Organic electronic materials and organic electronic elements

Abstract

To provide an organic electronics material capable of forming an organic layer with excellent solvent resistance. [Solution] An organic electronics material containing a charge-transporting branched polymer that includes structural units having a spirofluorene structure.

Description

Technical Field

[0001] Embodiments of the present invention relate to organic electronic materials, organic electronic devices, organic electroluminescent devices (organic EL devices), and organic photoelectric conversion devices.

Background Art

[0002] An organic electronic device is a device that performs electrical operations using organic materials and is expected to exhibit features such as energy savings, low cost, and flexibility. In an organic electronic device, a plurality of organic layers may be provided for the purpose of improving device characteristics.

[0003] As a method for forming a plurality of organic layers by a wet process, a method using a compound having a polymerizable group is known. Patent Document 1 describes an organic electroluminescent device having a cathode and an anode on a substrate and a plurality of organic layers therebetween, wherein at least one of the organic layers is a layer containing an organic molecule having 10 or less repeating units obtained by coating and polymerizing a compound having at least one polymerizable group.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An embodiment of the present invention aims to provide an organic electronic material capable of forming an organic layer having excellent solvent resistance. Another embodiment of the present invention aims to provide an organic electronic device, an organic electroluminescent device, and an organic photoelectric conversion device including an organic layer having excellent solvent resistance. [Means for solving the problem]

[0006] The present invention includes, but is not limited to, the following embodiments. (1) An organic electronics material containing a charge-transporting branched polymer that includes structural units having a spirofluorene structure. (2) The organic electronic material according to (1), wherein the structural unit having the spirofluorene structure includes a structural unit represented by the following formula (1-1). [ka] (In the formula, R represents an independent substituent, n represents an independent integer between 0 and 3, and * represents a bonding site with another structural unit.) (3) The organic electronics material according to (1) or (2), wherein the charge-transporting branched polymer has polymerizable functional groups. (4) The organic electronic material according to any one of (1) to (3), wherein the polymerizable functional group includes a group having a carbon-carbon multiple bond. (5) The organic electronic material according to any one of (1) to (4) above, wherein the charge-transporting branched polymer includes a structural unit represented by the following formula (3-2). [ka] (In the formula, R represents an independent substituent, n represents an integer from 0 to 3, and * represents a bonding site with another structural unit.) (6) The organic electronic material according to any one of (1) to (5), wherein the charge-transporting branched polymer includes at least one selected from the group consisting of structural units represented by the following formula (3-1) and structural units represented by the following formula (3-2). [ka] (In the formula, n represents an independent integer between 0 and 3, and * represents a bonding site with another structural unit.) [ka] (In the formula, n independently represents an integer of 0 to 3, and * represents a bonding site with other structural units.) (7) The charge-transporting branched polymer is the organic electronics material according to any one of (1) to (6) above, which has an alkoxy group. (8) The organic electronics material according to any one of (1) to (7) above, which is for a hole injection / transport layer. (9) The organic electronics material according to any one of (1) to (8) above, which is for an organic electroluminescence device or a perovskite solar cell. (10) An organic electronics device including an organic layer formed using the organic electronics material according to any one of (1) to (9) above. (11) An organic electroluminescence device including an organic layer formed using the organic electronics material according to any one of (1) to (9) above. (12) An organic optoelectronic conversion device including an organic layer formed using the organic electronics material according to any one of (1) to (9) above.

Advantages of the Invention

[0007] According to an embodiment of the present invention, an organic electronics material capable of forming an organic layer having excellent solvent resistance can be provided. Further, according to another embodiment of the present invention, an organic electronics material, an organic electronics device, an organic electroluminescence device, and an organic optoelectronic conversion device including an organic layer having excellent solvent resistance can be provided.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device. [Figure 2] FIG. 2 is a schematic cross-sectional view showing a hole-only device for conductivity evaluation fabricated in an example.

Modes for Carrying Out the Invention

[0009] Embodiments of the present invention will be described. The present invention is not limited to the following embodiments. The following embodiments can be implemented alone or in combination. Combinations of multiple embodiments are also included in the present invention. In the present disclosure, a numerical range indicated using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In a numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value of a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. The upper limit value or the lower limit value of a numerical range described in the present disclosure may be replaced with the value shown in the examples. From the upper limit numerical value and the lower limit numerical value described stepwise in the present disclosure, a certain numerical value may be selected respectively to form a stepwise numerical range. The upper limit numerical value and the lower limit numerical value described in the present disclosure may be replaced with the values shown in the examples. In the present disclosure, unless otherwise specified, "including A or B" means that either one of A and B may be included, or both may be included. In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, each structure in the polymer may contain a plurality of corresponding structures. When there are a plurality of structures corresponding to each structure in the polymer, the content rate or content of each structure means the total content rate or content of the plurality of structures present in the polymer, unless otherwise specified. In the present disclosure, "layer" includes a continuous layer and a discontinuous layer. The thickness of the "layer" may be uniform or non-uniform. The outer edge in the plane direction and the outer edge in the thickness direction of the "layer" may be clear or unclear, respectively. The same applies to "film".

[0010] <organic electronic material> In embodiments of the present invention, the organic electronic material contains a charge-transporting branched polymer comprising structural units having a spirofluorene structure. The organic electronic material may further contain any components such as dopants and polymerization initiators.

[0011] [Charge-transporting branched polymer] A charge-transporting branched polymer contains at least structural units having a spirofluorene structure. The charge-transporting branched polymer may further contain structural units without a spirofluorene structure, polymerizable functional groups, substituents, etc. A charge-transporting branched polymer is a branched polymer containing branching points in its polymer chain. In embodiments of the present invention, "charge-transporting branched polymer" may be referred to simply as "charge-transporting polymer."

[0012] (Structural units having a spirofluorene structure) The spirofluorene structure may be a substituted spirofluorene structure or an unsubstituted spirofluorene structure. The structural unit having a spirofluorene structure may be a 1-4 valent structural unit having 1-4 bonding sites with other structural units. The trivalent or tetravalent structural unit is a branched unit.

[0013] If the spirofluorene structure has substituents, examples of substituents include alkyl groups, aryl groups, halogen groups, halogen-substituted alkyl groups, nitro groups, cyano groups, sulfonic acid groups, sulfoxide groups, amino groups, hydroxyl groups, alkoxy groups, thio groups, alkylthio groups, trialkylsilyl groups, and groups containing polymerizable functional groups. The alkyl groups included in the substituents may be linear, branched, or cyclic. The spirofluorene structure may be an unsubstituted spirofluorene structure.

[0014] According to embodiments of the present invention, an organic layer formed using an organic electronics material has excellent solvent resistance. The charge-transporting polymer contains a twisted structure within its molecule due to having a spirofluorene structure. In particular, when the structural unit having a spirofluorene structure is a branched unit, the polymer molecular chains are orthogonal to each other starting from the spiro atom. This is presumed to cause entanglement of molecular chains within and between polymer molecules, resulting in the organic layer having excellent solvent resistance. By using a charge-transporting polymer containing a structural unit having a spirofluorene structure, for example, an organic layer with excellent solvent resistance can be formed by heating at a low temperature of 150°C or less, even if the charge-transporting polymer does not contain polymerizable functional groups. Furthermore, if the charge-transporting polymer contains polymerizable functional groups, an organic layer with even better heat resistance can be obtained. However, the present invention is not limited by these presumptions.

[0015] If an organic layer has excellent solvent resistance, it is possible to prevent the lower layer from dissolving in the solvent when another organic layer (upper layer) is formed on top of it using a wet process. By suppressing the dissolution of the lower layer, it is possible to prevent the two materials from mixing when forming the upper layer, making it possible to form multiple adjacent organic layers in good condition. By preventing mixing and forming organic layers in good condition, it is possible to prevent an increase in the driving voltage of organic electronic elements, a decrease in the efficiency of active layers such as light-emitting layers and photoelectric conversion layers, and a decrease in lifespan. An example of an organic layer (lower layer) is a hole transport layer, and an example of an organic layer (upper layer) is a light-emitting layer.

[0016] Examples of structural units having a spirofluorene structure include the structural unit represented by the following formula (1). [ka]

[0017] In the formula, A independently represents a hydrogen atom, a substituent, or a bonding site to another structural unit. At least one of A is a bonding site to another structural unit.

[0018] Examples of substituents are as described above. The number of substituents may be 0-8, 0-4, 0-2, or 0. The R atoms that are not bonded to other structural units or substituents are hydrogen atoms. The number of hydrogen atoms may be 0-15, 4-14, or 8-12.

[0019] At least one of R is a binding site to another structural unit. The number of binding sites may be 1 to 4, 2 to 4, or 4. That is, the structural unit represented by formula (1) may be 1 to 4-valent, 2 to 4-valent, or 4-valent.

[0020] The charge-transport polymer includes, for example, at least one selected from the structural units represented by formulas (1-1) to (1-3) below, and preferably includes the structural unit represented by formula (1-1). Using a charge-transport polymer containing the structural unit represented by formula (1-1) below allows for the formation of an layer with better solvent resistance. [ka]

[0021] In formulas (1-1) to (1-3), R represents an independent substituent, n represents an independent integer from 0 to 3, and * represents a bonding site with another structural unit. Examples of substituents are as described above. If multiple Rs exist, they may be the same or different from each other.

[0022] The structural unit having a spirofluorene structure preferably includes a structural unit represented by the following formula. [ka]

[0023] In the formula, * represents a bonding site with another structural unit.

[0024] (Structural units that do not have a spirofluorene structure) The charge-transport polymer may contain structural units that do not have a spirofluorene structure. In embodiments of the present invention, "structural units that do not have a spirofluorene structure" may be referred to as "any structural unit." Any structural unit may be, for example, a substituted or unsubstituted aromatic amine structure, a substituted or unsubstituted carbazole structure, a substituted or unsubstituted thiophene structure, a substituted or unsubstituted fluorene structure, a substituted or unsubstituted benzene structure, a substituted or unsubstituted biphenyl structure, a substituted or unsubstituted terphenyl structure, a substituted or unsubstituted naphthalene structure, a substituted or unsubstituted anthracene structure, a substituted or unsubstituted tetracene structure, a substituted or unsubstituted phenanthrene structure, a substituted or unsubstituted dihydrophenanthrene structure, a substituted or unsubstituted pyridine structure, a substituted or unsubstituted pyrazine structure, a substituted or unsubstituted quinoline structure, a substituted or unsubstituted isoquinoline structure, a substituted or unsubstituted quinoxaline structure, or a substituted or unsubstituted A structural unit is selected from a substituted acridine structure, a substituted or unsubstituted diazaphenanthrene structure, a substituted or unsubstituted furan structure, a substituted or unsubstituted pyrrole structure, a substituted or unsubstituted oxazole structure, a substituted or unsubstituted oxadiazole structure, a substituted or unsubstituted thiazole structure, a substituted or unsubstituted thiadiazole structure, a substituted or unsubstituted triazole structure, a substituted or unsubstituted benzothiophene structure, a substituted or unsubstituted benzoxazole structure, a substituted or unsubstituted benzoxadiazole structure, a substituted or unsubstituted benzothiazole structure, a substituted or unsubstituted benzothiadiazole structure, a substituted or unsubstituted benzotriazole structure, and structural units having one or more of these.

[0025] Any structural unit preferably includes at least one selected from the group consisting of structural units having a substituted or unsubstituted aromatic amine structure, structural units having a substituted or unsubstituted carbazole structure, and structural units having a substituted or unsubstituted benzene structure, and more preferably includes structural units having a substituted or unsubstituted aromatic amine structure and structural units having a substituted or unsubstituted benzene structure. Examples of structural units having a substituted or unsubstituted aromatic amine structure include structural units having a substituted or unsubstituted triarylamine structure, structural units having a substituted or unsubstituted diarylamine structure, and structural units having a substituted or unsubstituted monoarylamine structure.

[0026] Any structural unit may be monovalent or more, preferably 1 to 6-valent, and more preferably 1 to 4-valent. Examples of substituents included in any structural unit include alkyl groups, aryl groups, halogen groups, halogen-substituted alkyl groups, nitro groups, cyano groups, sulfonic acid groups, sulfoxide groups, amino groups, hydroxyl groups, alkoxy groups, thio groups, alkylthio groups, trialkylsilyl groups, and groups containing polymerizable functional groups. The alkyl group included in the substituent may be linear, branched, or cyclic. The alkyl group included in the substituent may be, for example, an alkyl group included in a substituent such as an alkyl group, a halogen-substituted alkyl group, or an alkoxy group.

[0027] For example, the charge-transport polymer includes structural units having a spirofluorene structure, structural units having a triarylamine structure, and structural units having a benzene structure, preferably including tetravalent structural units having a spirofluorene structure, divalent structural units having a triarylamine structure, and monovalent structural units having a benzene structure. The charge-transport polymer may contain a ">N-Ar-spirofluorene structure-Ar-N<" structure (Ar is the aryl group in the triarylamine structure) in the polymer chain. For example, the charge-transport polymer includes structural units having a spirofluorene structure, structural units having a monoarylamine structure, and structural units having a benzene structure, preferably including tetravalent structural units having a spirofluorene structure, divalent structural units having a monoarylamine structure, and monovalent structural units having a benzene structure. The charge-transport polymer may contain a ">N-spirofluorene structure-N<" structure in the polymer chain. When a charge-transporting polymer contains structural units having a triarylamine structure or a monoarylamine structure, good charge transport properties are easily obtained. When a charge-transporting polymer contains structural units having a monoarylamine structure, good solubility of the charge-transporting polymer in solvents and good solvent resistance of the organic layer are easily obtained.

[0028] A structural unit having a triarylamine structure may be, for example, a structural unit represented by the following formula (2-1). [ka]

[0029] In the formula, each R independently represents a substituent, n represents an integer from 0 to 3, and * represents a bonding site with another structural unit. Examples of substituents are as described above. If multiple Rs exist, they may be the same or different from each other.

[0030] The structural unit having a triarylamine structure preferably includes a structural unit represented by the following formula (2-1a). [ka]

[0031] In the formula, R 1 * represents an alkyl group, and * represents a bonding site with other structural units.

[0032] The alkyl group may have 1 to 22 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably linear.

[0033] Charge-transport polymers containing the structural unit represented by formula (2-1a) contain an "alkyl-O-benzene ring-N<" structure and tend to exhibit excellent conductivity when adjusted to an appropriate HOMO level with an electron-donating group. In addition to electron-donating groups, electron-withdrawing groups may also be used as a method to adjust to an appropriate HOMO level.

[0034] A structural unit having a monoarylamine structure may be, for example, a structural unit represented by the following formula (2-2). [ka]

[0035] In the formula, each R independently represents a substituent, n represents an integer from 0 to 3, and * represents a bonding site with another structural unit. Examples of substituents are as described above. If multiple Rs exist, they may be the same or different from each other.

[0036] The structural unit having a monoarylamine structure preferably includes a structural unit represented by the following formula (2-2a). [ka]

[0037] In the formula, R 1 * represents an alkyl group, and * represents a bonding site with other structural units.

[0038] The alkyl group may have 1 to 22 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, and is preferably linear.

[0039] Charge-transport polymers containing the structural unit represented by formula (2-2a) tend to exhibit excellent conductivity when adjusted to an appropriate HOMO level with an electron-donating group, due to the presence of the "alkyl-O-benzene ring-N<" structure. In addition to electron-donating groups, electron-withdrawing groups may also be used as a method for adjusting to an appropriate HOMO level.

[0040] A structural unit having a benzene structure may be, for example, a structural unit represented by the following formula (3). [ka]

[0041] In the formula, each R independently represents a substituent, n represents an integer from 0 to 3, and * represents a bonding site with another structural unit. Examples of substituents are as described above. If multiple Rs exist, they may be the same or different from each other.

[0042] A structural unit having a benzene structure includes, for example, at least one structural unit selected from the group consisting of structural units represented by formula (3-1) to structural units represented by formula (3-3), and preferably includes at least one structural unit selected from the group consisting of structural units represented by formula (3-1) and structural units represented by formula (3-2), and a structural unit represented by formula (3-3). [ka]

[0043] In the formula, n represents an integer between 3 and 17, and * represents a bonding site with other structural units. [ka]

[0044] In the formula, n represents an integer between 3 and 17, and * represents a bonding site with other structural units.

[0045] When the charge-transport polymer contains structural units represented by formula (3-1) or formula (3-2), superior solvent resistance tends to be obtained. From the viewpoint of solvent resistance and film-forming properties, n is preferably 4 to 18, and more preferably 4 to 8. When the charge-transport polymer contains structural units represented by formula (3-1) or formula (3-2), it is presumed that the solvent resistance of the organic layer is further improved by the entanglement of alkyl groups or alkoxy groups. Furthermore, when the charge-transport polymer contains structural units represented by formula (3-1) or formula (3-2), it is thought that the solubility of the charge-transport polymer in the solvent is improved when the organic layer is formed in a wet process, thus improving film-forming properties. However, the present invention is not limited by these presumptions.

[0046] [ka]

[0047] In the formula, Vinyl represents a substituted or unsubstituted vinyl group, L represents a direct bond or linking group, and * represents a bonding site with another structural unit.

[0048] Examples of linking groups include alkylene groups, sulfinyl groups (*-SO-*), sulfonyl groups (*-SO2-*), imino groups (*-NH-*), oxy groups (*-O-*), carbonyl groups (*-CO-*), and groups containing two or more selected from these. The number of carbon atoms in the alkylene group is, for example, 1 to 18. The alkylene group may be linear, branched, or cyclic, and is preferably a linear alkylene group. In formula (3-2), when L is a direct bond, the vinyl group is directly bonded to the benzene ring. That is, the structural unit represented by formula (3-3) is *-Ph-Vinyl (Ph is the benzene ring).

[0049] When L is directly bonded, organic electronic devices tend to exhibit good lifetime characteristics. When L is a linear alkylene group having 4 to 18 carbon atoms, or a group containing a linear alkylene group having 4 to 18 carbon atoms and an oxy group, charge-transport polymers tend to exhibit good solubility in solvents in wet processes.

[0050] When a charge-transporting polymer contains structural units represented by formula (3-1) and structural units represented by formula (3-3), the content of structural units represented by formula (3-1) and structural units represented by formula (3-3) are, for example, 30-95 mol%:70-5 mol%, 40-85 mol%:60-15 mol%, or 50-75 mol%:25-50 mol%, with the total content of both being 100 mol%. When a charge-transporting polymer contains structural units represented by formula (3-2) and structural units represented by formula (3-3), the content of structural units represented by formula (3-2) and structural units represented by formula (3-3) are, for example, 30-95 mol%:70-5 mol%, 40-85 mol%:60-15 mol%, or 50-75 mol%:25-50 mol%, with the total content of both being 100 mol%.

[0051] (Polymerizable functional group) The charge-transporting polymer may have polymerizable functional groups. In the charge-transporting polymer, it is preferable that structural units having polymerizable functional groups are included at the ends of the polymer chain. Because the charge-transporting polymer has polymerizable functional groups, it exhibits curability, and thus the solvent resistance of the resulting organic layer is improved.

[0052] Examples of polymerizable functional groups include substituted or unsubstituted carbon-carbon multiple bonded groups (e.g., vinyl group, styryl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino group, vinyloxy group, vinylamino group), substituted or unsubstituted cyclic alkyl groups (e.g., cyclopropyl group, benzocyclobutenyl group, cyclobutyl group), substituted or unsubstituted cyclic ether structures (e.g., epoxy group (oxyranyl group), oxetane group (oxetanyl group)), and fused ring groups of substituted or unsubstituted cyclic alkyl groups and benzene rings (benzocyclobutene group). When these groups are substituted, the substituents are not particularly limited, but examples include linear, branched, or cyclic alkyl groups. The number of carbon atoms in the alkyl group is more preferably 1 to 10, and even more preferably 1 to 4.

[0053] From the viewpoint of curability, for example, the polymerizable functional group preferably contains a group having a carbon-carbon multiple bond, and more preferably contains a vinyl group. Alternatively, the charge transport polymer does not need to have a polymerizable functional group. Since the charge transport polymer contains a spirofluorene structure, an organic layer with good solvent resistance can be formed even without a polymerizable functional group. Charge transport polymers without polymerizable functional groups are easy to synthesize and tend to have good storage stability.

[0054] (alkoxy group) The charge-transport polymer may have an alkoxy group. The number of carbon atoms in the alkoxy group may be, for example, 1 to 18, 1 to 12, 2 to 8, or 4 to 6. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic alkyl groups.

[0055] Examples of alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, and 3,7-dimethyloctyl group; and cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. The alkyl group may be, for example, a linear alkyl group, a linear alkyl group having 2 to 8 carbon atoms, or an ethyl group, an n-propyl group, or an n-butyl group.

[0056] (Content of each structural unit) The charge-transport polymer contains, for example, 10-30 mol%, 15-25 mol%, or 17-20 mol% of structural units having a spirofluorene structure, based on the total number of structural units, from the viewpoint of solvent resistance of the organic layer. Considering conductivity, the content of the spirofluorene structure may be, for example, 5-25 mol%, 5-20 mol%, or 10-15 mol%, and the charge-transport polymer contains, for example, 70-90 mol%, 75-85 mol%, or 80-83 mol% of arbitrary structural units, based on the total number of structural units.

[0057] The charge-transport polymer contains, for example, 2 to 45 mol%, 5 to 40 mol%, or 25 to 35 mol% of structural units having polymerizable functional groups, based on the total number of structural units. When the content of structural units having polymerizable functional groups is 2 mol% or more, the solvent resistance of the organic layer tends to improve further. The content of structural units having polymerizable functional groups may also be, for example, less than 5 mol%, less than 3 mol%, or less than 1 mol%.

[0058] Charge-transporting polymers, for example, contain structural units having linear alkyl groups in amounts of 10-40 mol%, 15-35 mol%, or 15-25 mol% relative to the total number of structural units. When the content of structural units having linear alkyl groups is 5 mol% or more, better solvent resistance tends to be obtained. Charge-transporting polymers, for example, contain structural units having linear alkoxy groups in amounts of 30-60 mol%, 35-55 mol%, or 40-50 mol% relative to the total number of structural units. When the content of structural units having linear alkoxy groups is 30 mol% or more, superior solvent resistance tends to be obtained.

[0059] Charge-transporting polymers, for example, contain structural units having an aromatic amine structure in amounts of 40-65 mol%, 45-60 mol%, or 50-55 mol% relative to the total number of structural units. When the content of structural units having an aromatic amine structure is 40 mol% or more, excellent charge transport properties tend to be obtained.

[0060] The content of structural units can be determined using the amount of monomer corresponding to each structural unit used to synthesize the charge-transport polymer. Furthermore, the proportion of structural units in the charge-transport polymer is determined by the amount of monomer used for each structural unit. 1 The average value can be calculated by using the integral values ​​of the spectra derived from each structural unit in the 1H NMR spectrum. Because it is simple, if the amount used is known, it is preferable to use the value obtained using the amount used.

[0061] (number average molecular weight) The number-average molecular weight of the charge-transport polymer can be adjusted as appropriate, taking into consideration its solubility in solvents, film-forming properties, etc. From the viewpoint of excellent solvent resistance and charge transport properties, the number-average molecular weight may be 8,000 or more, 10,000 or more, or 15,000 or more. From the viewpoint of maintaining good solubility of the charge-transport polymer in solvents and facilitating the preparation of liquid compositions, the number-average molecular weight may be 50,000 or less, 30,000 or less, or 20,000 or less.

[0062] (Weight average molecular weight) The weight-average molecular weight of the charge-transport polymer can be adjusted as appropriate, taking into consideration its solubility in solvents, film-forming properties, etc. From the viewpoint of excellent solvent resistance and charge transport properties, the weight-average molecular weight may be 30,000 or more, 50,000 or more, 60,000 or more, or 100,000 or more. From the viewpoint of maintaining good solubility of the charge-transport polymer in solvents and facilitating the preparation of liquid compositions, the weight-average molecular weight may be 500,000 or less, 300,000 or less, 200,000 or less, or 100,000 or less.

[0063] The number-average molecular weight and weight-average molecular weight can be measured by gel permeation chromatography (GPC) using a calibration curve for standard polystyrene. Examples of measurement conditions include those described in the examples.

[0064] (Method for producing charge-transport polymers) Charge-transport polymers can be produced using monomers containing structural units having a spirofluorene structure, and monomers containing any structural unit as needed. Examples of optional monomers include monomers containing structural units having a triarylamine structure, monomers containing structural units having a monoarylamine structure, and monomers containing structural units having a benzene structure. In the method for producing charge-transport polymers, for example, monomers are polymerized by a coupling reaction. The monomers may include polyfunctional monomers with three or more functions, difunctional monomers, and monofunctional monomers.

[0065] For example, a charge-transport polymer can be obtained using a monomer comprising a structural unit having a spirofluorene structure, a monomer comprising a structural unit having a triarylamine structure, and a monomer comprising a structural unit having a benzene structure. Preferably, it can be obtained using a monomer comprising a tetrafunctional monomer comprising a structural unit having a spirofluorene structure, a difunctional monomer comprising a structural unit having a triarylamine structure, and a monofunctional monomer comprising a structural unit having a benzene structure.

[0066] As coupling reactions, known reactions such as the Suzuki-Miyaura coupling, Negishi coupling, Sonogashira coupling, Still coupling, and Buchwald-Hartwig coupling can be used. The Suzuki-Miyaura coupling involves, for example, a cross-coupling reaction using a Pd catalyst between an aromatic boronic acid compound or aromatic boronic acid ester compound and an aromatic halogen compound. The Suzuki-Miyaura coupling allows for the simple production of charge-transporting polymers by bonding desired aromatic rings. The Buchwald-Hartwig coupling involves, for example, a cross-coupling reaction using a Pd catalyst between an aromatic halogen compound and an aromatic amine compound. The Buchwald-Hartwig coupling allows for the simple production of charge-transporting polymers by bonding desired aromatic rings and amino groups. Examples of reactive functional groups in coupling reactions include bromo groups, boronic acid groups, boronic acid ester groups, and amino groups. For example, charge-transporting polymers include polymers produced by the Suzuki-Miyaura coupling. For example, charge-transporting polymers include polymers formed by Buchwald-Hartwig coupling.

[0067] In the Suzuki-Miyaura coupling reaction, catalysts such as Pd(O) compounds, Pd(II) compounds, Ni compounds, and Ru compounds are used. Alternatively, catalyst species generated by mixing tris(dibenzylideneacetone)dipalladium(O) and palladium(II) acetate as precursors with phosphine ligands in the reaction system can be used. Organic solvents are used as reaction solvents, and a mixed solvent of water and the organic solvent is preferred. Examples of organic solvents include aromatic ethers such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, and diphenylmethane; and tetrahydrofuran, acetone, acetonitrile, and N,N-dimethylformamide. In the reaction, alkali metal carbonates, alkali metal hydroxides, alkali metal phosphates, and water-soluble organic bases can also be used as bases. The reaction can also be accelerated by adding a phase-transfer catalyst.

[0068] In the Buchwald-Hartwig coupling, a palladium-containing catalyst can be suitably used as the catalyst. The palladium-containing catalyst may be a catalyst containing palladium and a ligand, and may be 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 ligand precursor.

[0069] Ligands with a bulky structure are preferred, with phosphine ligands and Buchwald ligands being specific examples. The ligand may also be an N-heterocyclic carbene (NHC). Among these, phosphine ligands such as tri-t-butylphosphine, tri-o-tolylphosphine, and triphenylphosphine are more preferred.

[0070] The palladium-containing catalyst may be a palladium(O) complex or a palladium(II) salt. Specific examples of palladium-containing catalysts include bis(tri-t-butylphosphine)palladium(O), tetrakis(triphenylphosphine)palladium(O), bis[1,2-bis(diphenylphosphine)ethane]palladium(O), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(tri-o-tolylphosphine)palladium(II), bis[di-t-butyl(4-dimethylaminophenyl)phosphine]dichloropalladium(II), and [1,1'-bis(di-t-butylphosphine) Examples include rosene]dichloropalladium(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), chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II), and Umicore CX31 and CX32 having an NHC ligand. These compounds can also be used in combination with the above ligands or ligand precursors.

[0071] By using a palladium-containing catalyst precursor, activated palladium can also be generated in situ from the precursor using organometallic reagents, phosphines, amines, and other components present in the reaction system. Examples of such precursors include bis(dibenzylideneacetone)palladium(O), palladium(II) acetate, palladium(II) chloride, di-μ-chlorobis[(η-allyl)palladium(II)], dichlorobis(acetonitrile)palladium(II), and dichlorobis(benzonitrile)palladium(II).

[0072] When using a palladium-containing catalyst precursor, it is preferable to use a ligand precursor such as a triphosphonium salt in combination. A specific example of a triphosphonium salt is tri-t-butylphosphonium tetrafluoroborate. This compound produces tri-t-butylphosphine in situ and functions as a ligand for palladium.

[0073] [Dopant] Organic electronic materials may contain any additives, for example, dopants. The dopant is not particularly limited, as long as it can exert a doping effect when added to the organic electronic material, thereby improving charge transport. P-type doping is preferred for improving hole transport, and n-type doping is preferred for improving electron transport.

[0074] Dopants used in p-type doping are electron-accepting compounds, such as Lewis acids, protonic acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Organic electronic materials may contain ionic compounds. Among ionic compounds, onium salts are particularly preferred. An onium salt may be a compound consisting of a cation containing an onium ion, such as carbonium, sulfonium, iodonium, or ammonium, and its corresponding anion.

[0075] Dopants used in n-type doping are electron-donating compounds, such as alkali metals like Li and Cs; alkaline earth metals like Mg and Ca; alkali metal and / or alkaline earth metal salts like LiF and Cs2CO3; metal complexes; and electron-donating organic compounds.

[0076] To improve the solvent resistance of the organic layer, if the charge-transporting polymer has polymerizable functional groups, a compound that can act as a polymerization initiator for the polymerizable functional groups may be used as a dopant. According to embodiments of the present invention, since the charge-transporting polymer contains a spirofluorene structure, an organic layer with excellent solvent resistance can be formed using a charge-transporting polymer that does not have polymerizable functional groups, without the use of a polymerization initiator. Organic layers adjacent to active layers such as light-emitting layers and photoelectric conversion layers may be layers formed without the use of a polymerization initiator, taking into consideration the effect on the active layer.

[0077] [Other optional components] The organic electronic material may further contain charge-transporting low-molecular-weight compounds, other polymers, additives, etc.

[0078] [Content] The organic electronic material may contain the aforementioned charge-transporting polymer alone or in combination of two or more types. From the viewpoint of obtaining good charge transport properties, the content of the charge-transporting polymer in the organic electronic material is 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 (excluding the mass of the solvent if the material contains a solvent). There is no particular upper limit to the content of the charge-transporting polymer, and it is possible to set it to 100% by mass. Considering the inclusion of additives such as dopants, the content of the charge-transporting polymer may be, for example, 95% by mass or less or 90% by mass or less.

[0079] When an organic electronic material contains a dopant, the dopant may be contained as a single type or as a combination of two or more types. When a dopant is included, from the viewpoint of improving the charge transport properties of the organic electronic material, the dopant content 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, relative to the total mass of the organic electronic material (excluding the mass of the solvent if the material contains a solvent). Furthermore, from the viewpoint of maintaining good film-forming properties, the dopant content is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, relative to the total mass of the organic electronic material.

[0080] <Liquid composition> In embodiments of the present invention, the organic electronic material may be a liquid composition containing a solvent. The solvent-containing liquid composition allows for easy formation of the organic layer by a wet process. The liquid composition can be used as an ink composition. Because the charge-transporting polymer of the organic electronic material contains a spirofluorene structure, it also exhibits excellent solubility in solvents. Therefore, for example, it can improve the selection likelihood of the solvent used in a wet process, contributing to the wet process itself.

[0081] [solvent] Any solvent can be used as a solvent, such as water, organic solvents, or mixtures thereof. Organic solvents include alcohols such as methanol, ethanol, and isopropyl alcohol; alkanes such as pentane, hexane, and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, and diphenylmethane; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate, and cyclopentyl methyl ether; and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole. Examples include aromatic ethers such as soles; aliphatic cyclic ketones such as cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, 2-methylcyclopentanone, and 2-methylcyclohexanone; 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; aromatic halides such as chlorobenzene, o-dichlorobenzene, and 1-chloronaphthalene; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; and dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, and methylene chloride. The liquid composition may contain one solvent alone or two or more solvents.

[0082] [Additives] The liquid composition may further contain additives as optional components. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reduction inhibitors, oxidizing agents, reducing agents, surface modifiers, emulsifiers, defoaming agents, dispersants, and surfactants.

[0083] [Content] The solvent content in the liquid composition can be determined considering its application to various coating methods. For example, the solvent content is preferably such that the ratio of the charge-transporting polymer to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. Furthermore, the solvent content is preferably such that the ratio of the charge-transporting polymer to the solvent is 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0084] <Organic layer> In embodiments of the present invention, the organic layer is a layer formed using the organic electronic material. The organic electronic material may be for organic layers such as hole injection transport layers, hole injection layers, hole transport layers, photoelectric conversion layers, and buffer layers. The organic layer exhibits good solvent resistance. By using a liquid composition, the organic layer can be formed well and easily by a coating method. Examples of coating methods include known methods such as spin coating, casting, dipping, plated 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.

[0085] When forming an organic layer by a coating method, the layer containing the charge-transporting polymer obtained after coating may be dried using a hot plate or oven to remove the solvent. By applying heat, light, or both to the layer containing the charge-transporting polymer, a solvent-resistant organic layer can be formed. When heat is applied to the layer containing the charge-transporting polymer, the heating temperature is, for example, 100-180°C, 110-160°C, or 120-150°C. The higher the heating temperature, the stronger the entanglement of molecular chains within and between polymer molecules tends to be. By using a charge-transporting polymer containing structural units having a spirofluorene structure, an organic layer with good solvent resistance can be formed even at low heating temperatures.

[0086] From the viewpoint of improving the efficiency of charge transport, the thickness of the organic layer is preferably 0.1 nm or more, more preferably 1 nm or more, and even more preferably 3 nm or more. Furthermore, from the viewpoint of reducing electrical resistance, the thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.

[0087] <Organic Electronics Components> In embodiments of the present invention, the organic electronic element has at least the organic layer. Examples of organic electronic elements include organic EL elements such as organic light-emitting diodes (OLEDs), organic photoelectric conversion elements, and organic transistors. Preferably, the organic electronic element has a structure in which an organic layer is disposed between at least one pair of electrodes.

[0088] <Organic electroluminescent elements (organic EL elements)> In embodiments of the present invention, the organic EL element has at least the organic layer. The organic EL element typically comprises an emissive layer, an anode, a cathode, and a substrate, and optionally includes 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 vapor deposition or by coating. Known materials can be used to form each layer. For known materials, see, for example, International Publication No. 2010 / 140553. The organic EL element may have an organic layer as an emissive layer or a functional layer, preferably as a functional layer, more preferably as a hole injection transport layer, and even more preferably as at least one of a hole injection layer and a hole transport layer. For the structure and manufacturing method of the organic EL element, see, for example, International Publication No. 2010 / 140553. The organic EL element may have a multilayer structure including at least two adjacent organic layers. Figure 1 shows an example of an organic EL element. The organic EL element shown in Figure 1 is an element comprising multiple adjacent organic layers, where 1 is the light-emitting layer, 2 is the anode, 3 is the hole injection layer, 4 is the cathode, 5 is the electron injection layer, 6 is the hole transport layer, 7 is the electron transport layer, and 8 is the substrate. The organic electronic material according to the embodiment of the present invention can be preferably used in the manufacture of organic EL elements because it can sufficiently improve the solvent resistance of the organic layer even at low heating temperatures.

[0089] The organic layer formed using the organic electronics material is preferably used as at least one of a hole injection layer and a hole transport layer, and more preferably as at least a hole injection layer. These layers can be easily formed by using a liquid composition as the organic electronics material.

[0090] If the organic EL element has an organic layer formed using the organic electronics material as a hole transport layer and further has a hole injection layer, known materials can be used for the hole injection layer. It is also preferable to use the organic electronics material for both the hole injection layer and the hole transport layer.

[0091] <Display elements, lighting devices, display devices> In embodiments of the present invention, the display element comprises the organic EL elements. For example, by using organic EL elements as elements corresponding to red, green, and blue (RGB) pixels, a color display element can be obtained. The image formation method includes 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 placed in each element for driving.

[0092] The lighting device includes the aforementioned organic EL element. The display device includes the lighting device and a liquid crystal element as a display means. For example, the display device can be a display device that uses the lighting device as a backlight and a known liquid crystal element as a display means, i.e., a liquid crystal display device.

[0093] <Organic photoelectric conversion element> In embodiments of the present invention, the organic photoelectric element includes at least the organic layer. The organic photoelectric element includes organic solar cells, organic image sensors, and the like. The organic photoelectric element comprises, for example, a photoelectric conversion layer, electrodes, and a substrate. Furthermore, it may have other layers such as a buffer layer and an electron transport layer for the purpose of improving conversion efficiency or stability in air. The organic photoelectric element has at least the organic layer, and the organic layer can be used as a photoelectric conversion layer and a buffer layer, and is preferably used as a buffer layer. Therefore, an example of an organic photoelectric element has an anode, an organic layer as a buffer layer, a photoelectric conversion layer, and a cathode in this order, and may have any additional layers between these layers.

[0094] Any material can be used for the photoelectric conversion layer as long as it absorbs light, causes charge separation, and generates electromotive force. The material of the photoelectric conversion layer may, for example, be a mixture of a p-type organic semiconductor and an n-type organic semiconductor from the viewpoint of conversion efficiency. Examples of p-type organic semiconductors include polymers or oligomers such as oligothiophenes, polyalkylthiophenes, poly(3-hexylthiophene) (P3HT), and polyphenylene vinylene (PPV); porphyrins, phthalocyanines, copper phthalocyanines; and derivatives thereof. Examples of n-type organic semiconductors include polymers or oligomers containing -CN or -CF3 groups such as CN-poly(phenylene-vinylene) (CN-PPV), MEH-CN-PPV, and their -CF3-substituted polymers; polymers or oligomers such as poly(fluorene) derivatives and fluorene-benzothiadiazole copolymers; and fullerene (C 60 Examples include naphthalenetetracarboxylic anhydride (NTCDA), perylenetetracarboxylic anhydride (PTCDA), quinacridone; and derivatives thereof. Furthermore, from the viewpoint of conversion efficiency, flexibility, productivity, etc., the material of the photoelectric conversion layer may be a material containing a perovskite compound. The organic electronics material according to the embodiment of the present invention can sufficiently improve the solvent resistance of the organic layer even at low heating temperatures, and is therefore preferably used in the manufacture of solar cells having a photoelectric conversion layer containing a perovskite compound (sometimes referred to as "for perovskite solar cells").

[0095] The method for forming the photoelectric conversion layer is not particularly limited and may be formed by vapor deposition or by coating. Forming by coating is more preferable because it allows for the inexpensive manufacture of organic photoelectric conversion elements. As a method for forming by coating, the method described in the method for forming the organic layer can be used.

[0096] The organic photoelectric conversion element may have the buffer layer in addition to the photoelectric conversion layer, and may also have layers such as an electron transport layer. The buffer layer may be the organic layer, and the electron transport layer may be a layer containing LiF, TiOx, ZnOx, etc. [Examples]

[0097] Embodiments of the present invention will be described with reference to examples. Embodiments of the present invention are not limited to the following examples.

[0098] <Preparation of Organic Electronic Materials> The raw material monomers used in the examples and comparative examples are shown below.

[0099] [Table 1]

[0100] [Example 1] Charge-transport polymers were synthesized using the monomers shown in Table 1 via Suzuki-Miyaura coupling.

[0101] (Preparation and purification of polymers) A reaction vessel equipped with a Liebig condenser and stirring function was prepared, and an oil bath was positioned relative to the reaction vessel so as to be able to move back and forth. The following raw material monomers, bases, and additives were added to the nitrogen-purged reaction vessel while injecting nitrogen, and a nitrogen gas supply device was connected to the end of the Liebig condenser to dissolve the added components at 60°C. Next, the following catalyst was added to the reaction vessel, and the reaction was carried out for 2 hours while stirring in the oil bath (bath temperature 120°C) until the organic solvent refluxed. Raw material monomers: Monomer A2 (1.975 mg, 3.125 mmol), Monomer B1 (5.694 mg, 10 mmol), Monomer C1 (2.019 mg, 7.5 mmol) Organic solvent: Dehydrated toluene (82.2 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) stored under a nitrogen atmosphere. Base: 3.0 mol% potassium hydroxide aqueous solution (15.6 mL) Catalyst: Bis[di-t-butyl(4-dimethylaminophenyl)phosphine]dichloropalladium(II) (35.4 mg, manufactured by Fujifilm Wako Pure Chemical Corporation) Additive: Methyltri-n-octylammonium chloride (0.081g, Aliquat336, manufactured by Alfa Aesar)

[0102] Next, the reaction vessel was heated in an oil bath (bath temperature 120°C) until the organic solvent refluxed, and the reaction was carried out for 2 hours with stirring. After the reaction, the temperature of the reaction mixture in the reaction vessel was lowered to room temperature, and 40 mL of an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), adjusted to 0.1 mol / L, was added and stirred. The separated organic phase was reprecipitation using methanol, and the resulting precipitate was filtered by suction. Hexane was added to the obtained precipitate, and the mixture was stirred in an oil bath at 60°C for 15 minutes, and the precipitate was washed with hexane. After washing, the precipitate was recovered by suction filtration. The precipitate was washed once more with hexane as described above to remove any remaining monomers and hexane-soluble components from the precipitate. Next, the precipitate was dried under reduced pressure to obtain a polymer (pale yellow powder) in a yield of 63% by mass.

[0103] Proton nuclear magnetic resonance of polymers 1 By measuring the 1H-NMR spectrum, it was confirmed that the polymer has a structure obtained by polycondensation of monomers A2, B1, and C1. 1 1H-NMR spectra were measured using a Bruker AVANCE-600 NMR spectrometer.

[0104] The number-average molecular weight and weight-average molecular weight of the polymer were measured by gel permeation chromatography (GPC), and the amount of impurities in the polymer was measured by energy-dispersive X-ray fluorescence analysis. The measurement conditions were as follows. The number-average molecular weight (Mn), weight-average molecular weight (Mw), Mw / Mn, and impurity concentration are shown in Table 3.

[0105] (Measurement of number-average molecular weight and weight-average molecular weight) The number-average molecular weight and weight-average molecular weight of the polymer were measured using gel permeation chromatography (GPC) under the following conditions. Equipment: High-performance liquid chromatograph Prominence GPC system (Shimadzu Corporation) Liquid transfer pump (LC-20AD) Degassing unit (DGU-20A) Autosampler (SIL-20AHT) Column oven (CTO-20A) PDA detector (SPD-M20A) Differential refractive index detector (RID-20A) Column: Styrene gel column Gelshok GL-A160S (serial number: 686-1J27) GL-A150S (serial number: 685-1J27) It was used after being reconditioned with standard polystyrene at 40°C. Eluent: Tetrahydrofuran (THF) (for HPLC, containing stabilizer) (Fujifilm Wako Pure Chemical Industries, Ltd.) Flow rate: 1mL / min Column temperature: 40℃ Detection wavelength: 254nm Molecular weight standard material: PStQuick B / C / D (Tosoh Corporation)

[0106] (Measurement of impurity levels) The content of palladium (Pd), Br, and Cl as impurities in the polymer was measured using an energy-dispersive X-ray fluorescence spectrometer (EDX) under the following conditions. Equipment: EDX-7000 (Shimadzu Corporation) X-ray tube: Rh target Atmosphere: Atmosphere Measurement time (seconds): Pd: 600, Br: 100, Cl: 1000 Analysis range (keV): Pd: 20.72~21.52, Br: 11.66~12.16, Cl: 2.42~2.82

[0107] [Comparative Example 1] Charge-transport polymers were synthesized by Suzuki-Miyaura coupling using the monomers shown in Table 1, in the same manner as in Example 1. Raw material monomers: Monomer A1 (1.928 mg, 4 mmol), Monomer B1 (5.694 mg, 10 mmol), Monomer C1 (2.154 mg, 8 mmol) Organic solvent: Dehydrated toluene (83.0 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) stored under a nitrogen atmosphere. Base: 3.0 mol% potassium hydroxide aqueous solution (17.1 mL) Catalyst: Bis[di-t-butyl(4-dimethylaminophenyl)phosphine]dichloropalladium(II) (35.4 mg, manufactured by Fujifilm Wako Pure Chemical Corporation) Additive: Methyltri-n-octylammonium chloride (0.089g, Aliquat336, manufactured by Alfa Aesar)

[0108] Next, the reaction vessel was heated in an oil bath (bath temperature 120°C) until the organic solvent refluxed, and the reaction was carried out for 2 hours with stirring. After the reaction, the temperature of the reaction mixture in the reaction vessel was lowered to room temperature, and 40 mL of an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), adjusted to 0.1 mol / L, was added and stirred. The separated organic phase was reprecipitated using a methanol:water (9:1) mixture, and the resulting precipitate was filtered by suction. Ethyl acetate was added to the obtained precipitate, and the mixture was stirred in an oil bath at 60°C for 15 minutes, washing the precipitate with ethyl acetate. After washing, the precipitate was recovered by suction filtration. The precipitate was washed once more with ethyl acetate as described above to remove any remaining monomers and ethyl acetate-soluble reactants from the precipitate. Next, the precipitate was dried under reduced pressure to obtain a polymer (pale yellow powder) in a yield of 51% by mass. Various measurements of the polymer were performed in the same manner as in Example 1. The results are shown in Table 3. In Table 3, "ND" means that the target impurity was not detected.

[0109] [Example 2] Charge-transport polymers were synthesized using the monomers shown in Table 1 via Buchwald-Hartwig coupling.

[0110] A reaction vessel equipped with a Liebig condenser and a stirring function was prepared, and an oil bath was positioned relative to the reaction vessel so as to be able to move back and forth. The following components were added to the nitrogen-purged reaction vessel while injecting nitrogen, and a nitrogen gas supply device was connected to the end of the Liebig condenser to create a nitrogen atmosphere for the reaction. Raw material monomers: Monomer A2 (2.173 mg, 3.438 mmol), Monomer B2 (1.372 mg, 10 mmol), Monomer C1 (1.683 mg, 6.25 mmol) Organic solvent: Xylene (60.4 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) stored under a nitrogen atmosphere. Base: t-butoxysodium (2.883 mg (3.0 mol% based on amine monomer B2), manufactured by Tokyo Chemical Industry Co., Ltd.) Catalyst: Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (39.3 mg, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0111] Next, the reaction vessel was heated in an oil bath (bath temperature 160°C) until the organic solvent 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 mixture of water:methanol (8:2) and 40 mL of an aqueous solution of N,N-diethyldithiocarbamate sodium trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) adjusted to 0.5 mol / L were added and stirred. The resulting mixture was separated into an aqueous phase and an organic phase, and the organic phase was recovered. The organic phase was reprecipitated with methanol, and the resulting precipitate was filtered by suction. Ethyl acetate was added to the obtained precipitate, and the mixture was stirred in an oil bath at 60°C for 15 minutes, and the precipitate was washed with hexane. After washing, the precipitate was recovered by suction filtration. The precipitate was washed once more with hexane as described above to remove any remaining monomers and hexane-soluble reactants from the precipitate. Next, the precipitate was dried under reduced pressure to obtain a polymer (pale yellow powder) in a yield of 72% by mass. Various measurements of the polymer were performed in the same manner as in Example 1. The results are shown in Table 3.

[0112] [Comparative Example 2] Charge-transport polymers were synthesized using the monomers shown in Table 1 via Buchwald-Hartwig coupling, in the same manner as in Example 2. Raw material monomers: Monomer A1 (2.571 mg, 5.333 mmol), Monomer B2 (1.372 mg, 10 mmol), Monomer C1 (1.077 mg, 4 mmol) Organic solvent: Xylene (58.0 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) stored under a nitrogen atmosphere. Base: t-butoxysodium (2.883 mg (3.0 mol% based on amine monomer B2), manufactured by Tokyo Chemical Industry Co., Ltd.) Catalyst: Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (39.3 mg, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0113] After the reaction, the temperature of the reaction mixture in the reaction vessel was lowered to room temperature, and 40 mL of a water:methanol (8:2) mixture and an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) adjusted to 0.5 mol / L were added and stirred. The resulting mixture was separated into an aqueous phase and an organic phase, and the organic phase was recovered. The organic phase was reprecipitated using a methanol:water (9:1) mixture, and the resulting precipitate was filtered by suction. 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 precipitate after washing was then recovered by suction filtration. The precipitate was washed once more with ethyl acetate as described above to remove any remaining monomers and ethyl acetate-soluble reactants from the precipitate. Next, the precipitate was dried under reduced pressure to obtain a polymer (pale yellow powder) in a yield of 45% by mass. Various measurements of the polymer were performed in the same manner as in Example 1. The results are shown in Table 3.

[0114] [Examples 3-8] As shown in Table 2, polymers were prepared in the same manner as in Example 2, except that the raw material monomers and their amounts were changed. Various measurements were performed on the obtained polymers in the same manner as in Example 1. The results are shown in Table 3.

[0115] [Comparative Examples 3 and 4] As shown in Table 2, polymers were prepared in the same manner as in Comparative Example 2, except that the raw material monomers and their proportions were changed. Various measurements were performed on the obtained polymers in the same manner as in Example 1. The results are shown in Table 3.

[0116] [Table 2]

[0117] [Table 3]

[0118] <Evaluation of Organic Electronic Materials> (Evaluation of the solubility of charge-transport polymers in solvents) The solubility of the charge-transport polymers of Examples 1-8 and Comparative Examples 1-4 in solvents was evaluated using the following method. The results are shown in Table 4.

[0119] 50.0 mg of charge-transporting polymer was weighed into a 6 mL screw-cap tube, and 1,096 μL of toluene was added. The mixture was stirred using a 10 mm stirrer bar at 25°C for 500 mins. -1 The mixture was stirred under these conditions, and the time it took for the mixture to become clear was measured. Solubility was evaluated using the following four-level criteria. (Evaluation Criteria) A: Dissolution time less than 1 minute B: Dissolution time: 1 minute or more but less than 3 minutes C: Dissolution time: 3 minutes or more but less than 5 minutes D: Dissolution time 5 minutes or more

[0120] (Evaluation of solvent resistance (residual film rate) of the organic layer) Organic layers were formed using the charge-transport polymers of Examples 1-8 and Comparative Examples 1-4 by the following method, and the solvent resistance (residual film rate) of the organic layers was evaluated. The results are shown in Table 4. In Table 4, "Polymerization component - Present" means that the polymer has polymerizable functional groups, and "Polymerization component - Absent" means that the polymer does not have polymerizable functional groups.

[0121] A polymer (50.0 mg) and the following ionic compound (1) (0.5 mg) were weighed into a 9 mL screw-cap tube, and toluene (4949.5 mg) was added to dissolve them and prepare an ink composition. The ink composition was then filtered using a PTFE filter (pore size 0.2 μm). The filtered ink composition was dropped onto a quartz substrate (22 mm long x 29 mm wide x 0.7 mm thick) and deposited using a spin coater. Subsequently, heating was performed at 120°C for 30 minutes under atmospheric conditions, or at 150°C for 30 minutes under atmospheric conditions, to form an organic layer with a thickness of 30 nm on the quartz substrate. [ka]

[0122] Next, the absorbance A of the organic layer formed on the quartz substrate was measured using a spectrophotometer (UV-2700, manufactured by Shimadzu Corporation). Subsequently, the organic layer was immersed in toluene (10 ml) for 10 minutes at 25°C, with the measured organic layer facing upwards. The absorbance B of the organic layer after toluene immersion was measured. The residual film percentage was calculated from the absorbance A of the organic layer and the absorbance B of the organic layer after toluene immersion using the following formula. The absorbance value used was the absorbance (Abs) at the maximum absorption wavelength (λmax) of the organic layer.

number

[0123] [Table 4]

[0124] (Evaluation of HOMO levels in charge-transport polymers) The HOMO levels of the charge-transport polymers in Examples 1-8 were evaluated using the following method. The results are shown in Table 5.

[0125] A polymer (50.0 mg) and the above-mentioned ionic compound (1) (0.5 mg) were weighed into a 9 mL screw-top tube, and toluene (4949.5 mg) was added to dissolve them and prepare an ink composition. Next, the ink composition was filtered using a PTFE filter (pore size 0.2 μm). The filtered ink composition was dropped onto a quartz substrate (22 mm long × 29 mm wide × 0.7 mm thick) and deposited using a spin coater. Subsequently, heating was carried out at 150°C for 30 minutes under atmospheric conditions to form an organic layer with a thickness of 30 nm on the quartz substrate. The surface work function of an organic layer formed on a quartz substrate was measured in air using a photoelectron yield spectrometer (model AC-5, manufactured by RIKEN Keiki Co., Ltd.). The HOMO level was determined from the surface work function value.

[0126] (Evaluation of the conductivity of the organic layer) The conductivity (hole-only devices) of the organic layers formed using the charge-transport polymers of Examples 1 to 8 was evaluated using the following method. The results are shown in Table 5.

[0127] (1) Fabrication of a Hole-Only Device (HOD) A polymer (50.0 mg) and the above-mentioned ionic compound (1) (1.5 mg) were weighed into a 9 mL screw-cap tube, and toluene (2448.5 mg) was added to dissolve them and prepare an ink composition. The ink composition was filtered through a PTFE filter (pore size 0.2 μm). The filtered ink composition was dropped onto a quartz substrate (22 mm long x 29 mm wide x 0.7 mm thick, hereafter referred to as the ITO substrate) patterned with ITO to a width of 1.6 mm, and a film was formed using a spin coater. Subsequently, heating was carried out at 150°C for 30 minutes under a nitrogen atmosphere to form an organic layer (cured or dried film) with a thickness of 60 nm on the ITO substrate. The organic layer formed on the ITO substrate was transferred to a vacuum deposition machine, and 100 nm of aluminum (Al) was deposited onto the organic layer using a vapor deposition method. Further sealing treatment was performed to fabricate a hole-only device (hereinafter referred to as HOD) for conductivity evaluation. Figure 2 is a schematic cross-sectional view showing the structure of the HOD. As shown in Figure 2, the HOD is a laminate having an anode 12, an organic layer (hole injection layer) 13, and a cathode 14 in that order on a substrate 11, and sealing treatment (not shown) is applied to surround this laminate.

[0128] (2) Evaluation of the conductivity of HOD A voltage was applied to the HOD, and its conductivity (hole injection function) was confirmed when the voltage was applied. The conductivity was evaluated using the following two-stage criteria. A: Conductive B: No conductivity (3) Measurement of the current density of the HOD A voltage of 0.2V or 1.0V was applied to the HOD, and the current density was measured.

[0129] [Table 5] [Explanation of symbols]

[0130] 1. Emitting layer 2 Anode 3. Hole injection layer 4 cathode 5 Electron injection layer 6. Hole transport layer 7 Electron transport layer 8 circuit boards 11 circuit boards 12 Anode 13. Organic layer (hole injection layer) 14 Cathode

Claims

1. An organic electronics material containing a charge-transporting branched polymer that includes structural units having a spirofluorene structure.

2. The organic electronic material according to claim 1, wherein the structural unit having the spirofluorene structure includes a structural unit represented by the following formula (1-1). 【Chemistry 1】 (In the formula, R represents an independent substituent, n represents an independent integer from 0 to 3, and * represents a bonding site with another structural unit.)

3. The organic electronics material according to claim 1, wherein the charge-transporting branched polymer has polymerizable functional groups.

4. The organic electronic material according to claim 3, wherein the polymerizable functional group includes a group having a carbon-carbon multiple bond.

5. The organic electronics material according to claim 1, wherein the charge-transporting branched polymer includes a structural unit represented by the following formula (3-2). 【Chemistry 2】 (In the formula, R represents an independent substituent, n represents an integer from 0 to 3, and * represents a bonding site with another structural unit.)

6. The organic electronic material according to claim 1, wherein the charge-transporting branched polymer comprises at least one selected from the group consisting of structural units represented by the following formula (3-1) and structural units represented by the following formula (3-2). 【Transformation 3】 (In the formula, n represents an integer from 0 to 3 independently, and * represents a bonding site with another structural unit.) 【Chemistry 4】 (In the formula, n represents an integer from 0 to 3 independently, and * represents a bonding site with another structural unit.)

7. The organic electronics material according to claim 1, wherein the charge-transporting branched polymer has an alkoxy group.

8. The organic electronic material according to claim 1, for use in a hole injection transport layer.

9. The organic electronic material according to claim 1, for use in organic electroluminescent elements or perovskite solar cells.

10. An organic electronic element comprising an organic layer formed using an organic electronic material according to any one of claims 1 to 9.

11. An organic electroluminescent element comprising an organic layer formed using an organic electronic material according to any one of claims 1 to 9.

12. An organic photoelectric element comprising an organic layer formed using an organic electronic material according to any one of claims 1 to 9.

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