvent (B);
  The polymer or oligomer (A) is a polymer or oligomer having a branched structure and having three or more terminals, and having the pyrrolyl group at three or more of all terminals.
  A composition whose solubility is changed by applying heat, light, or both heat and light. The composition according to claim 1 or 2 , further comprising an initiator (C). The composition according to any one of claims 1 to 3 , wherein the unit having a hole transporting property includes at least one unit selected from the group consisting of a unit containing an aromatic amine structure and a unit containing a carbazole structure. The polymer or oligomer (A) is at least one selected from the group consisting of a structure represented by the following formula (Ia), a structure represented by the formula (Ib), and a structure represented by the formula (Ic) The composition according to any one of claims 1 to 4, which has the following structure.

(R ^{1 to} R ^{4 in} formulas (Ia) to (Ic) each independently represent a hydrogen atom or an alkyl group, and at least one of R ^{2 to} R ⁴ is a hydrogen atom.) Polymer or oligomer (A) is one of claims 1 to 5 having at least one structure selected from the group consisting of structures represented by the structural-formula represented by the following formula (IIa) (II c) Or a composition according to claim 1.

(R ^{1 to} R ^{4 in} formulas (IIa) to (IIc) each independently represent a hydrogen atom or an alkyl group, at least one of R ^{2 to} R ⁴ is a hydrogen atom, and Ar ^a is an arenediyl Represents a group or a heteroarenediyl group.) The composition according to claim 6, wherein the polymer or oligomer (A) further has at least one structure selected from the group consisting of a structure represented by the following formula (IIIa) to a structure represented by the formula (IIIc). object.

(R ^{1 to} R ^{4 in} formulas (IIIa) to (IIIc) each independently represent a hydrogen atom or an alkyl group, at least one of R ^{2 to} R ⁴ is a hydrogen atom, and Ar ^b is an arene Represents a triyl group or a heteroarene triyl group.)   The composition according to any one of claims 1 to 7, wherein the initiator (C) is an oxidizing agent.   The composition according to any one of claims 1 to 8, wherein the initiator (C) is an onium salt.   The composition according to any one of claims 1 to 9, wherein the polymer or oligomer (A) has a weight average molecular weight of 1,000 to 1,000,000.   The hole transport material composition containing the composition in any one of Claims 1-10.   An ink composition comprising the composition according to claim 1.   The organic layer (I) formed by apply | coating the composition in any one of Claims 1-10, the positive hole transport material composition of Claim 11, or the ink composition of Claim 12.   The method for changing the solubility of the organic layer (I) according to claim 13, comprising the step of applying heat, light, or both heat and light to the organic layer (I).   An organic layer (II) having a different solubility from the organic layer (I) according to claim 13, wherein the organic layer (I) is obtained by applying heat, light, or both heat and light to the organic layer (I). (II).   16. An organic electronic device having at least two electrodes and an organic layer (II) according to claim 15 located between the electrodes.   The organic electroluminescent element which has an anode, the organic layer (II) of Claim 15, a light emitting layer, and a cathode.   The display element using the organic electroluminescent element of Claim 17.   The illuminating device using the organic electroluminescent element of Claim 17.   The organic photoelectric conversion element which has an anode, the organic layer (II) of Claim 15, a photoelectric converting layer, and a cathode.