Method for producing arylamine polymer

Abstract

To provide a method for producing an arylamine polymer by which the separation and purification of the arylamine polymer can successfully be carried out and the arylamine polymer having less impurities can easily be obtained.SOLUTION: There is provided a method for producing an arylamine polymer, the method comprising: reacting a starting material monomer that contains an aromatic compound (A) having two or more triflate groups or halogen atoms directly bonded to an aromatic ring and an aromatic compound (B) having an amino group in the presence of a palladium-containing catalyst and a water-insoluble organic solvent to obtain a reaction liquid that contains an arylamine polymer; obtaining a mixed liquid comprising the reaction liquid, water, and a water-soluble organic solvent that is compatible with the water-insoluble organic solvent; separating the mixed liquid into an organic phase and an aqueous phase; and recovering the organic phase.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] SUMMARY OF THE DISCLOSURE Embodiments of the present invention relate to methods for making arylamine polymers. [Background technology]

[0002] As elements that perform electrical operations using organic materials, organic electronic elements such as organic electroluminescence elements (hereinafter referred to as organic EL elements), organic photoelectric conversion elements, and organic transistors are known. Among them, organic EL elements have been attracting attention as large-area solid-state light sources, for example, as replacements for incandescent lamps and gas-filled lamps. They have also been attracting attention as the most promising self-luminous displays to replace liquid crystal displays (LCDs) in the field of flat panel displays (FPDs), and commercialization is progressing.

[0003] Various studies have been conducted on organic electronic materials for constructing organic electronic elements. In particular, in the field of organic EL elements, the development of charge-transporting polymers that can be easily formed into films by wet processes such as plate printing, such as letterpress printing and intaglio printing, and plateless printing, such as inkjet printing, has been promoted.

[0004] As an example of a charge transporting polymer, arylamine polymers are widely known, and studies are being conducted to improve the properties of organic electroluminescence devices by molecular design of polymers. As a method for synthesizing arylamine polymers, coupling reactions such as Kumada coupling, Stille coupling, Negishi coupling, Suzuki-Miyaura coupling, Hiyama coupling, and Buchwald-Hartwig reaction can be suitably used (Patent Document 1).

[0005] Among them, the Buchwald-Hartwig reaction is useful for the molecular design of arylamine polymers because the raw monomer compounds are easily available. However, impurities derived from halogen compounds used as raw materials in the reaction tend to remain in the polymer. In addition, impurities derived from complexes containing heavy metals such as palladium used as catalysts in the reaction may remain in the polymer.

[0006] When arylamine polymers (hereinafter referred to as polymers) obtained by the Buchwald-Hartwig reaction are used as organic electronic materials, impurities remaining in the polymers cause deterioration of the properties of organic electronic devices, such as an increase in the emission onset voltage, a decrease in the emission efficiency, and a decrease in stability. Therefore, a simple manufacturing method that can provide high-purity arylamine polymers is desired to improve the properties of organic electronic devices. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2011-105790 A [Patent Document 2] JP 2020-122099 A Summary of the Invention [Problem to be solved by the invention]

[0008] In response to this, Patent Document 2 discloses a separation and purification method for reducing impurities contained in a polymer by mixing anisole with a reaction solution containing a polymer obtained by the Buchwald-Hartwig reaction. However, the present inventors have found that in the development of a polymer, if the reaction solution after polymer synthesis becomes a suspension, an emulsion is likely to be formed during separation and purification, making it difficult to apply the above method. In particular, when a polymer having a branched structure is produced by the Buchwald-Hartwig reaction, the reaction solution is likely to become a suspension, and tends to form an emulsion during separation and purification. Therefore, there is a demand for a production method that can suppress the formation of an emulsion, perform separation and purification well, and easily obtain a polymer with few impurities even when the reaction solution containing a polymer becomes a suspension.

[0009] Therefore, the embodiment of the present invention provides a method for producing an arylamine polymer, which enables the separation and purification of an arylamine polymer to be carried out satisfactorily and enables the production of an arylamine polymer with few impurities to be easily obtained. [Means for solving the problem]

[0010] The present inventors have conducted extensive research into methods for producing arylamine polymers and have found that the above-mentioned problems can be solved by using a water-soluble organic solvent that is compatible with the water-insoluble organic solvent contained in the reaction solution of an arylamine polymer in the separation and purification of the arylamine polymer, thereby completing the present invention.

[0011] That is, the embodiments of the present invention relate to the following, but the present invention is not limited to the following embodiments and includes various embodiments.

[0012] <1> a reaction of raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring with an aromatic compound (B) having an amino group in the presence of a palladium-containing catalyst and a non-water-soluble organic solvent to obtain a reaction liquid including an arylamine polymer; obtaining a mixed solution of the reaction solution, water, and a water-soluble organic solvent that is compatible with the water-insoluble organic solvent; separating the mixture into an organic phase and an aqueous phase; and recovering said organic phase. A method for producing an arylamine polymer, comprising:

[0013] <2> The arylamine polymer has at least a branched structure represented by the following formula (I): <1> The manufacturing method described in

[0014] [ka]

[0015] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine; Ar 2 represents an aryl group derived from aromatic hydrocarbon having 6 to 30 carbon atoms, and * represents a bonding site with another structure.

[0016] <3> In the formula (I), Ar 2 has a structure represented by the following formula (b-1): <2> The manufacturing method described in

[0017] [ka]

[0018] In the formula, R 1 represents an alkyl group having 1 to 12 carbon atoms, an electron-withdrawing group, or an electron-donating group; and a represents an integer of 0 to 5.

[0019] <4> The raw material monomer further contains an aromatic compound (C), and the aromatic compound (C) has one halogen atom or one triflate group directly bonded to an aromatic ring and a polymerizable functional group. <1> ~ <3> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device.

[0020] <5> The reaction of the raw material monomer further comprises the use of a base. <1> ~ <4> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device.

[0021] <6> The base comprises an organic alkali metal compound. <5> The manufacturing method described in

[0022] <7> The method of the present invention further comprises adding a heavy metal scavenger to the mixture. <1> ~ <6> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device.

[0023] <8> The water-soluble organic solvent contains an alcohol. <1> ~ <7> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device.

[0024] <9> The non-water-soluble organic solvent includes an aromatic hydrocarbon solvent. <1> ~ <8> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device.

[0025] <10> The palladium-containing catalyst includes at least one selected from the group consisting of bis(di-t-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), bis(tri-t-butylphosphine)palladium(0), PdArBrP(t-Bu)3 (wherein Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), and chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium. <1> ~ <9> 13. The method for producing a semiconductor device according to claim 12, wherein the semiconductor device is a semiconductor device. Effect of the Invention

[0026] According to an embodiment of the present invention, it is possible to provide a method for producing an arylamine polymer, which allows for good separation and purification of an arylamine polymer and easily produces an arylamine polymer with few impurities. [Brief description of the drawings]

[0027] [Figure 1] FIG. 1 is a cross-sectional view showing an example of an organic EL element according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view showing the structure of the hole-only device prepared in the example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Hereinafter, an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiment, and various modifications are possible without departing from the gist of the present invention.

[0029] In some embodiments, the method for producing an arylamine polymer may include a step of synthesizing an arylamine polymer and a step of isolating and purifying the arylamine polymer. The step of synthesizing the arylamine polymer includes reacting a raw material monomer in the presence of a palladium-containing catalyst and a non-water-soluble organic solvent to obtain a reaction solution containing an arylamine polymer. This reaction can be carried out according to the Buchwald-Hartwig reaction.

[0030] The synthesis step comprises reacting raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring with an aromatic compound (B) having an amino group in the presence of a palladium-containing catalyst and a non-water-soluble organic solvent to obtain a reaction solution including an arylamine polymer. In one embodiment, the raw material monomer preferably further includes an aromatic compound (C) having one halogen atom or triflate group directly bonded to an aromatic ring in the molecule. The separation and purification step includes forming a mixture of the reaction solution, water, and a water-soluble organic solvent that is compatible with the water-insoluble organic solvent, and separating the mixture into an organic phase and an aqueous phase. The separation and purification step may further include recovering the organic phase after separation. The separation step may also include recovering a polymer from the organic phase.

[0031] Each step will now be described in more detail. <Synthesis process> The Buchwald-Hartwig reaction is a reaction to form a N-C bond by coupling an amine compound with, typically, a halogen compound, and can be carried out by methods known in the art. In one embodiment, the synthesis step involves reacting raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring with an aromatic compound (B) having an amino group in the presence of a palladium-containing catalyst and a non-water-soluble organic solvent. This reaction can produce a reaction solution containing an arylamine polymer. In one embodiment, the raw material monomer preferably further includes an aromatic compound (C) having one halogen atom or triflate group in the molecule. The aromatic compounds (A), (B) and (C) that can be used as raw material monomers, and the structure of the arylamine polymer obtained by the reaction will be described later.

[0032] (Palladium-containing catalyst) The palladium-containing catalyst used in the synthesis step means a catalyst containing palladium and a ligand. The palladium-containing catalyst includes a complex compound or salt containing palladium and a ligand, or a combination of a precursor of the palladium-containing catalyst and a ligand or a ligand precursor. In the production method of this embodiment, a known catalyst used in the Buchwald-Hartwig reaction can be used.

[0033] The above-mentioned ligand is preferably one having a bulky structure, and specific examples thereof include phosphine ligands and Buchwald ligands. N-heterocyclic carbene (NHC) can also be used as the ligand. Among them, phosphine ligands such as tri-t-butylphosphine, tri-o-tolylphosphine, and triphenylphosphine are more preferred.

[0034] The palladium-containing catalyst may be a palladium(0) complex or a palladium(II) salt. Specific examples of the palladium-containing catalyst include bis(tri-t-butylphosphine)palladium(0), tetrakis(triphenylphosphine)palladium(0), bis[1,2-bis(diphenylphosphino)ethane]palladium(0), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(tri-o-tolylphosphine)palladium(II), dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II), dichloro[1,2-bis(diphenylphosphino)ethane]palladium(II), and dichloro[1,3-bis(diphenylphosphino)propane]palladium(II). These compounds may also be used in combination with the above-mentioned ligand or ligand precursor.

[0035] Also, a precursor of a palladium-containing catalyst can be used to generate active palladium in the reaction system from the precursor, using organometallic reagents, phosphines, amines, and other components present in the reaction system. Examples of the precursor include bis(dibenzylideneacetone)palladium(0), palladium acetate(II), palladium chloride(II), di-μ-chlorobis[(η-allyl)palladium(II)], dichlorobis(acetonitrile)palladium(II), and dichlorobis(benzonitrile)palladium(II).

[0036] When using the precursor of the above-mentioned palladium-containing catalyst, it is preferable to use a precursor of a ligand such as a triphosphonium salt in combination. A specific example of the triphosphonium salt is tri-t-butylphosphonium tetrafluoroborate. This compound generates tri-t-butylphosphine in the system and functions as a ligand for palladium. Although not particularly limited, in one embodiment, it is preferable to use a combination of bis(tri-t-butylphosphine)palladium(0) and tri-t-butylphosphonium tetrafluoroborate as the palladium-containing catalyst.

[0037] In one embodiment, a palladium-containing catalyst having at least a structure represented by the following formula (1) can be suitably used as the catalyst. PdArBrP(t-Bu)3(1)

[0038] In the formula, Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Ar may be, for example, a substituted or unsubstituted phenyl group. At least one hydrogen atom in the aromatic ring of the aryl group may be substituted with an alkyl group having 1 to 12 carbon atoms.

[0039] A specific example of the palladium-containing catalyst having the above structure is the compound represented by the following formula (2): This compound can be produced, for example, by reacting tris(dibenzylideneacetone)dipalladium(0), o-bromotoluene, and tri-tert-butylphosphine.

[0040] [ka]

[0041] In another embodiment, a palladium-containing catalyst having at least a structure represented by the following formula (3) can be suitably used as the catalyst. [ka]

[0042] In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents a ligand. Z represents a leaving group. The leaving group may be one selected from the group consisting of a halogen atom, a methylsulfonyloxy group (-OSO2CH3), a tosyl group (-OSO2C6H5CH3), and a trifluoromethylsulfonyloxy group (-OSO2CH3).

[0043] Specific examples of the catalyst having the structure represented by the above formula (3) include the following. [ka]

[0044] The palladium-containing catalyst that can be suitably used in the production method of this embodiment can be produced according to a known method, but can also be obtained as a commercial product. For example, the XphosPd series manufactured by Aldrich Co., Ltd. can be used. Among them, the catalysts represented by the above formulas (3-1) to (3-4) can be obtained as XphosPd G1, XphosPd G2, XphosPd G3, and XphosPd G4. In one embodiment, the catalysts represented by the above formulas (3-2) and (3-4) can be more preferably used, and these can be obtained as XphosPd G2 and XphosPd G4, respectively.

[0045] The amount of the palladium-containing catalyst used is not particularly limited. The amount of the catalyst used may typically be in the range of 0.1 mol% or more and 20 mol% or less with respect to the aromatic compound (B) having an amino group used as a raw material monomer. By adjusting the amount of the catalyst used within the above range, the reaction can be efficiently carried out and the production of by-products can be easily suppressed. In one embodiment, the amount of the catalyst used may be preferably 0.1 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%, and even more preferably 0.2 mol% to 2 mol%, with respect to the aromatic compound (B) having an amino group. According to the production method of the present embodiment, even if the amount of the catalyst used is small, the reaction can proceed efficiently. Therefore, by adjusting the amount of the catalyst used, the amount of impurities derived from the catalyst contained in the polymer can be easily reduced.

[0046] In one embodiment, the palladium-containing catalyst may further include an additive. The additive is preferably a compound that functions as a ligand for palladium metal. Specific examples of compounds that can be used as additives include P(t-Bu)3·HBF3, PCy3·HBF3, and Xphos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl). Among these, P(t-Bu)3·HBF3 is preferred. When such an additive is used, the reactivity of the palladium catalyst tends to be further improved.

[0047] (base) In the reaction of the raw material monomer containing the aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to the aromatic ring and the aromatic compound (B) having an amino group, it is preferable to use a base in addition to the palladium-containing catalyst. The base is not particularly limited and may be either an inorganic base or an organic base. Although not particularly limited, in one embodiment, an organic base is preferable, and for example, an organic alkali metal compound such as t-butoxy sodium or n-butyl lithium can be suitably used.

[0048] The amount of base used is not particularly limited, but may be typically in the range of 1.0 molar equivalent or more and 4 molar equivalent or less with respect to the number of moles of aromatic compound (B) having an amino group used as raw material monomer. By adjusting the amount of base used within the above range, the reaction can be efficiently carried out and the generation of by-products can be easily suppressed. In one embodiment, it is preferable to use a palladium-containing catalyst and a base in combination during the reaction of the raw material monomer. It is more preferable to use a palladium-containing catalyst and an organic alkali metal compound in combination.

[0049] (Non-water-soluble organic solvent) The reaction of raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring and an aromatic compound (B) having an amino group is preferably carried out in the presence of a water-insoluble organic solvent. In this specification, the water-insoluble organic solvent means a solvent that, when a mixture is prepared by gently stirring the same volume of pure water at 20°C under 1 atmosphere, maintains a uniform appearance of the mixture even after the flow caused by stirring has ceased, and is a solvent other than the water-soluble organic solvents described below.

[0050] Examples of the non-water-soluble organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, and anisole, aliphatic ether solvents such as dioxane, tetrahydrofuran, and dimethoxyethane, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, and dimethylsulfoxide. In one embodiment, the reaction is preferably carried out in the presence of an aromatic hydrocarbon solvent. Among them, toluene or anisole may be more preferable, and toluene may be even more preferable.

[0051] The reaction temperature is not particularly limited and can be appropriately set depending on the boiling point of the non-water-soluble organic solvent used in the reaction. For example, the reaction temperature may be in the range of 0 to 200°C. In one embodiment, the reaction temperature is preferably in the range of 80 to 180°C, more preferably in the range of 100 to 160°C. In one embodiment, when toluene is used, the reaction can be allowed to proceed at a temperature of about 120°C. When anisole is used, the reaction can be allowed to proceed at a temperature of about 160°C. When anisole is used, a higher temperature can be applied, so that the reaction can be allowed to proceed more efficiently. The reaction time is preferably 1 to 48 hours, more preferably 1 to 24 hours, and further preferably 1 to 12 hours. Completion of the reaction can be confirmed by a known method such as gas chromatography.

[0052] The raw material monomer may be a mixture containing at least an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring, and an aromatic compound (B) having an amino group. In the raw material monomer, the blending ratio of the aromatic compound (A) to the aromatic compound (B) is not particularly limited. However, if unreacted raw material monomers remain in excess in the reaction system, undesirable side reactions may occur, so it is preferable to appropriately adjust the blending ratio. The blending ratio can be appropriately adjusted taking into consideration the structures of the aromatic compounds (A) and (B) used and the structure of the desired arylamine polymer.

[0053] In one embodiment, the compounding ratio (A):(B) of the aromatic compound (A) and the aromatic compound (B) contained in the raw material monomer may be preferably 0.5 to 1.5:1.0, and more preferably 0.6 to 1.4:1.0, in terms of the ratio of the number of reactive sites based on amino groups.

[0054] In one embodiment, the raw material monomer may further include an aromatic compound (C) having one halogen atom or triflate group in the molecule in addition to the aromatic compounds (A) and (B). In this case, the blending ratio of the aromatic compounds (A):(B):(C) may be preferably 0.2-0.9:1.0:0.0-1.0, more preferably 0.3-0.7:1.0:0.1-0.9, and even more preferably 0.4-0.6:1.0:0.2-0.8, in terms of the ratio of the number of reactive sites based on the amino group.

[0055] <Separation and purification process> Polymers obtained by the Buchwald-Hartwig reaction tend to contain residual impurities derived from the catalyst and raw monomers used during the reaction. Furthermore, the present inventors have found that when a polymer having a branched structure is synthesized, the reaction solution tends to be in a suspended state, and tends to form an emulsion when water is added. When an emulsion is formed, it becomes difficult to separate into an organic phase and an aqueous phase even if more water is added in the subsequent separation and purification process. As a result, it becomes difficult to recover the polymer from the organic phase. Even if the polymer can be recovered, a large amount of impurities will remain in the polymer.

[0056] In contrast, in the manufacturing method of the present embodiment, a reaction liquid, water, and a water-soluble organic solvent (hereinafter, also referred to as a water-soluble organic solvent) compatible with a non-water-soluble organic solvent are mixed to form a mixed liquid. By using a water-soluble organic solvent during the above mixing, problems caused by emulsions are eliminated (they can be demulsified), and the mixed liquid can be easily separated into an organic phase and an aqueous phase. Therefore, the polymer can be easily recovered from the organic phase, and the content of impurities remaining in the polymer can be reduced.

[0057] In the production method of this embodiment, the separation and purification step only needs to include obtaining a mixed solution of the reaction solution, water, and a water-soluble organic solvent that is compatible with the water-insoluble organic solvent, and the rest of the steps can be performed according to a method well known to those skilled in the art.

[0058] In this specification, the water-soluble organic solvent means a solvent that, when mixed with the same volume of pure water at 20° C. and under 1 atmosphere and slowly stirred, maintains a uniform appearance even after stirring is stopped. When mixed with a water-soluble organic solvent, the water-soluble organic solvent is preferably mixed with a water-insoluble organic solvent and does not separate from each other. In other words, the water-soluble organic solvent is preferably compatible with the water-insoluble organic solvent.

[0059] Examples of the water-soluble organic solvent that can be used in the production method of this embodiment include alcohols, ethers, ketones, and nitrogen atom-containing solvents. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.

[0060] Examples of the ether include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and diethylene glycol diethyl ether. Examples of the nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. Examples of the ketone include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol.

[0061] As the water-soluble organic solvent compatible with the non-water-soluble organic solvent, one of the above-mentioned solvents may be used alone or two or more of them may be used in combination. In one embodiment, alcohol is preferred, and among them, methanol can be preferably used.

[0062] As the water-soluble organic solvent, it is preferable to use a solvent that is compatible with the water-insoluble organic solvent contained in the reaction liquid from among the above solvents. For example, it is preferable that the water-insoluble organic solvent and the water-soluble organic solvent form a single phase in the mass ratio contained in the mixed liquid.

[0063] Without being bound by theory, in the Buchwald-Hartwig reaction, salts such as NaBr are formed due to the raw monomers and bases used, and such salts are poorly soluble in the non-aqueous organic solvents used in the synthesis of the polymer. In addition, tert-BuOH formed as a by-product during the reaction reduces the solubility of the polymer. Furthermore, compared to reaction solutions containing polymers with linear structures, reaction solutions containing polymers with branched structures tend to have lower solubility of the polymer and become suspended in water. For these reasons, it is believed that reaction solutions containing arylamine polymers, especially arylamine polymers with branched structures, tend to form emulsions during separation and purification.

[0064] In contrast, according to the present embodiment, the formation of an emulsion can be suppressed by mixing the reaction liquid, water, and a water-soluble organic solvent compatible with the water-insoluble organic solvent during separation and purification. Here, the water-insoluble organic solvent refers to the water-insoluble organic solvent used in the polymer synthesis process. When the reaction liquid and the water-soluble organic solvent (e.g., methanol) are mixed, salts such as NaBr are compatible with water-soluble organic solvents such as methanol. Therefore, when water is further added during the above mixing, not only tert-BuOH but also salts such as NaBr move to the aqueous phase together with methanol. From these factors, it is considered that the formation of an emulsion is suppressed, separation of the organic phase and the aqueous phase is facilitated, and components that become impurities can be easily reduced.

[0065] From the above viewpoint, the amount of the water-soluble organic solvent used is preferably adjusted appropriately so that the salt (solid matter) in the reaction solution is dissolved. Also, the amount of water used is preferably adjusted appropriately so that the organic phase and the aqueous phase are easily separated. In one embodiment, the ratio of water to the water-soluble organic solvent added to the reaction solution is preferably 9 / 1 to 5 / 5, more preferably 8 / 26 / 4, in terms of the mass ratio of water / water-soluble organic solvent.

[0066] The method of forming a mixture of a polymer-containing reaction solution, water, and a water-soluble organic solvent compatible with a non-water-soluble organic solvent is not particularly limited. In one embodiment, the mixture may be formed by simultaneously adding water and the water-soluble organic solvent to a polymer-containing reaction solution and further mixing. Here, water and the water-soluble organic solvent may be mixed in advance as necessary. In another embodiment, the mixture may be formed by mixing a polymer-containing reaction solution with the water-soluble organic solvent, and then adding water and mixing.

[0067] In one embodiment, a heavy metal trap may be further added during mixing to form a mixed solution of the reaction solution, water, and the water-soluble organic solvent. By adding a heavy metal trap during the mixing, impurities derived from the catalyst and the like can be more effectively removed. The heavy metal trap may be a compound capable of trapping a heavy metal such as palladium used as a catalyst by chelating it, or a compound capable of specifically binding to and adsorbing a heavy metal. For example, a silica compound having a specific functional group, a dithiocarbamate, or the like can be used as the heavy metal trap.

[0068] The amount of the heavy metal trap used is not particularly limited. As described above, in the separation and purification step, it is preferable to adjust the amount of the heavy metal trap used from the viewpoint of further enhancing the effect of removing impurities from the polymer by using a water-soluble organic solvent. In one embodiment, based on the number of moles of palladium (Pd) in the palladium-containing catalyst, the heavy metal trap is preferably used in an amount of 1 molar equivalent or more and 2000 molar equivalents or less, and more preferably in an amount of 1 molar equivalent or more and 500 molar equivalents or less.

[0069] In the above embodiment, dithiocarbamate can be suitably used as the heavy metal scavenger. Since the chelate in which dithiocarbamate is arranged with a heavy metal is easily dissolved in water, when water is added and the liquid is separated, it is easy to transfer the heavy metal such as Pd derived from the catalyst to the aqueous phase. The dithiocarbamate is not particularly limited as long as it is a compound having a dithiocarbamyl group in the molecule, but alkyldithiocarbamate is preferred. Among them, from the viewpoint of water solubility, alkyldithiocarbamate having an alkyl group having 1 to 6 carbon atoms is more preferred.

[0070] Specific examples include dimethyldithiocarbamate, diethyldithiocarbamate, dipropyldithiocarbamate, dibutyldithiocarbamate, ethylenebisdithiocarbamate, methyldithiocarbamate, ethyldithiocarbamate, n-propyldithiocarbamate, etc., and the salt form of each may be a sodium salt, a potassium salt, etc. Among them, sodium N,N-diethyldithiocarbamate (NaS2CN(C2H5)2) can be preferably used.

[0071] The method for recovering the polymer from the mixed liquid is not particularly limited, and can be carried out by applying a method well known to those skilled in the art. For example, the mixed liquid obtained by the above mixing can be separated into an organic phase and an aqueous phase according to a separation method. This separation method can easily recover the desired polymer while removing impurities. In one embodiment, when the mixed liquid is separated into an organic phase and an aqueous phase, the separation can be made easier by adding water as necessary. Here, the water is preferably deionized water.

[0072] In one embodiment, the separation and purification step may include adding water and a water-soluble organic solvent (preferably methanol) to a reaction solution (preferably a toluene solution) containing a polymer to form a mixed solution, and further adding water as necessary during separation of the mixed solution. The desired polymer can be obtained by distilling off the water-insoluble organic solvent from the organic phase obtained by separation.

[0073] In another embodiment, the separation and purification step may include mixing the reaction solution containing the polymer, the water-soluble organic solvent, and an aqueous solution containing dimethyldithiocarbamate, and further adding and mixing water as necessary. It may also include separating the mixed solution thus obtained to remove the aqueous phase, and removing the water-insoluble organic solvent from the organic phase obtained after the separation to obtain the desired polymer. It may also include dissolving the obtained polymer again in a water-soluble organic solvent such as methanol and recrystallizing it as necessary.

[0074] In one embodiment, from the viewpoint of providing a polymer with a purity suitable for use as an organic electronics material, the palladium content in the polymer is preferably 100 ppm or less, more preferably 80 ppm or less, and even more preferably 50 ppm or less. The halogen atom content (total amount) in the polymer is preferably 300 ppm or less, more preferably 100 ppm or less, and even more preferably 60 ppm or less.

[0075] In contrast, the production method of the above embodiment can easily provide a polymer in which the palladium content and the content of halogen atoms such as bromine atoms and chlorine atoms are all within the above ranges, and therefore the production method of the above embodiment can provide a polymer that can be suitably used as an organic electronics material.

[0076] <Arylamine polymer> In the manufacturing method of the above embodiment, the arylamine polymer (hereinafter sometimes abbreviated as polymer) may be any polymer obtained by reacting raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring and an aromatic compound (B) having an amino group, and the structure is not particularly limited. Depending on the raw material monomer used, the polymer may have either a linear or branched structure.

[0077] The polymer, for example, contains at least a divalent structural unit L and a monovalent structural unit T having charge transport properties, and may further contain a trivalent or higher structural unit B constituting a branched portion. The polymer preferably contains at least a trivalent or higher structural unit B and a monovalent structural unit T having charge transport properties, and may further contain a divalent structural unit. The molecular chain of the polymer has a chain structure containing a divalent structural unit and / or a trivalent structural unit. The polymer may contain only one type of each structural unit, or may contain multiple types of each structural unit. In the charge transport polymer, the structural units are bonded to each other at a "monovalent" to "trivalent or higher" bonding site.

[0078] Examples of partial structures contained in the charge transporting polymer include the following. The charge transporting polymer is not limited to polymers having the following partial structures. In the partial structures, "L" represents a structural unit L, "T" represents a structural unit T, and "B" represents a structural unit B. In the following, "*" represents a bonding site with other structural units. In the following partial structures, multiple L's may be the same structural unit or different structural units. The same applies to T and B.

[0079] (Example of partial structure of linear polymer)

[0080] [ka]

[0081] (Example of partial structure of branched polymer)

[0082] [ka]

[0083] When a polymer has a branched structure, emulsions tend to be easily formed during separation and purification, and the effect obtained by the manufacturing method of the above embodiment is remarkable. From this viewpoint, in one embodiment, the polymer manufactured by the above manufacturing method preferably has a branched structure. A polymer having a branched structure is excellent in heat resistance, and since a large number of terminal groups can be introduced, it is also preferable from the viewpoint of exhibiting good solubility and curability. Hereinafter, an arylamine polymer having a branched structure (also called a branched polymer) will be described as an example of a polymer that can be manufactured by the above manufacturing method.

[0084] The branched polymer that can be produced by the production method of the present embodiment preferably contains at least a trivalent structural unit represented by the following formula (a) as the structural unit B, and at least a divalent structural unit represented by the following formula (b) as the structural unit L, and contains a structure represented by the following formula (I) formed by directly bonding at least one bonding site in each structural unit to each other.

[0085] [ka]

[0086] [ka]

[0087] The branched polymer preferably contains a structure represented by the following formula (I-1) or (I-2), and more preferably contains a structure represented by the following formula (I-2).

[0088] [ka]

[0089] In the formula, Ar 1 represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine; Ar 2represents a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, and * represents a bonding site with other structures. Ar 1 and Ar 2 Details will be provided later.

[0090] In order to produce a branched polymer containing at least the structure represented by the above formula (I), an aromatic compound (A) having three halogen atoms or triflate groups directly bonded to an aromatic ring and an aromatic compound (B) having a primary amino group can be used as raw material monomers.

[0091] Hereinafter, each structural unit constituting the branched polymer and the raw material monomers will be described in more detail. (Structural unit B) The structural unit B is a trivalent or higher structural unit constituting a branched portion of a branched polymer. From the viewpoint of improving the durability of an organic electronics element, the structural unit B is preferably hexavalent or lower, more preferably trivalent or tetravalent. The structural unit B preferably has charge transport properties. For example, the structural unit B may be an organic group derived from an aromatic hydrocarbon, an aromatic heterocycle, or a triarylamine. Among them, from the viewpoint of improving the durability of an organic electronics element, for example, a substituted or unsubstituted organic group (structure) derived from a triarylamine, carbazole, or a condensed polycyclic aromatic hydrocarbon can be preferably selected as the structural unit B.

[0092] In this embodiment, the branched polymer contains at least a trivalent structural unit represented by the following formula (a) (hereinafter, also referred to as structural unit B1) as the structural unit B. This structural unit B1 can be derived, for example, from an aromatic compound represented by the following formula (A1).

[0093] [ka]

[0094] In the formula, Ar 1represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle, or a triarylamine. The trivalent organic group is also called an arenetriyl group or a heteroarenetriyl group. Ar 1 is an atomic group formed by removing three hydrogen atoms from an aromatic hydrocarbon or aromatic heterocycle, or from an aromatic ring in a triarylamine. In one embodiment, Ar 1 may be a trivalent organic group preferably derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine. In the formula, * represents a bonding site with another structure.

[0095] In the formula, Q represents a halogen atom or a triflate group. The halogen atom may be a chlorine atom, a bromine atom, or an iodine atom. The triflate group has a structure (CF3SO2-) in which one hydrogen atom is removed from trifluoromethanesulfonic acid. Q is preferably a halogen atom, more preferably a bromine atom.

[0096] Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, 9,10-dihydrophenanthrene, triphenylene, pyrene, chrysene, perylene, triphenylene, pentacene, and benzopyrene.

[0097] Examples of the aromatic heterocycle include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, carbazole, furan, benzofuran, dibenzofuran, pyrrole, thiophene, benzothiophene, dibenzothiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole, benzothiadiazole, benzotriazole, and benzothiophene.

[0098] The aromatic hydrocarbon and aromatic heterocycle may be a single ring or a condensed ring. In addition, they may have a polycyclic structure in which two or more selected from the single ring and the condensed ring are bonded via a single bond. Examples of aromatic hydrocarbons having such a polycyclic structure include biphenyl, terphenyl, and triphenylbenzene.

[0099] In one embodiment, Ar 1 may be a trivalent organic group derived from triarylamine. Triarylamine means a tertiary aromatic amine in which three aryl groups (aromatic groups) are bonded to a nitrogen atom. Here, the aryl group is a monovalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms. The aromatic hydrocarbon and aromatic heterocycle may be specifically as described above. In triarylamine, specific examples of the aryl group derived from an aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a biphenyl group. Specific examples of the aryl group derived from an aromatic heterocycle group include a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, and an imidazolyl group. In one embodiment, the triarylamine is preferably triphenylamine.

[0100] The aromatic hydrocarbon and aromatic heterocycle contained in the monovalent organic group and the trivalent organic group may be unsubstituted or may have one or more substituents R. Each of the substituents R is independently -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 , a halogen atom, and a group containing a polymerizable functional group as described below. 1 It is more preferable that: R 1 ~R 8 each independently represents a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms (provided that R 1is a hydrogen atom), or an aryl group or heteroaryl group having 2 to 30 carbon atoms. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. The alkyl group may be further substituted with an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group may be further substituted with a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms.

[0101] Specific examples of the structural unit B1 include the structures shown below. Among them, structures derived from triarylamine and structures derived from N-arylcarbazole are preferred. The structural unit B1 shown below can be derived, for example, from a compound having a halogen atom or a triflate group at the bonding site "*" as a raw material monomer.

[0102] [ka]

[0103] In the formula, Ar each independently represents a divalent linking group, for example, each independently represents an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. In the formula, * represents a bonding site to another structure.

[0104] In one embodiment, the structural unit B1 preferably contains at least one of a structural unit derived from a triphenylamine structure represented by the following formula (B1-1) and a structural unit derived from an N-phenylcarbazole structure represented by the following formula (B1-2): These structural units can be derived, for example, from a raw material monomer, a compound having a halogen atom or a triflate group at the bonding site "*" in the structure shown below.

[0105] [ka]

[0106] In the structural unit (B1-1), l, m, and n each independently represent an integer of 0 to 4, and each independently represent the number of substituents R. l, m, and n each independently represent an integer of 0 to 2, and more preferably an integer of 0 or 1. In one embodiment, the number of substituents in the structural unit (B1-1) is preferably 1 or 2. In another embodiment, the number of substituents in the structural unit (B1-1) is preferably 0.

[0107] In the structural unit (B1-2), l is an integer of 0 to 4, and m and n are each independently an integer of 0 to 3, each indicating the number of substituents R. l is preferably an integer of 0 to 2, more preferably an integer of 0 or 1. m and n are each independently an integer of 0 to 2, more preferably an integer of 0 or 1. In one embodiment, the number of substituents in the structural unit (B1-2) is preferably 1 or 2. In another embodiment, the number of substituents in the structural unit (B1-2) is preferably 0.

[0108] In each of the above structural units, "*" indicates a bonding site with other structures, and at least one of the bonding sites is bonded to a nitrogen atom (N). In the structural unit (B1-1) or (B1-2), it is preferable that two or three of the three bonding sites are bonded to a nitrogen atom. It is more preferable that all of the three bonding sites are bonded to a nitrogen atom. When the charge transport polymer contains an N-Ph bond, doping and conjugation become easy, and it tends to be easy to obtain better electrical conductivity. From this viewpoint, it is preferable that the structural unit B contains either the structural unit (B1-1) derived from triphenylamine or the structural unit (B1-2) derived from N-phenylcarbazole. By containing these structural units, it is easy to obtain good electrical conductivity.

[0109] In the structural units (B1-1) and (B1-2), the substituent R is the same as the substituent R described above for the structure represented by formula (I). In one embodiment, when the structural unit B has the structural unit (B1-1) or (B1-2), the substituent R may have a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The aromatic ring in the aryl group may be further substituted with a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. In another embodiment, it is preferable that both of the structural units (B1-1) and (B1-2) are unsubstituted.

[0110] In one embodiment, the structural unit B may include a tetravalent or higher structural unit B2 in addition to the structural unit B1. For example, specific examples of the structural unit B2 include the following. Among them, a structure including a triarylamine structure and a structure including a carbazole structure are preferred. These structural units B2 can be derived, for example, from a compound having a halogen atom or a triflate group at the bonding site "*" in the structure shown below as a raw material monomer.

[0111] [ka]

[0112] In the formula, each Ar independently represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, and examples thereof include divalent groups obtained by removing one hydrogen atom from a group having one or more hydrogen atoms among R (excluding groups containing a polymerizable functional group) in the structural unit L described below. Z represents any one of a carbon atom, a silicon atom, and a phosphorus atom. In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include the substituent R in the structural unit B1 described above.

[0113] (Structural unit L) The structural unit L is a divalent structural unit having charge transportability, and is not particularly limited as long as it contains an atomic group having the ability to transport charge. From the viewpoint of directly bonding with the structural unit (a) described above to form a structure represented by formula (I), the structural unit L contains at least a divalent structural unit represented by the following formula (b) (hereinafter also referred to as structural unit L1). This structural unit L1 can be derived using an aromatic compound represented by the following formula (B1).

[0114] [ka]

[0115] In the formula, Ar 2 is a monovalent organic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, and is an atomic group obtained by removing one hydrogen atom from the aromatic ring of the aromatic hydrocarbon. 2 is also called an aryl group. 2 is an aryl group having 6 to 30 carbon atoms forming a ring, and has a structure in which at least one hydrogen atom of the aromatic ring in the aryl group is substituted with an electron-withdrawing group or an electron-donating group. 2 In the above formula, the number of carbon atoms forming the ring is more preferably 6 to 24.

[0116] Specific examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, biphenyl, terphenyl, triphenylbenzene, etc. Here, the aromatic ring in the aromatic hydrocarbon has one or more electron-withdrawing groups or electron-donating groups as substituents, and may further have other substituents as necessary. The substituents may be the same as the substituent R described above.

[0117] In one embodiment, the Ar 2 may have a structure represented by the following formula (b-1): [ka] In the formula, R 1is an electron withdrawing group, an electron donating group, or an alkyl group having 1 to 12 carbon atoms, and a is an integer of 1 to 5. When a is 2 or more, R 1 may be all the same or a combination of different groups. In one embodiment, a may be preferably 1 to 4, more preferably 1 to 3, and further preferably 1 or 2.

[0118] The above "electron-withdrawing group" refers to a substituent that is more likely to attract electrons from the bonding atom than a hydrogen atom. On the other hand, the "electron-donating group" refers to a substituent that is more likely to donate electrons to the bonding atom than a hydrogen atom, and does not include alkyl groups. When a charge-transporting polymer contains a specific structure in which a hydrogen atom in an aromatic ring bonded to an N atom is replaced with an electron-withdrawing group or an electron-donating group, the HOMO level tends to be easily adjusted.

[0119] For example, when an electron-withdrawing group is introduced into a specific portion of a charge-transporting polymer as described above, the HOMO level can be deepened. Also, when an electron-withdrawing group is introduced into a specific portion, the solubility of the charge-transporting polymer tends to be improved. From this viewpoint, in one embodiment, in a branched polymer having a structure of formula (I), Ar 2 At least one hydrogen atom of the aromatic ring is preferably substituted with an electron-withdrawing group.

[0120] The electron-withdrawing group is not particularly limited, and specific examples thereof include a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group. More specifically, examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodine group. The number of carbon atoms in the alkyl group in the halogen-substituted alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. From the viewpoint of the strength of the electron-withdrawing property, the halogen group is preferably a fluoro group, and the halogen-substituted alkyl group is preferably a fluoroalkyl group. In one embodiment, the fluoroalkyl group may be a perfluoroalkyl group.

[0121] Considering the thermal stability of the charge transporting polymer, the electron-withdrawing group is preferably at least one selected from the group consisting of a fluoro group, a fluoroalkyl group, a nitro group, a cyano group, a sulfonic acid group, and a sulfoxide group. More preferably, it may be at least one selected from the group consisting of a fluoro group, a fluoroalkyl group, a sulfonic acid group, and a sulfoxide group. More preferably, it may be at least one of a fluoro group and a fluoroalkyl group. When the aryl group contains multiple electron-withdrawing groups, the multiple electron-withdrawing groups may be the same or different from each other.

[0122] In one embodiment, Ar in formula (I) 2 preferably has a structure represented by the following formula (b-1a) or (b-1b).

[0123] [ka]

[0124] In each formula, Ew represents an electron-withdrawing group. In the structure represented by the above formula (b-1a) or (b-1b), the electron-withdrawing group (Ew) is preferably a halogen atom or a halogen-substituted alkyl group. Among them, a fluorine atom (F) or trifluoromethane (CF3) is more preferable.

[0125] The electron donating group is not particularly limited, but specific examples include -OR, -OH, and -NRR'. The alkyl groups (R, R') of the alkyloxy group (-OR) and the alkylamine (-NRR') may each have a linear, branched, or cyclic structure. The number of carbon atoms in the alkyl group may be preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0126] In one embodiment, Ar in formula (I) 2 preferably has a structure represented by the following formula (b-1c) or (b-1d).

[0127] [ka]

[0128] In each formula, Ea represents an electron-withdrawing group. In the structure represented by the above formula (b-1c) or (b-1d), the electron-withdrawing group (Ea) is preferably -OR, and more preferably a methoxy group.

[0129] As described above, the branched polymer having the structure represented by the above formula (I) is 2 In one embodiment, the branched polymer further includes an alkyl group having 1 to 12 carbon atoms as the substituent on the aromatic ring, in addition to the at least one electron-withdrawing group or electron-donating group.

[0130] The alkyl group having 1 to 12 carbon atoms may have any of a linear, branched, or cyclic structure. In one embodiment, the alkyl group preferably has a linear or branched structure. In one embodiment, in consideration of application to a wet process, R 1 is preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and further preferably an alkyl group having 4 to 12 carbon atoms.

[0131] In one embodiment, the structural unit L may further include a structural unit L2 having a structure different from the structural unit L1 in addition to the structural unit L1. The structural unit L2 is selected from a substituted or unsubstituted aromatic tertiary amine structure (also referred to as a triarylamine structure), a carbazole structure, a thiophene structure, a bithiophene structure, a fluorene structure, a benzene structure, a biphenylene structure, a terphenylene structure, a naphthalene structure, an anthracene structure, a tetracene structure, a phenanthrene structure, a dihydrophenanthrene structure, a pyridine structure, a pyrazine structure, a quinoline structure, an isoquinoline structure, a quinoxaline structure, an acridine structure, a diazaphenanthrene structure, a furan structure, a pyrrole structure, an oxazole structure, an oxadiazole structure, a thiazole structure, a thiadiazole structure, a triazole structure, a benzothiophene structure, a benzoxazole structure, a benzoxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, an N-arylphenoxazine structure, and a structure containing one or more of these. The triarylamine structure is more preferably a triphenylamine structure.

[0132] In one embodiment, from the viewpoint of obtaining excellent hole transport properties, the structural unit L2 preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted triarylamine structure, a carbazole structure, a thiophene structure, a bithiophene structure, a benzene structure, a fluorene structure, and a pyrrole structure, and more preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted triarylamine structure and a carbazole structure. In another embodiment, from the viewpoint of obtaining excellent electron transport properties, the structural unit L2 preferably contains one or more structures selected from the group consisting of a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, and a quinoline structure.

[0133] The structural unit L2 can be derived, for example, by using the aromatic compounds shown below as raw material monomers. Q-L2-Q In the formula, Q represents a halogen atom or a triflate group.

[0134] The structural unit L2 can also be derived, for example, by using the aromatic compounds shown below as raw material monomers. Ar-NH-L2-NH-Ar In the formula, each Ar independently represents an aryl group or heteroaryl group having 2 to 30 carbon atoms.

[0135] Specific examples of the structural unit L2 include the following: However, the structural unit L2 is not limited to the following. [ka]

[0136] [ka]

[0137] Each R independently represents a hydrogen atom or a substituent. Preferably, each R independently represents -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 and a group containing a polymerizable functional group as described below. 1 ~R 8 each independently represents a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. The alkyl group may be further substituted with an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group may be further substituted with a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms.

[0138] In one embodiment, R is -R 1It is preferable that Ar is an arylene group or a heteroarylene group having 2 to 30 carbon atoms. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. Ar is preferably an arylene group, and more preferably a phenylene group.

[0139] The aromatic hydrocarbon may be a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more rings selected from a monocyclic ring and a condensed ring are bonded via a single bond. The aromatic heterocyclic ring may be a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more rings selected from a monocyclic ring and a condensed ring are bonded via a single bond.

[0140] (Structural unit T) The structural unit T is a monovalent structural unit constituting the terminal portion of the charge transporting polymer. The structural unit T is not particularly limited, and is selected from, for example, a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of these. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure, from the viewpoint of imparting durability without reducing the charge transportability. The structural unit T may have the same structure as the structural unit L, except for the valence. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure, more preferably a substituted or unsubstituted benzene structure, from the viewpoint of imparting durability without reducing the charge transportability.

[0141] Specific examples of the structural unit T include the following. However, the structural unit T is not limited to the following. The structural unit T can be derived, for example, from an aromatic compound having a halogen atom or a triflate group at the bonding site "*" in the following structure as a raw material monomer.

[0142] [ka]

[0143] Each R independently represents a hydrogen atom or a substituent. The substituent R is -R 1 , -OR 2 , -SR 3 , -OCOR 4 , -COOR 5 , -SiR 6 R 7 R 8 R is selected from the group consisting of polymerizable functional groups described below. 1 ~R 8 is R in structural unit L 1 ~R 8 In the above structure, the number of the substituents may be an integer of 0 to 5, preferably 1 to 3, and more preferably 1 or 2. The substituents are -R 1 and at least one of the polymerizable functional groups described below. 1 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may have any of a linear, cyclic, or branched structure.

[0144] (Polymerizable functional group) In one embodiment, the branched polymer may have a polymerizable functional group in the molecule. The polymerizable functional group is a functional group that can form a bond by applying heat and / or light. When the charge transporting polymer contains a polymerizable functional group, an organic layer made of a cured film can be formed by curing a coating film formed using the charge transporting polymer. The organic layer made of such a cured film has the solvent resistance required for further laminating an upper layer on the organic layer by a wet process. Therefore, when the charge transporting polymer contains a polymerizable functional group, it becomes easy to form a multilayer by a wet process.

[0145] Examples of the polymerizable functional group include a group having a carbon-carbon multiple bond (e.g., a vinyl group, an allyl group, a butenyl group, an ethynyl group, an acryloyl group, an acryloyloxy group, an acryloylamino group, a methacryloyl group, a methacryloyloxy group, a methacryloylamino group, a vinyloxy group, a vinylamino group, etc.), a group having a small ring (e.g., a cyclic alkyl group such as a cyclopropyl group or a cyclobutyl group; a cyclic ether group such as an epoxy group (oxiranyl group) or an oxetane group (oxetanyl group); a cyclic thioether group such as an episulfide group; a cyclic ester group such as a diketene group or a lactone group; a cyclic amide group such as a lactam group), a heterocyclic group (e.g., a furan-yl group, a pyrrol-yl group, a thiophen-yl group, a silol-yl group), a benzocyclobutene group, etc.

[0146] The polymerizable functional group preferably includes one or more selected from the group consisting of a group having a carbon-carbon multiple bond, a group having a small ring, and a heterocyclic group, and more preferably includes one or more selected from the group consisting of a group having a carbon-carbon double bond, a cyclic ether group, and a heterocyclic group. Specifically, the polymerizable functional group is preferably a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, an oxetane group, a pyrrolyl group, and a thiophene-yl group, and from the viewpoint of the solubility and curability of the charge transport polymer, a vinyl group, an oxetane group, and a thiophene-yl group are more preferable. The polymerizable functional group may be a substituted or unsubstituted polymerizable functional group. Examples of the substituent that the polymerizable functional group can have include alkyl groups having 1 to 6 carbon atoms, such as a methyl group and an ethyl group.

[0147] The polymerizable functional group may be directly bonded to the aromatic ring or may be bonded to the aromatic ring via a divalent group such as a linking group. That is, in one embodiment, the charge transporting polymer may further have a monovalent structural unit represented by the following formula (c). -Ar 3 -(X)a-(Y)bZ (c)

[0148] In the formula, Ar 3represents a divalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, X represents a linking group, Y represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, Z represents a substituted or unsubstituted polymerizable functional group, and a and b each independently represent 0 or 1.

[0149] In formula (c), X may be at least one linking group selected from the group consisting of the following formulae (x1) to (x10): In one embodiment, the linking group X is preferably x1. [ka]

[0150] In the above formula, R each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. In one embodiment, R is preferably a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms. The number of carbon atoms is more preferably 2 to 16, further preferably 3 to 12, and particularly preferably 4 to 8. In another embodiment, R is preferably an aryl group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and further preferably a phenyl group.

[0151] In the above formula (c), Y is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, or a combination thereof. The aliphatic hydrocarbon group may be saturated or unsaturated. In one embodiment, Y is preferably an aliphatic hydrocarbon group having a linear structure, and more preferably a saturated one, from the viewpoint of easy availability of the raw material monomer. From these viewpoints, in formula (c), Y is -(CH2) n -, and n is 1 to 10. n may be preferably 1 to 8, and more preferably 1 to 6. From the viewpoint of heat resistance, n is further preferably 1 to 4, and n is most preferably 1 or 2.

[0152] In view of the above, in one embodiment, the charge transporting polymer preferably has a structural moiety represented by the following formula (c1). -Ar 3 -(O)a-(CH2) n -Z (c1) In the formula, Ar 3 represents a divalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms; Z represents a substituted or unsubstituted polymerizable functional group; a is 0 or 1; and n is 0 or an integer of 1 to 10.

[0153] In one embodiment, the charge transporting polymer preferably has a structural moiety represented by at least one of the following formulae (c-1) and (c-2). -Ar-Z (c-1) -Ar-O-(CH2) n -Z (c-2) In the formula, Ar represents a substituted or unsubstituted arylene group or heteroarylene group having 2 to 30 carbon atoms, Z represents a substituted or unsubstituted polymerizable functional group, and n is an integer of 1 to 10. The details of each are as described above.

[0154] Although not particularly limited, Z in the above formula (c-1) is preferably an allyl group. From the viewpoint of storage stability, Z in the above formula (c-2) is preferably an oxetane group represented by the following formula (z1). In the formula, R may be a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms. R is particularly preferably a methyl group or an ethyl group.

[0155] [ka]

[0156] A charge transporting polymer having at least one structural portion represented by the above formula (c) contains at least one polymerizable functional group Z in its structure. A compound containing a polymerizable functional group can be cured by a polymerization reaction, and its solubility in a solvent can be changed by curing. Therefore, the organic electronics material of this embodiment, which is composed of a charge transporting polymer having a polymerizable functional group, has excellent curability and is suitable for wet processes.

[0157] When the charge transporting polymer has a polymerizable functional group, at least one of the structural units B, L, and T constituting the polymer may contain the structural moiety represented by the above formula (c), and the position of introduction is not particularly limited. In a preferred embodiment, from the viewpoint of enhancing curability, the structural moiety represented by the above formula (c) is preferably present in the structural unit T constituting at least one terminal part of the charge transporting polymer. The structural moiety represented by the above formula (c) is preferably present in the structural unit T constituting the terminal part, also from the viewpoint of facilitating synthesis of the monomer compound constituting the charge transporting polymer.

[0158] From the above viewpoint, in one embodiment, the charge transporting polymer preferably contains a structural unit T1 having a structure represented by the following formula (c) as the structural unit T. Such a structural unit T1 can be derived, for example, by using an aromatic compound represented by the following formula (C1) as the aromatic compound (C) of the raw material monomer aromatic compound described in the production method of this embodiment. *-Ar 3 -(X)a-(Y)bZ (c) Q-Ar 3 -(X)a-(Y)bZ (C1) In each formula, Ar 3 , X, Y, Z, a, and b are as described above. * represents a bonding site with other structures. Q represents a halogen atom or a triflate group. Q is preferably a halogen atom, and more preferably a bromine atom.

[0159] In one embodiment, the structural unit T1 preferably contains a structural unit represented by the following formula (T1-1) and a structural unit represented by the following formula (T1-2): In the formula, Ph is a phenyl group, Z is a polymerizable functional group, and n is an integer of 1 to 10. -Ph-Z (T1-1) -Ph-O-(CH2) n -Z (T1-2)

[0160] In one embodiment, the charge transporting polymer may further include, in addition to the structural unit T1, a structural unit T2 having a structure different from the structural unit T1, preferably a structure not including a polymerizable functional group.

[0161] In the charge transporting polymer, the polymerizable functional group is preferably introduced at least to the terminal portion (i.e., the structural unit T) of the charge transporting polymer. The polymerizable functional group may be introduced to a portion other than the terminal portion (i.e., the structural unit L or B), or may be introduced to both the terminal portion and the portion other than the terminal portion. From the viewpoint of achieving both curability and charge transportability, it is preferable that the polymerizable functional group is introduced only to the terminal portion. In addition, in the charge transporting polymer having a branched structure, the polymerizable functional group may be introduced to the main chain of the charge transporting polymer, may be introduced to the side chain, or may be introduced to both the main chain and the side chain.

[0162] For example, the number of polymerizable functional groups per molecule of the charge transporting polymer is preferably 2 or more, more preferably 3 or more, from the viewpoint of obtaining a sufficient change in solubility, and is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of maintaining the charge transporting property.

[0163] In addition, from the viewpoint of obtaining good curability, the ratio of polymerizable functional groups in the charge transporting polymer is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 3 mol% or more, based on the total structural units. In addition, from the viewpoint of obtaining good charge transportability, the ratio of polymerizable functional groups is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. Here, the "ratio of polymerizable functional groups" refers to the ratio of structural units having polymerizable functional groups.

[0164] The content and ratio of the polymerizable functional group per molecule of the charge transport polymer can be calculated as an average value using the amount of the polymerizable functional group used to synthesize the charge transport polymer (for example, the amount of the monomer having the polymerizable functional group multiplied by the number of polymerizable functional groups per monomer), the amount of the monomer corresponding to each structural unit, the mass average molecular weight of the charge transport polymer, etc. 1 It can be calculated as an average value using the ratio of the integral value of the signal derived from the polymerizable functional group to the integral value of the entire spectrum in the H NMR (nuclear magnetic resonance) spectrum, the mass average molecular weight of the charge transport polymer, etc. When the amount of the charge is clear, it is preferable to use the value calculated using the amount of the charge, because it is simple.

[0165] (number average molecular weight) The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, etc. From the viewpoint of excellent charge transportability, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, even more preferably 2,000 or more, and even more preferably 5,000 or more. In addition, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of an ink composition, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less.

[0166] (Weight average molecular weight) The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming property, etc. From the viewpoint of excellent charge transportability, the weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and even more preferably 30,000 or more. In addition, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of an ink composition, the mass average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, even more preferably 400,000 or less, and even more preferably 200,000 or less, and 100,000 or less, in this order. In one embodiment, the weight average molecular weight of the charge transporting polymer may be preferably 2,000 to 500,000, more preferably 3,000 to 100,000, and further preferably 8,000 to 50,000.

[0167] The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.

[0168] (Structural unit ratio) The ratio of the structural unit B contained in the charge transporting polymer is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total structural units, from the viewpoint of improving the durability of the organic electronics element. In addition, the ratio of the structural unit B is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, from the viewpoint of suppressing an increase in viscosity and smoothly synthesizing the charge transporting polymer, or from the viewpoint of obtaining sufficient charge transportability. Here, the above ratio of the structural unit B means the total amount of the structural units B1 and B2. In one embodiment, the structural unit B may be composed of only the structural unit B1.

[0169] In the charge transporting polymer, the ratio of the structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total structural units, from the viewpoint of obtaining sufficient charge transportability. In addition, the ratio of the structural unit L is preferably 97 mol% or less, more preferably 92 mol% or less, and even more preferably 85 mol% or less, taking into consideration the structural unit T and the structural unit B. Here, the above ratio of the structural unit L means the total amount of the structural units L1 and L2. In one embodiment, the structural unit L may be composed of only the structural unit L1.

[0170] The ratio of the structural unit T contained in the charge transporting polymer is preferably 3 mol% or more, more preferably 8 mol% or more, and even more preferably 15 mol% or more, based on the total structural units, from the viewpoint of solubility and curability. The above range is also preferred from the viewpoint of improving the characteristics of an organic electronic device, or from the viewpoint of suppressing an increase in viscosity and smoothly synthesizing the charge transporting polymer. Moreover, from the viewpoint of obtaining sufficient charge transportability, the ratio of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

[0171] In consideration of the balance between charge transport properties, durability, productivity, and the like, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is preferably L:T:B=100:10 to 200:10 to 100, more preferably 100:20 to 180:20 to 90, and further preferably 100:40 to 160:30 to 80.

[0172] The ratio of the structural units can be determined by the amount of monomers corresponding to each structural unit used to synthesize the charge transporting polymer. 1 The average value can be calculated by using the integral value of the spectrum derived from each structural unit in the H NMR spectrum. When the amount of the charge is clear, the value calculated using the amount of the charge is preferably used because it is simple. The ratio of the terminal group described above can also be calculated in the same manner.

[0173] The degree of polymerization (the number of structural units) of the charge transporting polymer is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, from the viewpoint of stabilizing the film quality of the coating film. In addition, the degree of polymerization is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less, from the viewpoint of solubility in a solvent. The degree of polymerization can be determined as an average value using the mass average molecular weight of the charge transporting polymer, the molecular weight of the structural units, and the ratio of the structural units.

[0174] The charge transporting polymer of the above embodiment has a structure in which the structural unit B is bonded via at least the structural unit L1, and may further have a structure in which the structural unit L2 and the structural unit T are bonded, and the structural unit L1 forms a charge transporting polymer containing an N-Ph bond in the molecule. The charge transporting polymer containing an N-Ph bond tends to be easier to dope and conjugate than a charge transporting polymer containing a Ph-Ph bond formed by, for example, a method using Suzuki-Miyaura coupling. From this viewpoint, in one embodiment, the charge transporting polymer preferably has a partial structure represented by the following formula (i).

[0175] [ka]

[0176] From the viewpoint of easily introducing the partial structure represented by the above formula (i), it is preferable that the above structural unit B1 and the above structural unit L2 contain either a structure derived from a triphenylamine structure or a structure derived from an N-phenylcarbazole structure. In the above formula (i), n is an integer of 2 or more, and "*" represents a bonding site with another structure, preferably bonding to a phenyl group. In one embodiment, n is preferably an integer of 3 or more, more preferably an integer of 4 or more, and even more preferably an integer of 6 or more. Meanwhile, n may be preferably an integer of 3,000 or less, more preferably an integer of 1,500 or less, and even more preferably an integer of 500 or less. From the viewpoint of easily introducing the partial structure represented by the above formula (i), it is preferable that the above structural unit B1 and the optionally introduced structural unit L2 each contain either a structure derived from a triphenylamine structure or a structure derived from an N-phenylcarbazole structure.

[0177] In the charge transporting polymer, the content of N-Ph bonds formed by bonding each structural unit to each other may be preferably 10 to 80%, more preferably 20 to 70%, and further preferably 30 to 60%. Here, the above content is a value calculated from the amount of raw material monomer charged by performing NMR measurement, similar to the ratio of the structural units.

[0178] In the manufacturing method according to the above embodiment, at least an aromatic compound (A1) having three halogen atoms or triflate groups directly bonded to an aromatic ring and an aromatic compound (B1) having a primary amino group are used as raw material monomers to manufacture a branched polymer containing structural units derived from each compound. The structure of the aromatic compound (A1) is shown in the following formula A1, and the structure of the aromatic compound (B1) is shown in the following formula B1.

[0179] [ka] In the formula, Ar 1 and Ar 2 is as explained above. Q represents a halogen atom or a triflate group. Q is preferably a halogen atom, and more preferably a bromine atom.

[0180] By selecting an aromatic compound used as a raw material monomer, a branched polymer having two or more structures represented by the following formula (IA) can be easily obtained. [ka]

[0181] In the formula, Ar 1 and Ar 2is as explained above. n is an integer of 2 or more. n may be preferably 3 or more, more preferably 5 or more, and further preferably 10 or more. For example, n may be an integer that is appropriately set so that the weight average molecular weight (Mw) of the branched polymer is in the range of 1,000 or more and 500,000 or less, 2,000 or more and 500,000 or less, 3,000 or more and 500,000 or less, or 5,000 or more and 300,000 or less.

[0182] In the production method according to the above embodiment, the raw material monomer preferably further contains an aromatic compound (C) having one halogen atom or one triflate group directly bonded to an aromatic ring. In one embodiment, from the viewpoint of forming a branched polymer having a polymerizable functional group, the raw material monomer preferably further contains an aromatic compound represented by the following formula (C1). Q-Ar 3 -(X)a-(Y)bZ (C1) In each formula, Ar 3 X, Y, Z, a, and b are as described above. Q represents a halogen atom or a triflate group. Q is preferably a halogen atom, and more preferably a bromine atom.

[0183] In one embodiment, the branched polymer includes the structural units B1, L1, and T. Here, the structural unit T may be T1 and / or T2. In another embodiment, the branched polymer may further include the structural units B2 and / or L2 in addition to the structural units B1, L1, and T. In this case, an aromatic compound having a structure capable of inducing the additional structural unit and having a halogen atom or a triflate group directly bonded to the aromatic ring can be used as a raw material monomer. Similarly, an aromatic compound having two secondary amino groups in the molecule can also be used as a raw material monomer. In this way, a charge transporting polymer having a desired structure can be easily obtained by arbitrarily combining raw material monomers.

[0184] For example, in one embodiment, the raw material monomers that can be used to produce a polymer containing the structural units B1, L1, and T may include aromatic compounds (A1), (B1), and (C). In one embodiment, the raw material monomers may be a mixture consisting of only aromatic compounds (A1), (B1), and (C). When such a mixture is used as the raw material monomer, -(NAr-Ph) is formed without forming a Ph-Ph bond in the molecule. n It becomes possible to easily form a polymer having a -(n is an integer of 2 or more) structure. In one embodiment, the aromatic compound (C) preferably includes an aromatic compound (C1).

[0185] In another embodiment, the polymer may further include structural units B2 and / or L2. When these structural units are introduced, the raw material monomer may further include an aromatic compound having a halogen atom or a triflate group at the bonding site of these structural units. In another embodiment, in order to introduce the structural unit L2 into the polymer, a compound having a -NH-Ar group at the bonding site (*) of the structural unit L2 as shown in the following formula can also be used. Ar-NH-L2-NH-Ar In the formula, each Ar independently represents an aryl group or heteroaryl group having 2 to 30 carbon atoms.

[0186] According to the manufacturing method of the above embodiment, an arylamine polymer can be synthesized using the Buchwald-Hartwig reaction, and further separation and purification can be performed well, so that a polymer with few impurities can be obtained. The obtained polymer can be suitably used as an organic electronics material. Hereinafter, a representative embodiment using an arylamine polymer will be described.

[0187] One embodiment relates to an organic electronic material comprising the above-mentioned arylamine polymer as a charge transporting polymer. The content of the charge transporting polymer in the organic electronic material may be preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the organic electronic material. When the content of the charge transporting polymer is adjusted within the above range, excellent charge transportability can be easily obtained. In one embodiment, the content of the charge transporting polymer may be 100% by mass.

[0188] (Dopant) In one embodiment, an additive such as a dopant may be added in order to improve the charge transportability of the organic electronic material. When an additive such as a dopant is used, the content of the charge transporting polymer based on the total mass of the organic electronic material may be 95% or less, or may be 90% or less by mass.

[0189] The content of the dopant is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total mass of the organic electronic material. On the other hand, from the viewpoint of maintaining good film formability, the content of the dopant is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the organic electronic material.

[0190] From the viewpoint of applying a wet process as a film formation method, the organic electronic material preferably further contains a solvent. The organic electronic material may be configured as an ink composition (polymer solution) containing a charge transporting polymer and a solvent. The solvent used may be capable of dissolving the charge transporting polymer. By using an ink composition in which a charge transporting polymer is dissolved in a solvent, an organic layer can be easily formed by a simple method such as a wet process.

[0191] (solvent) As the solvent, any solvent medium can be used, such as water, an organic solvent, or a mixture thereof. As the organic solvent, alcohols such as methanol, ethanol, isopropyl alcohol, etc.; alkanes such as pentane, hexane, octane, etc.; cyclic alkanes such as cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, diphenylmethane, etc.; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate, etc.; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methylphenyl ether, etc.; Examples of the solvent include aromatic ethers such as methoxytoluene, 4-methoxytoluene, 3-phenoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, and methylene chloride. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers, and more preferred are aromatic hydrocarbons.

[0192] The content of the solvent in the organic electronic material (ink 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 charge transport polymer to the solvent is 0.1% by mass or more, more preferably such that the ratio is 0.2% by mass or more, and even more preferably such that the ratio is 0.5% by mass or more. The content of the solvent is preferably such that the ratio of the charge transport polymer to the solvent is 20% by mass or less, more preferably such that the ratio is 15% by mass or less, and even more preferably such that the ratio is 10% by mass or less.

[0193] In another embodiment, the organic electronic material may contain additives as optional components from the viewpoint of improving workability when forming an organic layer as an ink composition, further improving the function of the organic layer, etc. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reduction inhibitors, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, dispersants, surfactants, etc.

[0194] <Organic layer> One embodiment relates to an organic layer formed using the organic electronic material or the ink composition. The organic layer exhibits good charge transport properties. By using a polymer solution, an organic layer can be formed well and easily by a coating method. Examples of the coating method include known methods such as spin coating; casting; immersion; plate printing methods such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing, and gravure printing; and plateless printing methods such as inkjet printing. When the organic layer is formed by a coating method, the coating layer obtained after coating may be dried by heat treatment to remove the solvent.

[0195] The heat treatment can be carried out in an air atmosphere or an inert gas atmosphere. Examples of the inert gas include helium gas, argon gas, nitrogen gas, and mixtures thereof. The "inert gas atmosphere" is preferably an atmosphere in which the concentration of the inert gas is 99.5% or more by volume, more preferably 99.9% or more, and even more preferably 99.99% or more.

[0196] The heat treatment can be carried out using a heater such as a hot plate, an oven, etc. To carry out the heat treatment in an inert gas atmosphere, for example, a hot plate is used in an inert gas atmosphere, or the inside of an oven is made to be under an inert gas atmosphere.

[0197] From the viewpoint of efficiently removing the solvent, the heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent. In addition, when the polymerization reaction of the charge transporting polymer is to proceed, the temperature at which the polymerization reaction proceeds efficiently is preferable. In one embodiment, the temperature of the heat treatment is preferably 140°C or higher, more preferably 180°C or higher, and even more preferably 190°C or higher. On the other hand, from the viewpoint of suppressing deterioration due to the heat treatment, the temperature is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 250°C or lower.

[0198] The thickness of the organic layer after drying is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 3 nm or more, from the viewpoint of improving the efficiency of charge transport, and is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less, from the viewpoint of reducing the electrical resistance.

[0199] <Organic electronics elements> One embodiment relates to an organic electronics element having at least one of the organic layers. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor. The organic electronics element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes. The organic electronics element can be manufactured by a manufacturing method including forming an organic layer using the organic electronic material or the ink composition.

[0200] <Organic EL element> One embodiment relates to an organic EL device. The organic EL device has at least one of the organic layers. The organic EL device usually has a light-emitting layer, an anode, a cathode, and a substrate, and, if necessary, has other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. Each layer may be formed by a deposition method or a coating method. The organic EL device preferably has the organic layer as a light-emitting layer or other functional layer, more preferably has the organic layer as other functional layer, and further preferably has the organic layer as at least one of a hole injection layer and a hole transport layer.

[0201] Fig. 1 is a cross-sectional schematic diagram showing one embodiment of an organic EL element. The organic EL element in Fig. 1 has a multi-layer structure and includes a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, an emitting layer 1, an electron transport layer 7, an electron injection layer 5, and a cathode 4, in this order.

[0202] [Light-emitting layer] The light-emitting layer may be made of light-emitting materials such as low molecular weight compounds, polymers, and dendrimers. Polymers are preferred because they are highly soluble in solvents and suitable for coating methods. Light-emitting materials include fluorescent materials, phosphorescent materials, and thermally activated delayed fluorescent materials (TADF).

[0203] Examples of fluorescent materials include low molecular weight compounds such as perylene, coumarin, rubrene, quinacridone, stilbene, dyes for dye lasers, aluminum complexes, and derivatives thereof; polymers such as polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer, fluorene-triphenylamine copolymer, and derivatives thereof; and mixtures of these.

[0204] As the phosphorescent material, metal complexes containing metals such as Ir and Pt can be used. As an Ir complex, for example, FIr(pic) (iridium(III)bis[(4,6-difluorophenyl)-pyridinate-N,C], which emits blue light, can be used. 2 ]picolinate), which emits green light, Ir(ppy)3 (factris(2-phenylpyridine)iridium), which emits red light, and (btp)2Ir(acac) (bis[2-(2'-benzo[4,5-α]thienyl)pyridinato-N,C 3 ]iridium(acetylacetonate), Ir(piq)3 (tris(1-phenylisoquinoline)iridium), etc. Examples of Pt complexes include PtOEP (2,3,7,8,12,13,17,18-octaethyl-21H,23H-phorphine platinum) which emits red light, etc.

[0205] When the light-emitting layer contains a phosphorescent material, it is preferable that the light-emitting layer further contains a host material in addition to the phosphorescent material. As the host material, a low molecular weight compound, a polymer, or a dendrimer can be used. As the low molecular weight compound, for example, CBP (4,4'-bis(9H-carbazol-9-yl)biphenyl), mCP (1,3-bis(9-carbazolyl)benzene), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), their derivatives, etc., and as the polymer, the organic electronic material, polyvinylcarbazole, polyphenylene, polyfluorene, their derivatives, etc. can be mentioned.

[0206] Examples of thermally activated delayed fluorescence materials include PIC-TRZ (2-biphenyl-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine), Spiro-CN (2',7'-bis(di-P-tolylamino)-9,9'-spirobifluorene-s,7-dicarbonitrile), and CC2TA (2,4-bis{3-(9H-carbazol-9 -yl)-9H-carbazol-9-yl}-6-phenyl-1,3,5-triazine), CZ-PS(9,9'-(4,4'-sulfonylbis(4,1-phenylene))bis(3,6-di- tert-butyl-9H-carbazole)), 4CzPN(3,4,5,6-tetra(9H-carbazol-9-yl)phthalonitrile), HAP-3TPA(4,4',4''-(1,3,3a 1 ,4,6,7,9-heptaazaphenalene-2,5,8-triyl)tris(N,N-bis(4-(tert-butyl)phenyl)aniline)), 4CzIPN(1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), and other compounds.

[0207] [Hole injection layer, hole transport layer] The organic layer is preferably used as at least one of a hole injection layer and a hole transport layer. As described above, these layers can be easily formed by using an ink composition containing an organic electronic material and a solvent.

[0208] When the organic EL element has the organic layer as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer. When the organic EL element has the organic layer as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. Both the hole injection layer and the hole transport layer may be the organic layer. Examples of known materials include aromatic amine compounds (e.g., aromatic diamines such as N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (α-NPD)), phthalocyanine compounds, and thiophene compounds (e.g., thiophene conductive polymers such as poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)).

[0209] When the hole transport layer is an organic layer with a changed solubility, it is possible to easily form a light emitting layer on the hole transport layer by a wet process. In this case, the polymerization initiator may be contained in the organic layer that is the hole transport layer, or in the organic layer below the hole transport layer.

[0210] [Electron transport layer, electron injection layer] Examples of materials used for the electron transport layer and the electron injection layer include phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, condensed ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes, etc. The organic electronic materials described above can also be used.

[0211] [cathode] As the cathode material, for example, a metal or a metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, or CsF can be used.

[0212] [anode] The anode material may be, for example, a metal (e.g., Au) or another material having electrical conductivity, such as an oxide (e.g., ITO: indium oxide / tin oxide) or a conductive polymer (e.g., polythiophene-polystyrene sulfonate mixture (PEDOT:PSS)).

[0213] [substrate] The substrate may be made of glass, plastic, etc. The substrate is preferably transparent and flexible. Quartz glass, resin film, etc. are preferably used.

[0214] The resin film is preferably a light-transmitting resin film, such as a film mainly composed of polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, or the like.

[0215] When a resin film is used, the resin film may be coated with an inorganic material such as silicon oxide or silicon nitride in order to suppress the transmission of water vapor, oxygen, and the like.

[0216] [Sealing] The organic EL element may be sealed in order to reduce the influence of the outside air and extend the life. Materials used for sealing include glass, epoxy resin, acrylic resin, plastic films such as polyethylene terephthalate and polyethylene naphthalate, and inorganic materials such as silicon oxide and silicon nitride, but are not limited thereto. The sealing method is also not particularly limited, and can be performed by a known method.

[0217] [Emission color] The color of the emitted light from the organic EL element is not particularly limited. A white organic EL element is preferable because it can be used in various lighting fixtures such as home lighting, car lighting, clocks, and liquid crystal backlights.

[0218] A method for forming a white organic EL element can be a method in which multiple luminescent materials are used to simultaneously emit multiple luminescent colors and mix the colors. The combination of multiple luminescent colors is not particularly limited, but includes a combination containing three luminescent maximum wavelengths of blue, green, and red, and a combination containing two luminescent maximum wavelengths of blue and yellow, yellow-green and orange, etc. The luminescent color can be controlled by adjusting the type and amount of the luminescent material.

[0219] <Display elements, lighting devices, display devices> One embodiment relates to a display device including the organic EL element. For example, a color display device can be obtained by using organic EL elements as elements corresponding to each pixel of red, green, and blue (RGB). There are two methods for forming an image: a simple matrix type in which individual organic EL elements arranged on a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged in each element and driven.

[0220] One embodiment also relates to a lighting device including the organic EL element. Another embodiment also relates to a display device including the lighting device and a liquid crystal element as a display means. For example, the display device may be a display device using the lighting device as a backlight and a known liquid crystal element as a display means, i.e., a liquid crystal display device. EXAMPLES

[0221] The present invention will be described below with reference to examples, but the present invention is not limited to the following description.

[0222] <1> Polymer synthesis The raw material monomers used in the following Examples and Comparative Examples are shown below.

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] Example 1 A reaction vessel equipped with a Dimroth condenser and a stirring function was prepared, and an oil bath was placed so that it could move forward and backward relative to the reaction vessel. The following components were added to the reaction vessel, whose atmosphere had been replaced with nitrogen, while nitrogen was injected, and a nitrogen gas supply device was connected to the tip of the Dimroth condenser to create a reaction environment in a nitrogen atmosphere.

[0229] Starting monomers: Monomer A1 (1285 mg, 2.67 mmol), Monomer B3 (746 mg, 5.00 mmol), Monomer C1 (370 mg, 2.00 mmol) Organic solvent (toluene): Dehydrated toluene stored under nitrogen atmosphere, Fujifilm Wako Pure Chemical Industries, Ltd., 27.8 mL Base: sodium t-butoxide, manufactured by Tokyo Chemical Industry Co., Ltd., 1442 mg (3.0 equivalents (15 mmol) based on the monomer B3 having an amino group) Catalyst: Pd[P(t-Bu)3]2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 102 mg (4.0 mol % based on the monomer B3 having an amino group) Additive: P(t-Bu)3·HBF4, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 58 mg (4.0 mol % based on the amount of monomer B3 having an amino group)

[0230] Next, the reaction vessel was heated in an oil bath (bath temperature 120° C.) until the organic solvent in the reaction vessel refluxed, and the reaction was carried out for 2 hours with stirring. After the reaction, the temperature of the reaction solution in the reaction vessel was lowered to room temperature, and a suspended reaction solution was obtained.

[0231] On the other hand, sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in a water:methanol = 8:2 (volume ratio) solution and adjusted to 0.1 mol / L to obtain a solution containing sodium N,N-diethyldithiocarbamate trihydrate.

[0232] After the above reaction, 10 mL of the previously prepared solution containing sodium N,N-diethyldithiocarbamate trihydrate was added to approximately 30 mL of the suspended reaction solution, and the mixture was stirred to obtain a mixed solution. When the stirring was stopped, the mixed solution separated into an organic phase and an aqueous phase. The organic phase was then recovered from the separated mixed solution. The recovered organic phase (liquid) was reprecipitated using methanol-water (9:1), and the resulting precipitate was suction filtered.

[0233] Next, ethyl acetate was added to the obtained precipitate, and the precipitate was washed with ethyl acetate by stirring for 15 minutes while heating to 60°C in an oil bath. Next, the precipitate after washing was collected by suction filtration. The collected precipitate was washed once more with ethyl acetate in the same manner as above, and the remaining monomer and reactants soluble in ethyl acetate in the precipitate were removed. Next, the precipitate washed with ethyl acetate was dried under reduced pressure to obtain a polymer (light yellow powder).

[0234] Proton nuclear magnetic resonance of polymers ( 1By measuring the H-NMR spectrum, it was confirmed that the polymer had a structure obtained by polycondensation of monomers A1, B3, and C1. The polymer yield was 72%, the weight average molecular weight (Mw) was 47,500, the number average molecular weight (Mn) was 11,900, and the molecular weight distribution Mw / Mn was 4.0.

[0235] In addition, 1 The H-NMR spectrum was measured using an AVANCE-600 NMR spectrometer manufactured by Bruker. The Mw and Mn were measured using a Prominence GPC system manufactured by Shimadzu Corporation. The Mw and Mn were measured by gel permeation chromatography (GPC) using a styrene gel column, calibrated with standard polystyrene at 40° C., and then tetrahydrofuran was used as the eluent. The measurement conditions were as follows. The same applies to the examples and comparative examples described below.

[0236] Liquid delivery pump: L-6050 Hitachi High-Technologies Corporation UV-Vis Detector: L-3000 Hitachi High-Technologies Corporation Column: Gelpack (registered trademark) GL-A160S / GL-A150S, Resonac Inc. Eluent: THF (for HPLC, no stabilizers) Fujifilm Wako Pure Chemical Corporation Flow rate: 1ml / min Column temperature: room temperature Molecular weight standard: Standard polystyrene

[0237] (Examples 2 to 22) Polymers were produced in the same manner as in Example 1, except that the raw material monomers, blend amounts, and catalysts were changed as shown in Table 1. Next, a purified polymer was obtained in the same manner as in Example 1, except that the separation and purification conditions shown in Table 2 were applied to the obtained polymer.

[0238] (Comparative Examples 1 to 15) A polymer was produced in the same manner as in Example 1, except that the raw material monomers, blend amounts, and catalysts were changed as shown in Table 1. Next, a purified polymer was obtained in the same manner as in Example 1, except that the obtained polymer was subjected to the separation and purification conditions shown in Table 2. The separation and purification conditions were as follows.

[0239] In Comparative Examples 1 and 3, separation and purification itself was not performed. More specifically, after the above reaction, the temperature of the reaction solution in the reaction vessel was lowered to room temperature to obtain a suspended reaction solution. The reaction solution was mixed with water and stirred, resulting in a suspended mixture, which was difficult to separate. Therefore, the suspended mixture was re-precipitated using methanol-water (9:1). The precipitate was collected by suction filtration. Ethyl acetate was added to the collected precipitate, and the precipitate was washed with ethyl acetate by stirring for 15 minutes while heating at 60°C in an oil bath. The washed precipitate was then collected by suction filtration.

[0240] The collected precipitate was washed once more with ethyl acetate in the same manner as above to remove the remaining monomers and ethyl acetate-soluble reactants in the precipitate. The precipitate washed with ethyl acetate was then dried under reduced pressure to obtain a polymer (light yellow powder).

[0241] Methanol was not added during separation and purification in Comparative Examples 2 and 4 to 14. More specifically, after the above reaction, the temperature of the reaction solution in the reaction vessel was lowered to room temperature to obtain a suspended reaction solution. On the other hand, sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was mixed with water and adjusted to 0.1 mol / L to obtain an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate. After the reaction, 10 mL of the previously prepared aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate was added to the reaction mixture and stirred to obtain a mixed solution. The mixture obtained after stirring was in a suspended state, and separation was difficult. Therefore, the suspended mixture was reprecipitated using methanol-water (9:1), and the resulting precipitate was collected by suction filtration.

[0242] Ethyl acetate was added to the obtained precipitate, and the mixture was stirred for 15 minutes while being heated to 60°C in an oil bath, and the precipitate was washed with ethyl acetate. The washed precipitate was then collected by suction filtration. The washed precipitate was washed once more with ethyl acetate in the same manner as above, and the remaining monomers and reactants soluble in ethyl acetate in the precipitate were removed. The precipitate washed with ethyl acetate was then dried under reduced pressure to obtain a polymer (light yellow powder).

[0243] Details of the components used in the examples are as follows: Details of the components other than those described below are as explained above. (solvent) Anisole: Fujifilm Wako Pure Chemical (catalyst) Xphos Pd G2: Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium PdCl2(amphos)2: bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), manufactured by Aldrich Co., Ltd. PdArBrP(t-Bu)3: A compound represented by the following formula (2) (prepared by reacting tris(dibenzylideneacetone)dipalladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), o-bromotoluene (manufactured by Tokyo Chemical Industry Co., Ltd.), and tri-tert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)) [ka]

[0244] <2> Polymer properties (Method of analyzing impurity content) For each of the polymers obtained in the Examples and Comparative Examples, the contents of palladium (Pd), Br, and Cl as impurities in the polymer were measured. The measurements were performed using an energy dispersive X-ray fluorescence analyzer (hereinafter, EDX) under the following conditions. The results are shown in Table 2. In Table 2, "ND" stands for Not Detected, meaning that the content was below the detection limit.

[0245] Equipment: Shimadzu, EDX-7000 X-ray tube: Rh target Atmosphere:Atmospheric Measurement time (sec): Pd: 600, Br: 100, Cl: 1000 Analysis range (keV): Pd: 20.72-21.52, Br: 11.66-12.1 6. Cl: 2.42-2.82

[0246] [Table 1-1]

[0247] [Table 1-2]

[0248] [Table 2-1]

[0249] [Table 2-2]

[0250] As shown in Table 2, all of the reaction solutions after the coupling reaction were suspended, and when water was added, they became emulsions. In contrast, in the examples in which a water-soluble organic solvent such as methanol was added to the suspended reaction solution as a polymer separation and purification step, the emulsion state was eliminated, and the solution was easily separated into an organic phase and an aqueous phase. In addition, in the reaction solution separation and purification step, in comparison with Examples 1 to 22 in which methanol was added to the reaction solution and Comparative Examples 2 and 4 to 15 in which methanol was not added, it can be seen that the polymers of the examples have a significantly smaller amount of impurities. Therefore, according to the production method using a water-soluble organic solvent such as methanol, even if an emulsion is formed, it can be easily separated into an organic phase and an aqueous phase, and further, it can be seen that the amount of impurities derived from the components used during the reaction can be effectively reduced in the polymer recovered from the organic phase.

[0251] <3> Polymer properties (1) Fabrication of hole-only device (HOD) Ink compositions were prepared according to the methods described below using the arylamine polymers obtained in Example 6 and Comparative Example 2. Furthermore, HODs for evaluating electrical conductivity were prepared using the obtained ink compositions. The above arylamine polymer (50.0 mg) and the following ionic compound (1) (0.5 mg) were weighed out and placed in a 9 mL screw tube, and toluene (2449.5 mg) was added to dissolve them to prepare an ink composition. The above ink composition was filtered through a PTFE filter (pore size 0.2 μm).

[0252] [ka]

[0253] The filtered ink composition was dropped onto a quartz substrate (22 mm long x 29 mm wide x 0.7 mm thick, hereinafter referred to as ITO substrate) with ITO patterned to a width of 1.6 mm, and a film was formed using a spin coater. Then, the ink composition was cured and heated in a nitrogen atmosphere at 230°C for 30 minutes to form an organic layer (cured coating or dried coating) with a thickness of 60 nm on the ITO substrate.

[0254] The ITO substrates having the organic layers prepared as described above were transferred into a vacuum deposition machine, and aluminum (Al) was deposited to a thickness of 100 nm on the organic layers by a deposition method. A sealing process was then performed to prepare hole-only devices (hereinafter referred to as HODs) for evaluating electrical conductivity. FIG. 2 is a schematic cross-sectional view showing the structure of an HOD. As shown in FIG. 2, the HOD is a laminate having an anode 12, an organic layer (hole injection layer) 13, and a cathode 14 in this order on a substrate 11, and a sealing process (not shown) is performed to surround the laminate.

[0255] (2) Evaluation of HOD (2-1) Evaluation of electrical conductivity The voltage applied to the HODs for evaluating the electrical conductivity of Example 6 and Comparative Example 2 was measured. The results are shown in Table 3.

[0256] [Table 3]

[0257] In Table 3, details of items (1) and (2) are as follows: (1) Conductivity rating 1 The applied voltage was changed and the current density was 0.1 mA / cm 2 The voltage at this time was measured. (2) Conductivity rating 2 The applied voltage was changed to a current density of 20 mA / cm 2 The voltage at this time was measured.

[0258] (2-2) Evaluation of hole density Using the HODs for evaluating electrical conductivity of Example 1 and Comparative Example 2 prepared above, the hole density was evaluated by the method described below. (Evaluation method) Information on the hole density can be obtained by impedance spectroscopy (hereinafter, IS method). Specifically, the ITO and Al electrodes of the HODs of Example 6 and Comparative Example 2 were connected to an LCR meter under the following conditions. Then, the frequency dependence of the impedance of the HODs was measured and analyzed, and the hole density was calculated.

[0259] <Measurement conditions> Measuring device: LCR meter (NF Circuit Block, ZM2376) Frequency range: 0.1Hz~5.5MHz AC amplitude: 100mV

[0260] <How to calculate hole density> Assuming that the organic layer has an electrical resistance "R" and a capacitance "C", and approximating it with a parallel circuit model, the complex impedances "Z1 (Equation 1)" and "Z2 (Equation 2)" of the circuit model are obtained as shown below.

[0261]

number

[0262] In addition, in the analysis of the frequency dependency of impedance, the moduli "M1 (Equation 3)" and "M2 (Equation 4)" were used as shown below.

[0263]

number

[0264] The resistance and capacitance of each organic layer can be obtained by the relationship between the observed peaks and heights of "M1" and "M2" as shown in (Formula 6) and (Formula 7) below.

[0265]

number

[0266] In HOD doped with holes by an ionic compound (polymerization initiator), the holes move so that the HOMO level matches the work function of the metal at the interface with the metal, forming a depletion layer with a thickness of "d". At this time, the capacitance "C" and thickness "d" of the depletion layer are given by (Equation 7) as shown below.

[0267]

number

[0268] Furthermore, if the thickness of the depletion layer "d" is the space charge density (anion density) in the depletion layer "N", then when no bias voltage is applied, it is expressed by the following (Equation 8). Here, since the anion density "N" and the hole density are equal, the hole density can be calculated using (Equation 8).

[0269]

number

[0270] (Evaluation results of hole density) According to the above method, the hole density of the HODs prepared using the organic electronic materials (ink compositions) of Example 6 and Comparative Example 2 was calculated. In addition, a relative value was calculated with the hole density obtained with the ink composition of Comparative Example 2 as the reference (100). The results are shown in 4.

[0271] [Table 4]

[0272] As is clear from Table 4, the hole density of the organic electronic material (Example 6) containing the polymer obtained by the manufacturing method of this embodiment is far superior to that of Comparative Example 2. This shows that the manufacturing method of this embodiment can effectively reduce the amount of impurities in the polymer, thereby providing a polymer that can be suitably used as an organic electronic material. Therefore, it is possible to provide an organic electronic material that can easily form an organic layer that can improve conductivity and hole density by using the above polymer. [Explanation of symbols]

[0273] 1. Light-emitting layer 2 Anode 3. Hole injection layer 4 cathode 5 Electron injection layer 6. Hole transport layer 7 Electron transport layer 8 Substrate 11 Substrate 12 Anode 13 Organic layer (hole injection layer) 14 Cathode

Claims

1. a reaction of raw material monomers including an aromatic compound (A) having two or more halogen atoms or triflate groups directly bonded to an aromatic ring and an aromatic compound (B) having an amino group in the presence of a palladium-containing catalyst and a non-water-soluble organic solvent to obtain a reaction liquid including an arylamine polymer; obtaining a mixed solution of the reaction solution, water, and a water-soluble organic solvent that is compatible with the water-insoluble organic solvent; separating the mixture into an organic phase and an aqueous phase; and recovering said organic phase. A method for producing an arylamine polymer, comprising:

2. The method according to claim 1 , wherein the arylamine polymer has at least a branched structure represented by the following formula (I): 【Chemistry 1】 [In the formula, Ar １ represents a trivalent organic group derived from an aromatic hydrocarbon or aromatic heterocycle having 2 to 30 carbon atoms, or a triarylamine; Ar ２ represents an aryl group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, and * represents a bonding site with another structure.]

3. In the formula (I), Ar ２ The method according to claim 2, wherein the compound has a structure represented by the following formula (b-1): 【Chemistry 2】 [In the formula, R １ is an alkyl group having 1 to 12 carbon atoms, an electron-withdrawing group, or an electron-donating group, and a is an integer of 0 to 5.

4. 3. The production method according to claim 1 or 2, wherein the raw material monomer further comprises an aromatic compound (C), and the aromatic compound (C) has one halogen atom or one triflate group directly bonded to an aromatic ring, and a polymerizable functional group.

5. The method according to claim 1 or 2, further comprising using a base in the reaction of the raw material monomers.

6. The process of claim 5 , wherein the base comprises an organoalkali metal compound.

7. The method according to claim 1 or 2, further comprising adding a heavy metal scavenger to the mixed solution.

8. The method according to claim 1 or 2, wherein the water-soluble organic solvent comprises an alcohol.

9. The method according to claim 1 or 2, wherein the non-water-soluble organic solvent comprises an aromatic hydrocarbon solvent.

10. The palladium-containing catalyst is bis(di-t-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II), bis(tri-t-butylphosphine)palladium(0), PdArBrP(t-Bu), ３ (wherein Ar represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms), and chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium. The method according to claim 1 or 2,

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