JP2008133346A - Organic electroluminescent device and composition useful for production of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition having excellent charge injecting properties or charge transporting properties in the resultant device when used for producing the device etc. <P>SOLUTION: The composition comprises a conjugated polymer and a compound. The conjugated polymer has a repeating unit selected from a fluorenediyl group, benzofluorenediyl group, dibenzofurandiyl group, dibenzothiophenediyl group, carbazolediyl group, thiophenediyl group, furandiyl group, phenoxazinediyl group, pyrrolediyl group, benzothiadiazolediyl group, phenylenevinylenediyl group, thienylenevinylenediyl group and triphenylaminediyl group. The compound is represented by formula (1) (wherein, Ar<SP>1</SP>to Ar<SP>3</SP>represent each a bivalent 6-membered ring such as a phenylene group; and Q<SP>1</SP>and Q<SP>2</SP>represent each a monovalent group having an oxirane ring at the terminal or the like). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition excellent in charge transport property or charge injection property.

In recent years, research and development of semiconductor devices (organic semiconductor devices) using organic materials have been actively conducted in the electronics field. Examples of the organic semiconductor device include an organic electroluminescence element and an organic thin film solar cell.
The materials used for this organic semiconductor device are required to have high electron transport properties and electron injection properties, and as a result, characteristics such as a low drive voltage for organic electroluminescent elements and high conversion efficiency for organic thin film solar cells can be obtained. .
In particular, when a polymer material is used as the material of the organic semiconductor device, it can be dissolved in a solvent and an active layer in the element can be formed by a coating method, which meets the demand for a large area of the element. For this reason, in recent years, for example, polymer materials such as polymer light emitting materials have been proposed (Non-Patent Document 1).

Advanced Materials Vol.12 1737-1750 (2000)

  However, when this polymer material is used for the production of an organic semiconductor device such as an element, the resulting element has insufficient charge injection property and charge transport property.

  Then, an object of this invention is to provide the composition excellent in charge injection property or charge transport property in the element obtained when it uses for manufacture of organic-semiconductor devices, such as an element.

  As a result of studies to solve the above problems, the present inventors have found that charge transportability or charge injection property can be improved by using a composition containing a specific conjugated polymer and a compound having a specific structure. The present invention has been made.

（式中、Ａｒ¹、Ａｒ²及びＡｒ³は、それぞれ独立に、下記式：

で表されるいずれかの二価の基を表す。ここで、Ｒは炭素数１〜１８のアルキル基を表し、ａは１〜１０の整数、ｂ及びｃはそれぞれ独立に１〜８の整数、ｄ、ｅ、ｆ及びｇはそれぞれ独立に１〜６の整数、ｈは１〜４の整数を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。Ｑ¹及びＱ²は、それぞれ独立に、末端にオキシラン環を有する１価の基、アルカリ金属原子、水素原子、炭素数１〜１８のアルキル基、オキセタン基、アクリロイル基又はメタクリロイル基を表す。)
で表される化合物とを含有する組成物を提供する。 The present invention firstly includes an unsubstituted or substituted fluorenediyl group, an unsubstituted or substituted benzofluorenediyl group, an unsubstituted or substituted dibenzofurandiyl group, an unsubstituted or substituted dibenzothiophenediyl group, an unsubstituted or Substituted carbazolediyl group, unsubstituted or substituted thiophenediyl group, unsubstituted or substituted furandyl group, unsubstituted or substituted phenoxazinediyl group, unsubstituted or substituted pyrrolediyl group, unsubstituted or substituted benzothiadiazolediyl A repeating unit of one or more selected from the group consisting of a group, an unsubstituted or substituted phenylene vinylene diyl group, an unsubstituted or substituted thienylene vinylene diyl group, and an unsubstituted or substituted triphenylamine diyl group, Conjugated system in which adjacent repeating units are bonded directly or via a linking group And the child,
Following formula (1):

(In the formula, Ar ¹ , Ar ² and Ar ³ are each independently represented by the following formula:

Represents any divalent group represented by the formula: Here, R represents an alkyl group having 1 to 18 carbon atoms, a is an integer of 1 to 10, b and c are each independently an integer of 1 to 8, and d, e, f and g are each independently 1 to 1. An integer of 6 and h represents an integer of 1 to 4. When a plurality of R are present, they may be the same or different. Q ¹ and Q ² each independently represent a monovalent group having an oxirane ring at the terminal, an alkali metal atom, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an oxetane group, an acryloyl group, or a methacryloyl group. )
A composition containing the compound represented by:

  Secondly, the present invention provides an organic electroluminescent device and an organic thin-film solar cell having an electrode composed of an anode and a cathode, and a layer formed between the electrodes and using the composition.

  The composition of the present invention is particularly useful for an organic semiconductor device, and when used for manufacturing an organic semiconductor device such as an element, the resulting element is excellent in charge injection property or charge transport property. The composition of the present invention is also useful for the production of organic electroluminescent elements, organic thin-film solar cells, etc., and low driving voltage can be achieved with the obtained organic electroluminescent elements. Conversion efficiency can be achieved.

  Hereinafter, the present invention will be described in detail.

<Composition>
The composition of the present invention contains the conjugated polymer and the compound represented by the formula (1).

（式中、Ｒ、ａ、ｃ及びｈは、上記と同じ意味を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）
で表されるいずれかであり、より好ましくは下記式：

（式中、Ｒ、ｃ及びｈは、上記と同じ意味を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）
で表されるいずれかである。さらに、Ａｒ²は、特に好ましくは下記式：

（式中、Ｒ及びｃは、上記と同じ意味を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）
で表されるものである。 -Compound represented by Formula (1)-
In the formula (1), the divalent group represented by Ar ¹ , Ar ² and Ar ³ is preferably the following formula:

(In the formula, R, a, c and h represent the same meaning as described above. When a plurality of R exist, they may be the same or different.)
More preferably, the following formula:

(In the formula, R, c and h represent the same meaning as described above. When a plurality of Rs are present, they may be the same or different.)
It is one represented by. Furthermore, Ar ² is particularly preferably the following formula:

(In the formula, R and c represent the same meaning as above. When a plurality of Rs are present, they may be the same or different.)
It is represented by

In terms of solubility in an organic solvent, in formula (1), at least one of Q ¹ and Q ² is a monovalent group having an oxirane ring at the terminal, an alkyl group having 1 to 18 carbon atoms, an oxetane group, or acryloyl. It is preferably a group or a methacryloyl group, and at least one of Q ¹ and Q ² is preferably a monovalent group having an oxirane ring at the terminal or an alkyl group having 1 to 18 carbon atoms. In addition, when one or both of Q ¹ and Q ² is an epoxy group, an oxetane group, an acryloyl group or a methacryloyl group, the compound represented by the formula (1) has crosslinkability, By irradiating light or heat, a film having excellent thermal stability can be produced.

The alkyl group having 1 to 18 carbon atoms represented by Q ¹ and Q ² may be linear or branched. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Examples include an octyl group, an isooctyl group, an n-decyl group, an n-dodecyl group, an n-pentadecyl group, and an n-octadecyl group.

で表されるものが挙げられる。 As the monovalent group having an oxirane ring at the terminal represented by Q ¹ and Q ² , the following formula:

The thing represented by is mentioned.

Examples of the alkali metal atom represented by Q ¹ and Q ² include a lithium atom, a sodium atom, a potassium atom, a rubidium atom, a cesium atom, and a francium atom.

The alkyl group having 1 to 18 carbon atoms represented by R is the same as described and exemplified in the section of the alkyl group having 1 to 18 carbon atoms represented by Q ¹ and Q ^2. preferable.

（式中、Ｑ¹、Ｑ²、Ａｒ²、Ｒ及びｈは、上記と同じ意味を表す。複数存在するｈは、同一であっても異なっていてもよい。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）
で表されるものであることが好ましい。 The compound represented by the formula (1) is represented by the following formula (2):

(In the formula, Q ¹ , Q ² , Ar ² , R and h represent the same meaning as described above. A plurality of h may be the same or different. In the case where a plurality of R are present, They may be the same or different.)
It is preferable that it is represented by these.

で表されるものが挙げられる。 Specific examples of the compound represented by the formula (2) include the following formula:

The thing represented by is mentioned.

  The compound represented by the formula (1) or (2) contained in the composition of the present invention may be a single type or two or more types.

-Conjugated polymer-
The conjugated polymer is (1) a polymer consisting essentially of a structure in which double bonds and single bonds are arranged alternately, (2) a structure in which double bonds and single bonds are arranged via nitrogen atoms. (3) a polymer consisting essentially of a structure in which double bonds and single bonds are arranged alternately and a structure consisting essentially of a structure in which double bonds and single bonds are arranged via nitrogen atoms, etc. In the present specification, specifically, an unsubstituted or substituted fluorenediyl group, an unsubstituted or substituted benzofluorenediyl group, a dibenzofurandiyl group, an unsubstituted or substituted dibenzothiophenediyl group, an unsubstituted Or a substituted carbazolediyl group, an unsubstituted or substituted thiophenediyl group, an unsubstituted or substituted furandyl group, an unsubstituted or substituted pyrroldiyl group, an unsubstituted or substituted benzothiadiazolediyl group, an unsubstituted or substituted phenylenebi group One or two or more types selected from the group consisting of a rangenyl group, an unsubstituted or substituted thienylenevinylenediyl group, and an unsubstituted or substituted triphenylaminediyl group are used as a repeating unit, and the repeating units are directly or linking groups It is a polymer bonded via

  In the conjugated polymer, when the repeating units are bonded via a linking group, examples of the linking group include phenylene, biphenylene, naphthalenediyl, anthracenediyl, and the like.

The conjugated polymer preferably has a polystyrene-equivalent weight average molecular weight of 5 × 10 ² to 1 × 10 ⁷ from the viewpoint of film forming ability and solubility in a solvent, and preferably 1 × 10 ³ to 1 × 10 7. ⁶ is more preferable.

  The conjugated polymer contained in the composition of the present invention may be one kind alone or two or more kinds.

  The conjugated polymer is prepared by synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, and then dissolved in an organic solvent as necessary. For example, an alkali, an appropriate catalyst, or a ligand is used. It can be synthesized by polymerization by a known polymerization method such as aryl coupling.

The polymerization method by aryl coupling is not particularly limited. Examples of the functional group suitable for the polymerization reaction include a monomer having a boric acid group or a boric acid ester group, a halogen atom such as a bromine atom, an iodine atom, or a chlorine atom as a functional group, or a trifluoromethanesulfonate group, p- Monomers having a sulfonate group such as toluene sulfonate group and inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, potassium fluoride, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide In the presence of an organic base such as tetraethylammonium hydroxide, palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride, bis Pd or Ni complexes such as cyclooctadiene) nickel and, if necessary, further triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine , A method of polymerizing by a Suzuki coupling reaction using a catalyst comprising a ligand such as tri (tert-butyl) phosphine; monomers having a sulfonate group such as a halogen atom or a trifluoromethanesulfonate group are bis (cyclooctadiene) ) Using a catalyst comprising a nickel zero-valent complex such as nickel and a ligand such as bipyridyl, or [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel dichlori A catalyst comprising a Ni complex such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine and a reducing agent such as zinc or magnesium, if necessary And a method of polymerizing by a Yamamoto coupling reaction, if necessary, under a dehydrating condition; a compound having a magnesium halide group and a compound having a halogen atom are [bis (diphenylphosphino) ethane] nickel dichloride, [ Bis (diphenylphosphino) propane] Nickel catalyst such as nickel dichloride, reaction under dehydration conditions, polymerization by aryl coupling reaction, polymerization by Kumada-Tamao coupling reaction, FeC as a functional group A method of polymerization with an oxidizer ₃ or the like, a method in which electrochemical oxidation polymerization.

  The reaction solvent should be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, a mixed solvent of two or more thereof, or water and The two-phase system is exemplified.

  In the Suzuki coupling reaction, an organic solvent such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, a mixed solvent of two or more thereof, or with them A two-phase system with water is preferred. In general, the reaction solvent is preferably subjected to deoxygenation treatment in order to suppress side reactions.

  In the Yamamoto coupling reaction, organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and a mixed solvent of two or more thereof are preferable. In general, the reaction solvent is preferably subjected to deoxygenation treatment in order to suppress side reactions.

  Among the aryl coupling reactions, the Suzuki coupling reaction and the Yamamoto coupling reaction are preferable from the viewpoint of reactivity, and the Suzuki coupling reaction and the Yamamoto coupling reaction using a nickel zero-valent complex are more preferable. More specifically, with respect to polymerization by Suzuki coupling, see, for example, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 39, 1533-1556 (2001) can be referred to. With respect to polymerization by Yamamoto coupling, for example, known methods described in Macromolecules 1992, 25, 1214-1223 can be referred to.

  In addition, the polymer main chain synthesized in advance can be formylated or acylated by Friedel-Crafts reaction or the like, and further subjected to a reduction reaction or the like as necessary, and then reacted with these groups to form a bond. It can also be synthesized by reacting with a side chain precursor having a group.

  The reaction temperature in these reactions is not particularly limited as long as the reaction solution is kept in a liquid state, but the lower limit is preferably −100 ° C., more preferably −20 from the viewpoint of reactivity. The upper limit is preferably 200 ° C., more preferably 150 ° C., particularly preferably from the viewpoint of the stability of the conjugated polymer and the compound represented by the formula (1). Is 120 ° C.

  The conjugated polymer can be taken out according to a known method. For example, the conjugated polymer can be obtained by adding a reaction solution to a lower alcohol such as methanol and filtering and drying the deposited precipitate. When the purity of the obtained conjugated polymer is low, it can be purified by usual methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography and the like.

<Organic semiconductor devices>
The composition of this invention can be used for organic semiconductor devices, such as an organic electroluminescent element and an organic thin film solar cell, for example. In these applications, the composition of the present invention can be used for, for example, an active layer, a charge transport layer, a charge injection layer, and the like. Specifically, for example, an organic semiconductor device having a layer made of the composition of the present invention as any of an active layer, a charge transport layer, and a charge injection layer, a layer made of the composition as a light emitting layer, a charge transport layer, and a charge An organic electroluminescent device having any of an injection layer and an organic thin film solar cell having a layer made of the composition as any of an active layer, a charge transport layer and a charge injection layer.

An organic electroluminescence element has a layer formed using the composition. Specifically, for example, an electrode including an anode and a cathode and a layer formed between the electrodes and formed using the composition are provided. It is provided as any one of a light emitting layer, a charge transport layer, and a charge injection layer. In addition, for example, the following layer structures are exemplified.
a) Anode / hole injection layer (hole transport layer) / light emitting layer / cathode b) Anode / light emitting layer / electron injection layer (electron transport layer) / cathode c) Anode / hole injection layer (hole transport layer) / Light emitting layer / electron injection layer (electron transport layer) / cathode

  An organic thin film solar cell has an electrode composed of an anode and a cathode, and a layer (an organic thin film layer such as an active layer, a charge transport layer, a charge injection layer, etc.) provided between the electrodes and using the composition. is there.

  The active layer film and the charge transport film using the composition of the present invention are preferably formed by a coating method. The coating method is preferable in that the manufacturing process can be simplified and the productivity is excellent, and the casting method, spin coating method, bar coating method, blade coating method, roll coating method, gravure printing, screen printing, ink jet method, etc. Is mentioned. In the coating method, a composition (solution state) containing the conjugated polymer, the compound represented by the formula (1) or (2) and a solvent is prepared as a coating solution, and the coating solution is obtained as desired. A desired layer or film can be formed by coating on a layer or electrode and drying.

  As the solvent, a stable solvent capable of uniformly dissolving or dispersing the conjugated polymer and the compound represented by the formula (1) or (2) can be appropriately selected from known solvents. Examples of such solvents include alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), organic chlorines (chloroform, 1,2-dichloroethane, etc.), aromatic hydrocarbons (benzene, Toluene, xylene, etc.), aliphatic hydrocarbons (normal hexane, cyclohexane, etc.), amides (dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.) and the like. These solvents may be used alone or in combination of two or more.

The content of the compound represented by the formula (1) is usually 0.1 to 10,000 parts by weight, preferably 1 to 1000 parts by weight with respect to 100 parts by weight of the conjugated polymer.
In the coating solution, the total amount of the solvent is usually about 1,000 to 100,000 parts by weight with respect to 100 parts by weight of the total amount of the conjugated polymer and the compound represented by the formula (1) or (2). It is.

  In addition to the conjugated polymer and the compound represented by the formula (1) or (2), the composition of the present invention contains other components as long as the charge transport property and the charge injection property are not impaired. You may let them.

<Charge transport layer / charge injection layer>
The composition of this invention can be used for an organic semiconductor device, an organic electroluminescent element, an organic thin-film solar cell, etc. In these applications, the polymer semiconductor composition of the present invention can be used as any one of an active layer, a charge transport layer, and a charge injection layer.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

-Method for measuring molecular weight-
In Examples, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the peak top molecular weight (Mp) were determined in terms of polystyrene by gel permeation chromatography (GPC). Specifically, using a column in which three TSKgel SuperHM-H (manufactured by Tosoh) are connected in series by GPC (manufactured by Tosoh, product name: HLC-8220GPC), the flow rate is 0.5 mL / min using tetrahydrofuran as a developing solvent. And measured at 40 ° C. A differential refractive index detector was used as the detector.

で表される化合物Ａ 6.2171g、下記式：

で表される化合物Ｂ 0.5085g、下記式：

で表される化合物Ｃ 6.2225g、及び下記式：

で表される化合物Ｄ 0.5487gを取り、窒素置換した。トルエン100mlを加え、ジクロロビス（トリフェニルホスフィン）パラジウム（II） 7.6mg、炭酸ナトリウム水溶液24mlを加え、環流下で３時間攪拌した後、フェニルホウ酸0.40gを加え、終夜攪拌した。ナトリウムＮ，Ｎ−ジエチルジチオカルバメート水溶液を加え、さらに環流下で３時間攪拌した。得られた反応液を分液し、有機相を酢酸水溶液及び水で洗浄した後、メタノール中に滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥した後、トルエンに溶解させ、シリカゲル−アルミナカラムを通し、トルエンで洗浄した。得られたトルエン溶液をメタノール中に滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥した後、トルエンに溶解させ、メタノールに滴下ところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥して、7.72gの高分子化合物１（共役系高分子）を得た。高分子化合物１のポリスチレン換算の数平均分子量Ｍｎは１．２×１０⁵であり、ポリスチレン換算の重量平均分子量Ｍｗは２．９×１０⁵であった。 <Synthesis Example 1> (Synthesis of Polymer Compound 1)
Triscaprylylmethylammonium chloride (trade name: Aliquat336) 1.72 g in a 500 ml four-necked flask, the following formula:

6.2171 g of the compound A represented by the following formula:

Compound B 0.5085 g represented by the following formula:

6.2225 g of the compound C represented by the formula:

The compound D represented by the formula (0.5487 g) was taken and replaced with nitrogen. Toluene (100 ml) was added, dichlorobis (triphenylphosphine) palladium (II) (7.6 mg) and sodium carbonate aqueous solution (24 ml) were added, and the mixture was stirred for 3 hours under reflux. Then, phenylboric acid (0.40 g) was added and stirred overnight. Sodium N, N-diethyldithiocarbamate aqueous solution was added, and the mixture was further stirred under reflux for 3 hours. The obtained reaction solution was separated, and the organic phase was washed with an acetic acid aqueous solution and water, and then dropped into methanol, resulting in precipitation. The obtained precipitate was filtered, dried under reduced pressure, dissolved in toluene, passed through a silica gel-alumina column, and washed with toluene. When the obtained toluene solution was dropped into methanol, precipitation occurred. The obtained precipitate was filtered, dried under reduced pressure, dissolved in toluene, and dropped into methanol, resulting in precipitation. The resulting precipitate was filtered and dried under reduced pressure to obtain 7.72 g of polymer compound 1 (conjugated polymer). The number average molecular weight Mn in terms of polystyrene of the polymer compound 1 was 1.2 × 10 ⁵ , and the weight average molecular weight Mw in terms of polystyrene was 2.9 × 10 ⁵ .

で表される化合物Ｅ 234.06g、下記式：

で表される化合物Ｆ 172.06g、及び下記式：

で表される化合物Ｇ 28.5528gを取り、窒素置換した。アルゴンバブリングしたトルエン2620gを加え、攪拌しながら更に30分間バブリングした。酢酸パラジウム 99.1mg、トリス（ｏ−トリル）ホスフィン 937.0mgを加え、158gのトルエンで洗い流し、95℃に加熱した。17.5重量％炭酸ナトリウム水溶液855gを滴下後、バス温110℃に昇温し、9.5時間攪拌した後、フェニルホウ酸5.39gをトルエン96mlに溶解して加え、14時間攪拌した。200mlのトルエンを加え、反応液を分液し、有機相を３重量％酢酸水溶液850mlで２回、更に850mlの水とナトリウムＮ，Ｎ−ジエチルジチオカルバメート19.89gを加え、４時間攪拌した。分液後、シリカゲル−アルミナカラムを通し、トルエンで洗浄した。得られたトルエン溶液をメタノール50Lに滴下したところ、沈殿が生じた。得られた沈殿を、メタノールで洗浄した。減圧乾燥後、11Lのトルエンに溶解させ、得られたトルエン溶液をメタノール50Lに滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥して、278.39gの高分子化合物２を得た。高分子化合物２のポリスチレン換算の数平均分子量Ｍｎは７．７×１０⁴であり、ポリスチレン換算の重量平均分子量Ｍｗは３．８×１０⁵であった。 <Synthesis Example 2> (Synthesis of Polymer Compound 2)
Triscaprylylmethylammonium chloride (trade name: Aliquat336) 40.18 g in a 5 L separable flask, the following formula:

Compound E 234.06 g represented by the following formula:

172.06 g of the compound F represented by the following formula:

28.5528 g of the compound G represented by the formula (1) was taken and replaced with nitrogen. Arranged bubbling toluene (2020 g) was added and bubbling was continued for another 30 minutes. 99.1 mg of palladium acetate and 937.0 mg of tris (o-tolyl) phosphine were added, washed with 158 g of toluene, and heated to 95 ° C. After dropwise addition of 855 g of a 17.5 wt% sodium carbonate aqueous solution, the temperature was raised to a bath temperature of 110 ° C. and stirred for 9.5 hours. Then, 5.39 g of phenylboric acid was dissolved in 96 ml of toluene and stirred for 14 hours. 200 ml of toluene was added, the reaction solution was separated, and the organic phase was added twice with 850 ml of 3% by weight acetic acid aqueous solution, and further 850 ml of water and 19.89 g of sodium N, N-diethyldithiocarbamate were added and stirred for 4 hours. After separation, the solution was passed through a silica gel-alumina column and washed with toluene. When the obtained toluene solution was dropped into 50 L of methanol, precipitation occurred. The resulting precipitate was washed with methanol. After drying under reduced pressure, the product was dissolved in 11 L of toluene, and the resulting toluene solution was added dropwise to 50 L of methanol, resulting in precipitation. The resulting precipitate was filtered and dried under reduced pressure to obtain 278.39 g of polymer compound 2. The number average molecular weight Mn in terms of polystyrene of the polymer compound 2 was 7.7 × 10 ⁴ , and the weight average molecular weight Mw in terms of polystyrene was 3.8 × 10 ⁵ .

で表される１−（３−メチル−４−ヒドロキシフェニル）−４−（４−ヒドロキシフェニル）−１−シクロヘキセン（化合物３）を合成した。 <Synthesis Example 3> (Synthesis of Compound 3)
According to the method described in JP-A-2002-308809, the following formula:

1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene (compound 3) represented by

で表される１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセン（化合物４）５７重量部を得た。見掛収率が８１％であり、純度が８８．７％（ＬＣ面積百分率値）であり、溶融温度が１１７℃であった。 <Synthesis Example 4> (Synthesis of Compound 4)
Into a 1 L four-necked flask equipped with a thermometer, a condenser and a stirrer, was added 50 parts by weight of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene, and epichlorohydrin 200. Part by weight, 100 parts by weight of dimethyl sulfoxide, and 14.8 parts by weight of sodium hydroxide were charged, the pressure was reduced to about 6 kPa, and the mixture was refluxed and reacted at an internal temperature of about 50 ° C. for 4 hours. The temperature was further raised to 70 ° C., and the mixture was further refluxed and reacted at the same temperature for 1 hour. The water produced as the reaction progressed was distilled out of the reaction system.
After completion of the reaction, the pressure was once returned to normal pressure, and then the pressure was reduced to about 7 kPa, the internal temperature was raised to about 70 ° C., and the remaining epichlorohydrin was distilled off. Thereafter, 100 parts by weight of dimethyl sulfoxide was added, insoluble matters were filtered off at an internal temperature of 70 ° C., the obtained filtrate was cooled to room temperature, and the precipitated crystals were collected by filtration. The crystals collected by filtration were washed with 50 parts by weight of dimethyl sulfoxide and further washed twice with 100 parts by weight of methanol, and then dried under reduced pressure at 80 ° C. for 12 hours.

1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene (Compound 4) represented by the formula: The apparent yield was 81%, the purity was 88.7% (LC area percentage value), and the melting temperature was 117 ° C.

で表されるジアルキル化合物（化合物５）０．３５ｇと、下記式：

で表されるモノアルキル体混合物０．１６g（ＨＰＬＣ比で、化合物（３ａ）：化合物（３ｂ）＝１：３）を得た。 <Synthesis Example 5> (Synthesis of Compound 5)
In a 50 mL three-necked flask, 4- [4- (4-hydroxyphenyl) -1-cyclohexen-1-yl] -2-methylphenol (0.50 g, 1.78 mmol), DMF 20 mL, and tert-butoxypotassium (0 .40 g, 3.56 mmol) and n-octyl bromide (0.72 g, 3.73 mmol) were added, and the mixture was stirred at 80 ° C. for 12 hours. The reaction solution thus obtained is cooled, added to 50 mL of water, extracted twice using 50 mL of ethyl acetate, the organic phase is dried over magnesium sulfate, and the reaction solution is concentrated to dryness with an evaporator. By purifying the obtained residue by silica gel column chromatography (development with hexane: ethyl acetate = 4: 1 (volume ratio)), the following formula:

0.35 g of a dialkyl compound (Compound 5) represented by the following formula:

0.16 g of the monoalkyl mixture represented by the formula (HPLC ratio, compound (3a): compound (3b) = 1: 3) was obtained.

で表されるカリウム塩０．１１ｇを得た。これらのカリウム塩を化合物６とする。 <Synthesis Example 6> (Synthesis of Compound 6)
To a 50 mL eggplant flask, 0.16 g (0.41 mmol, HPLC ratio 1: 3) of the monoalkyl compound represented by the above formulas (3a) and (3b) and 20 mL of ethanol were added and stirred at room temperature for 30 minutes. . Thereto was added 0.046 g (0.41 mmol) of potassium tert-butoxy, and the mixture was further stirred for 30 minutes. The reaction solution was concentrated with an evaporator, and 30 ml of hexane was added to make a slurry, followed by filtration. The obtained cake was further washed with 30 mL of hexane, and then dried under reduced pressure (500 Pa, 4 hours), whereby the following formula:

0.11 g of a potassium salt represented by These potassium salts are referred to as Compound 6.

  <Examples 1 to 3, Comparative Example 1> (Production and Evaluation of Organic Electroluminescence Element)

<Creation and evaluation of organic EL element>
Spin on a glass substrate with an indium tin oxide (ITO) film having a thickness of 150 nm by sputtering using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (trade name: Baytron AI4083, manufactured by Starck). A film was formed by coating, and dried at 200 ° C. for 10 minutes on a hot plate in the atmosphere to produce a hole injection layer (film thickness: 60 nm). Next, a toluene solution of polymer compound 2 (filtered through a 0.2 μm Teflon (registered trademark) filter) was applied by spin coating, and baked at 200 ° C. for 15 minutes in a nitrogen atmosphere in a glove box. A hole transport layer (film thickness: 20 nm) was prepared. Furthermore, a toluene solution was prepared (filtered through a 0.2 μm Teflon (registered trademark) filter) according to the conditions shown in Table 1 (the presence or absence of the compound, the type of compound, and the composition), and the resulting solution was spin-coated to form a light emitting layer Was applied. The thickness of the light emitting layer was adjusted to 70 nm.
This was dried under reduced pressure at 90 ° C. for 1 hour, LiF was deposited by 4 nm, and Al was deposited by 100 nm. The degree of vacuum at the time of vapor deposition was in the range of 1 × 10 ⁻⁴ Pa to 9 × 10 ⁻³ Pa. The shape of the element was a regular square of 2 mm × 2 mm. By applying a voltage stepwise to the obtained device, current density and light emission luminance were measured. The luminous efficiency was calculated by dividing the luminous luminance by the current density. Table 1 shows the current density and the maximum luminous efficiency at a bias voltage of 9V.

-Evaluation-
As can be seen from Table 1, the light-emitting layer formed using the composition containing the conjugated polymer (polymer compound 1) and the compound represented by formula (1) (compounds 4 to 6), Compared with the light emitting layer formed using the composition which does not contain the compound represented by said Formula (1), the current density at the time of the bias voltage of 9V of the obtained organic electroluminescent element improved. Therefore, it was confirmed that the composition of the present invention was excellent in charge transporting property and charge injecting property. The maximum luminous efficiency was also good.

Claims (12)

Unsubstituted or substituted fluorenediyl group, unsubstituted or substituted benzofluorenediyl group, unsubstituted or substituted dibenzofurandiyl group, unsubstituted or substituted dibenzothiophenediyl group, unsubstituted or substituted carbazolediyl group, non Substituted or substituted thiophenediyl group, unsubstituted or substituted furandiyl group, unsubstituted or substituted phenoxazinediyl group, unsubstituted or substituted pyrroldiyl group, unsubstituted or substituted benzothiadiazole diyl group, unsubstituted or substituted One or two or more kinds selected from the group consisting of a phenylene vinylene diyl group, an unsubstituted or substituted thienylene vinylene diyl group, and an unsubstituted or substituted triphenylamine diyl group are used as repeating units, and the adjacent repeating units are A conjugated polymer formed by bonding directly or via a linking group;
Following formula (1):

(In the formula, Ar ¹ , Ar ² and Ar ³ are each independently represented by the following formula:

Represents any divalent group represented by the formula: Here, R represents an alkyl group having 1 to 18 carbon atoms, a is an integer of 1 to 10, b and c are each independently an integer of 1 to 8, and d, e, f and g are each independently 1 to 1. An integer of 6 and h represents an integer of 1 to 4. When a plurality of R are present, they may be the same or different. Q ¹ and Q ² each independently represent a monovalent group having an oxirane ring at the terminal, an alkali metal atom, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an oxetane group, an acryloyl group, or a methacryloyl group. )
The composition containing the compound represented by these. The compound represented by the formula (1) is represented by the following formula (2):

(In the formula, Q ¹ , Q ² , Ar ² , R and h represent the same meaning as described above. A plurality of h may be the same or different. In the case where a plurality of R are present, They may be the same or different.)
The composition according to claim 1, which is represented by: The Ar ² is represented by the following formula:

(In the formula, R, a, c and h represent the same meaning as described above. When a plurality of R exist, they may be the same or different.)
The composition according to claim 1, which represents any divalent group represented by: The Ar ² is represented by the following formula:

(In the formula, R, c and h represent the same meaning as described above. When a plurality of Rs are present, they may be the same or different.)
The composition according to claim 3, which represents any divalent group represented by: The Ar ² is represented by the following formula:

(In the formula, R and c represent the same meaning as above. When a plurality of Rs are present, they may be the same or different.)
The composition of Claim 4 showing the bivalent group represented by these. At least one of Q ¹ and Q ² is a monovalent group having an oxirane ring at the terminal, an alkyl group having 1 to 18 carbon atoms, an oxetane group, any one of claims 1 to 5 acryloyl group or a methacryloyl group A composition according to 1. The composition according to claim 6, wherein at least one of Q ¹ and Q ² is a monovalent group having an oxirane ring at the terminal or an alkyl group having 1 to 18 carbon atoms.   Said R is a methyl group, The composition as described in any one of Claims 1-7.   The composition according to any one of claims 1 to 8, wherein the content of the compound represented by the formula (1) is 0.1 to 10,000 parts by weight with respect to 100 parts by weight of the conjugated polymer. object.   It is an object for organic semiconductor devices, The composition as described in any one of Claims 1-9.   The organic electroluminescent element which has an electrode which consists of an anode and a cathode, and a layer which is provided between this electrode and uses the composition as described in any one of Claims 1-10. The organic thin-film solar cell which has an electrode which consists of an anode and a cathode, and a layer which is provided between this electrode and uses the composition as described in any one of Claims 1-10.