JP2019083259A - Charge transporting material and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge transporting material having improved curability, an ink composition, and an organic electroluminescence device using them. A first charge-transporting polymer having one or more benzocyclobutenyl group-containing groups and a second charge-transporting polymer having one or more carbon-carbon unsaturated bond group-containing groups are contained. , Charge transport material. [Selection diagram] None

Description

  The present disclosure relates to a charge transporting material, an ink composition, an organic layer, an organic electronic device, an organic electroluminescent device (also referred to as “organic EL device”), a display device, a lighting device, and a display device.

  Organic electronics elements are elements that perform electrical operations using organic substances, and are expected to exhibit features such as energy saving, low cost, flexibility, etc., and are noted as a technology to replace conventional inorganic semiconductors based mainly on silicon It is done. Examples of the organic electronic element include an organic EL element, an organic photoelectric conversion element, an organic transistor and the like.

  Among organic electronic devices, organic EL devices are attracting attention as large-area solid-state light source applications, for example, as a substitute for incandescent lamps and gas-filled lamps. In addition, it is attracting attention as a leading self-luminous display to replace liquid crystal displays (LCDs) in the flat panel display (FPD) field, and its commercialization is in progress.

  Organic EL elements are roughly classified into low molecular weight type organic EL elements using low molecular weight compounds and high molecular weight type organic EL elements using high molecular weight compounds from organic materials to be used. In addition, the method of manufacturing an organic EL element is mainly a dry process in which film formation is performed in a vacuum system, and a wet process in which film formation is performed by plate printing such as relief printing or intaglio printing, plateless printing such as inkjet It is divided roughly into two. A wet process is expected as an indispensable method for the future large screen organic EL display because simple film formation is possible compared with a dry process requiring a vacuum system. Therefore, in recent years, development of polymer compounds suitable for wet processes has been promoted.

  On the other hand, regarding the organic EL element, further improvement is desired in various element characteristics such as light emission efficiency. As a means of improving the performance of organic EL elements, attempts have been made to multilayer organic layers and to separate functions in each layer. When multilayering according to a wet process, the solvent resistance of the lower layer to the solvent of the coating solution used at the time of film formation of the upper layer is required.

  As a method of forming a multilayer, for example, a method using two kinds of compounds having different solubilities in water and an organic solvent as materials constituting adjacent layers is known. Specifically, water-soluble PEDOT: PSS is used as a compound for forming the lower layer such as a buffer layer or a hole injection layer, while toluene or the like is used as a compound for forming an upper layer such as a photoelectric conversion layer or a light emitting layer. There is a method of using a material soluble in an organic solvent. Since the lower layer formed of PEDOT: PSS is insoluble in an organic solvent such as toluene, this method makes it possible to produce a two-layer structure by a coating method.

  However, in the method using water-soluble PEDOT: PSS, water may easily remain in the formed organic layer, and the characteristics of the organic layer may be degraded. Moreover, in the multi-layering, materials which can be used are limited.

  As another method, a method of improving the solvent resistance of the lower layer toward multilayering is considered. For example, studies are being made to form a multilayer structure using a compound having a polymerizable functional group (see, for example, Patent Document 1).

JP, 2009-283509, A

  In the method of using a compound having a polymerizable functional group, for example, a material containing a polymerizable polymer, a polymerization initiator, and an organic solvent is used. Multilayering can be achieved by applying the material, forming a cured lower layer by heating or the like, and forming an upper layer thereon.

  However, in this method, when the upper layer is formed using an organic solvent, when the lower layer does not have sufficient solvent resistance, a part of the lower layer may dissolve out, and a good multilayer structure may be formed. It can be difficult.

  Therefore, in view of the above, it is an object of the present disclosure to provide a charge transporting material and an ink composition having improved curability. Another object of the present disclosure is to provide an organic layer suitable for forming a multilayer structure, and to provide an organic electronic device and an organic EL device having a multilayer structure. Furthermore, this indication makes it a subject to provide a display element, a lighting installation, and a display which improved various characteristics by using an organic electronics element or organic EL element which has multilayer structure.

  The invention includes various embodiments. Examples of embodiments are listed below. The present invention is not limited to the following embodiments.

  One embodiment includes a first charge transporting polymer having one or more benzocyclobutenyl group-containing groups and a second charge transporting polymer having one or more carbon-carbon unsaturated bond group-containing groups Related to charge transport materials.

  According to one embodiment, the first charge transporting polymer and the second charge transporting polymer each have a structure branched in three or more directions.

  According to one embodiment, the first charge transportable polymer and the second charge transportable polymer each consist of a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, and a fluorene structure It has one or more structures selected from the group.

  According to one embodiment, at least one of the one or more benzocyclobutenyl group-containing groups is present at the end of the first charge transporting polymer, and the one or more carbon-carbon unsaturated bond group At least one of the containing groups is present at the end of the second charge transportable polymer.

According to one embodiment, the benzocyclobutenyl group-containing group includes a group represented by the following formula (4).
(Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^g each independently represent a hydrogen atom or a substituent. 1 to m are integers. L is 0 or 1, n is 0 or 1, and m is 1 or more.)

According to one embodiment, the carbon-carbon unsaturated bond group-containing group includes a group represented by the following formula (9).
(Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. 1 to m are integers. L is 0 or 1, n is 0 or 1, and m is 1 or more.)

  According to one embodiment, any of the charge transporting materials is a hole injecting material or a hole transporting material.

  Another embodiment relates to an ink composition comprising any of the above charge transport materials and a solvent.

  Another embodiment relates to an organic electronic device having the charge transportable material of any of the above or an organic layer formed using the ink composition.

  Another embodiment relates to an organic electroluminescent element having an organic layer formed using any one of the charge transport materials or the ink composition.

  Another embodiment relates to the organic electroluminescent device, further comprising a flexible substrate.

  Another embodiment relates to the organic electroluminescent device, further comprising a resin substrate.

  Another embodiment relates to a display device comprising any of the above organic electroluminescent devices.

  Another embodiment relates to a lighting device comprising any of the organic electroluminescent devices.

  Another embodiment relates to a display device including the lighting device and a liquid crystal element as display means.

  According to the present disclosure, it is possible to provide a charge transporting material and an ink composition with improved curability. Moreover, according to the present disclosure, it is possible to provide an organic layer suitable for forming a multilayer structure, and to provide an organic electronic device and an organic EL device having a multilayer structure. Furthermore, according to the present disclosure, by using an organic electronic device or an organic EL device having a multilayer structure, it is possible to provide a display device, a lighting device, and a display device with improved various characteristics.

It is a cross-sectional schematic diagram which shows an example of the organic EL element which is one Embodiment of this invention. The fluorescence spectrum of the organic layer produced in the reference example is shown. The difference spectrum with the fluorescence spectrum of the organic layer produced in the reference example 1 and the fluorescence spectrum of the organic layer produced in the reference example 5 is shown. The fluorescence spectrum of the organic layer produced in the Example and the comparative example is shown. 13 shows a difference spectrum between the fluorescence spectrum of the organic layer produced in Example 11 and the fluorescence spectrum of the organic layer produced in Example 15.

  Embodiments of the present invention will be specifically described. The present invention is not limited to these embodiments.

<Charge transporting material>
In one embodiment, the charge transport material comprises at least two charge transport polymers capable of transporting charge and capable of reacting with one another. At least two charge transporting polymers are a first charge transporting polymer having one or more benzocyclobutenyl group-containing groups, and a second charge transporting polymer having one or more carbon-carbon unsaturated bond group-containing groups And an acid polymer. The charge transportable material is excellent by containing the first charge transportable polymer having a benzocyclobutenyl group-containing group and the second charge transportable polymer having a carbon-carbon unsaturated bond group-containing group It shows curability. In the present disclosure, the term "polymer" also includes "oligomer" which is a polymer having a low degree of polymerization. The charge transporting material can be preferably used as an organic electronic material.

  Generally, the polymerization of a compound having a vinyl group proceeds by an addition polymerization reaction via a double bond, and the polymerization of a compound having a benzocyclobutenyl group proceeds through an addition via a double bond resulting from ring opening of the benzocyclobutenyl group. It is considered to proceed by polymerization reaction. In addition, a compound having a vinyl group and a compound having a benzocyclobutenyl group can be a substrate of cycloaddition reaction such as Diels-Alder reaction by ring-opening the benzocyclobutenyl group-containing group by heating. The cycloaddition reaction occurring between the benzocyclobutenyl group-containing group and the vinyl group-containing group proceeds at a lower temperature than the addition polymerization reaction between the benzocyclobutenyl group-containing groups or the vinyl group-containing groups. . In addition, the cycloaddition reaction occurring between the benzocyclobutenyl group-containing group and the vinyl group-containing group is a reaction compared to the addition polymerization reaction between the benzocyclobutenyl group-containing groups or between the vinyl group-containing groups. Tend to occur easily.

  From the above, cyclization occurs when the first charge transporting polymer having a benzocyclobutenyl group-containing group and the second charge transporting polymer having a carbon-carbon unsaturated bond group-containing group are used in combination. As the addition reaction proceeds, it is considered that sufficient insolubilization (curing) of the organic layer can be achieved, as compared to the case of polymerizing each of them alone.

  When the first charge transporting polymer having a benzocyclobutenyl group-containing group and the second charge transporting polymer having a carbon-carbon unsaturated bond group-containing group are used in combination, the polymerization reaction proceeds efficiently. Sufficient insolubilization can be carried out without containing a large amount of a benzocyclobutenyl group-containing group or a carbon-carbon unsaturated bond group-containing group in the polymer.

  In addition, polymers having an oxetane group or an epoxy group are known as polymerizable polymers. Generally, in the polymerization of a compound having an oxetane group or an epoxy group, an oxetane group or an epoxy group which is ring-opened by an active species generated from a polymerization initiator with heating attacks an unopened oxetane group or an epoxy group Proceed by. When a polymer having an oxetane group or an epoxy group is used as a polymerizable polymer, heating is performed using a polymerization initiator in order to sufficiently insolubilize the polymer. On the other hand, a polymerization initiator is obtained by using the first charge transporting polymer having a benzocyclobutenyl group-containing group and the second charge transporting polymer having a carbon-carbon unsaturated bond group-containing group in combination. It is possible to carry out sufficient insolubilization without using.

  In a charge transporting material containing a first charge transporting polymer having a benzocyclobutenyl group-containing group and a second charge transporting polymer having a carbon-carbon unsaturated bond group-containing group, the content ratio of both Can be selected appropriately according to the application. It is preferable to adjust the content of the first charge transporting polymer and the second charge transporting polymer in consideration of the molar ratio between the benzocyclobutenyl group-containing group and the carbon-carbon unsaturated bond group-containing group. .

  In one embodiment, the ratio (molar ratio) of the benzocyclobutenyl group-containing group / carbon-carbon unsaturated bond group-containing group is preferably 0.05 or more, from the viewpoint of efficiently advancing the Diels-Alder reaction. 1 or more is more preferable, and 0.2 or more is still more preferable. Further, from the viewpoint of efficiently advancing the Diels-Alder reaction, the ratio (molar ratio) of the benzocyclobutenyl group-containing group / carbon-carbon unsaturated bond group-containing group is preferably 20 or less, more preferably 10 or less, 4 or less is more preferable.

  In one embodiment, from the viewpoint of obtaining high curability, the ratio of the benzocyclobutenyl group-containing group is preferably high. The ratio (molar ratio) of benzocyclobutenyl group-containing group / (benzocyclobutenyl group-containing group + carbon-carbon unsaturated bond group-containing group) is preferably 0.5 or more, more preferably 0.6 or more, 0.8 or more is more preferable. Further, from the viewpoint of improving the curability, the ratio (molar ratio) of the benzocyclobutenyl group-containing group / (benzocyclobutenyl group-containing group + carbon-carbon unsaturated bond group-containing group) is 0.99 or less Preferably, it is 0.95 or less, more preferably 0.92 or less.

  In one embodiment, the ratio of the carbon-carbon unsaturated bond group-containing group is preferably high from the viewpoint of suppressing the change of the fluorescence spectrum before and after curing of the organic layer. The organic layer formed using the first charge transporting polymer having a benzocyclobutenyl group-containing group tends to cause a change in fluorescence spectrum before and after curing. From the viewpoint of easily designing an organic electronic device, it may be desirable to suppress the change in fluorescence spectrum. The ratio (molar ratio) of the benzocyclobutenyl group-containing group / (benzocyclobutenyl group-containing group + carbon-carbon unsaturated bond group-containing group) is preferably 0.5 or less, more preferably 0.4 or less, 0.35 or less is still more preferable. Further, from the viewpoint of improving the curability, the ratio (molar ratio) of benzocyclobutenyl group-containing group / (benzocyclobutenyl group-containing group + carbon-carbon unsaturated bond group-containing group) is 0.01 or more. Preferably, it is 0.05 or more, more preferably 0.08 or more.

[Charge transporting polymer]
The first charge transporting polymer and the second charge transporting polymer will be described in detail below.
(Benzocyclobutenyl group-containing group)
The benzocyclobutenyl group-containing group in the first charge transporting polymer is a group containing one or more benzocyclobutenyl groups. The benzocyclobutenyl group is a monovalent group derived from benzocyclobutene, and has a structure capable of reacting with at least a carbon-carbon unsaturated bond group to form a bond. According to one embodiment, the benzocyclobutenyl group is a group having a structure capable of causing a Diels-Alder reaction, that is, a group capable of opening a ring, exhibiting reactivity and reacting with a carbon-carbon unsaturated bond group. is there. For example, a benzocyclobutenyl group includes a group represented by the following formula (1). In the present disclosure, “*” in the formula represents a binding site to another structure.

R ^a to R ^g each independently represent a hydrogen atom or a substituent. R ^{a to} R ^g may be bonded to each other to form a ring. The substituent is, for example, a substituent selected from -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , and a halogen atom Sometimes referred to as "substituent R ^A ".

In the present disclosure, R ^{1 to} R ⁸ each independently represent a hydrogen atom; an alkyl group having 1 to 22 carbon atoms; or an aryl group or a heteroaryl group having 2 to 30 carbon atoms (however, R ¹ Is a group selected from other than a hydrogen atom). The alkyl group may be further substituted by an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group is further substituted by an alkyl group having 1 to 22 carbon atoms May be

  In the present disclosure, the alkyl group may be a linear, branched or cyclic alkyl group. The linear, branched or cyclic alkyl group is an atomic group obtained by removing one hydrogen atom from a linear or branched saturated hydrocarbon, or an atomic group obtained by removing one hydrogen atom from a cyclic saturated hydrocarbon. The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. Examples of the aromatic hydrocarbon and the aromatic heterocycle are as mentioned in the description of the "aromatic ring" described later.

In one embodiment, in terms of obtaining sufficient curability, all of R ^{a to} R ^g are hydrogen atoms.

In one embodiment, any one or more of R ^{a to} R ^g is an alkyl group. The alkyl group may have 1 to 6 carbon atoms. Also, the alkyl group has any structure of a linear alkyl group (-C _n H _{2 n + 1} ), a branched alkyl group (-C _n H _{2 n + 1} ) and a cyclic alkyl group (-C _n H _{2 n-1} ) (N is an integer of 1 or more, for example, an integer of 1 to 6).

  The benzocyclobutenyl group-containing group is a group having a benzocyclobutenyl group. The first charge transporting polymer may have only one type of benzocyclobutenyl group-containing group, or may have two or more types. The benzocyclobutenyl group-containing group may contain only one benzocyclobutenyl group or two or more benzocyclobutenyl groups. When two or more are included, the two or more may be the same or different.

In one embodiment, the benzocyclobutenyl group-containing group may be a benzocyclobutenyl group itself. For example, the group represented by Formula (1) may be a benzocyclobutenyl group-containing group. In another embodiment, the benzocyclobutenyl group-containing group is attached to a substituted or unsubstituted aromatic ring structure and the aromatic ring structure directly or via a divalent linking group. It may be a group having a group. In the latter case, the benzocyclobutenyl group-containing group has a binding site to another structure on the aromatic ring structure. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, an ether bond, a carbonyl bond, a substituted or unsubstituted aromatic ring group, or a group formed by combining two or more selected from these. . The aromatic ring structure, the alkylene group and the substituent which the aromatic ring group may have are, for example, -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ A halogen atom, and a substituent selected from the group consisting of a benzocyclobutenyl group-containing group (this substituent may be referred to as “substituent R ^B ”).

  In the present disclosure, the alkylene group may be a linear, branched or cyclic alkylene group. The linear, branched or cyclic alkylene group is an atomic group obtained by removing two hydrogen atoms from a linear or branched saturated hydrocarbon, or an atomic group obtained by removing two hydrogen atoms from a cyclic saturated hydrocarbon.

  In the present disclosure, “aromatic ring” refers to a ring exhibiting aromaticity. The aromatic ring may be, for example, an aromatic hydrocarbon such as benzene, naphthalene, anthracene, tetracene, fluorene or phenanthrene. Also, for example, pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzooxazole, benzooxadiazole, benzothiadiazole, benzotriazole, or benzo It may be an aromatic heterocycle such as thiophene.

  The aromatic ring may be a single ring such as benzene, for example, and may be a fused polycyclic aromatic hydrocarbon such as naphthalene or a fused polycyclic aromatic heterocycle such as quinoline.

  The aromatic ring may have, for example, a structure in which two or more selected from an independent single ring and a fused ring are bonded, such as biphenyl, terphenyl and triphenylbenzene.

  Examples of benzocyclobutenyl group-containing groups are listed below. The benzocyclobutenyl group-containing group is not limited to the following examples.

Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^g each independently represent a hydrogen atom or a substituent. l to m represent an integer, l is 0 or 1, n is 0 or 1, and m is 1 or more. The upper limit of m is determined according to the structure of Ar and the number of l.
Examples of the substituent that the aromatic ring may have include the above-mentioned substituent R ^B , and examples of the substituent when at least one of R ^{a to} R ^g is a substituent, the above-mentioned substituent R ^A Can be mentioned.

  An example of the group represented by Formula (4) is shown below. The benzocyclobutenyl group-containing group is not limited to the following examples.

Ar represents a substituted or unsubstituted aromatic ring, and R ^{a to} R ^g each independently represent a hydrogen atom or a substituent. l and m represent an integer, l is 0 or 1, and m is 1 or more. The upper limit of m is determined according to the structure of Ar and the number of l. a to d represent integers, a is 0 to 1, b is 0 to 20, c is 0 to 5, and d is 0 to 3.
Examples of the substituent that the aromatic ring may have include the above-mentioned substituent R ^B , and examples of the substituent when at least one of R ^{a to} R ^g is a substituent, the above-mentioned substituent R ^A Can be mentioned.

  An example of the group represented by Formula (5) is given below. The benzocyclobutenyl group-containing group is not limited to the following examples.

R ^a to R ^g each independently represent a hydrogen atom or a substituent.
Examples of the substituent when at least one of R ^{a to} R ^g is a substituent include the above-mentioned substituent R ^A.

  An example of the group represented by Formula (5) is given below. The benzocyclobutenyl group-containing group is not limited to the following examples.

R ^a to R ^g each independently represent a hydrogen atom or a substituent. m is an integer of 1 to 5; a to d represent integers, a is 0 to 1, b is 0 to 20, c is 0 to 5, and d is 0 to 3.
Examples of the substituent when at least one of R ^{a to} R ^g is a substituent include the above-mentioned substituent R ^A.

  Specific examples of the benzocyclobutenyl group-containing group are shown below, but are not limited to the following specific examples.

(Carbon-carbon unsaturated bond-containing group)
The carbon-carbon unsaturated bond group-containing group in the second charge transportable polymer is a group containing one or more carbon-carbon unsaturated bond groups. The carbon-carbon unsaturated bond group has a structure capable of reacting with at least a benzocyclobutenyl group to form a bond. According to one embodiment, the carbon-carbon unsaturated bond group is a group having a structure capable of causing Diels-Alder reaction. Examples of the carbon-carbon unsaturated bond group include a carbon-carbon double bond group and a carbon-carbon triple bond group, a carbon-carbon double bond group is preferable, and a vinyl group is more preferable. Hereinafter, the carbon-carbon unsaturated bond group-containing group will be described by taking the case where the carbon-carbon unsaturated bond group is a vinyl group as an example. In the embodiment where the carbon-carbon unsaturated bond group-containing group has a carbon-carbon unsaturated bond group other than a vinyl group, "vinyl group" is replaced with "a carbon-carbon unsaturated bond group other than a vinyl group" The explanation is applicable. For example, a vinyl group is represented by the following formula (2).

R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. The substituent is, for example, a substituent R ^A.

In one embodiment, from the viewpoint of obtaining sufficient curability, R ^{a to} R ^c are, for example, all hydrogen atoms; R ^a and R ^b are hydrogen atoms, R ^c is a methyl group; R ^a and R ^b Is a hydrogen atom, R ^c is a phenyl group; or, R ^a is a methyl group, and R ^b and R ^c are hydrogen atoms.

  The vinyl group-containing group is a group having a vinyl group. The second charge transporting polymer may have only one type of vinyl group-containing group or may have two or more types of vinyl group-containing groups. The vinyl group-containing group may contain only one, or two or more vinyl groups. When two or more are included, the two or more may be the same or different.

In one embodiment, the vinyl group-containing group may be, for example, a vinyl group itself. For example, the group represented by Formula (2) may be a vinyl group-containing group. In another embodiment, the vinyl group-containing group is a group having a substituted or unsubstituted aromatic ring structure and a vinyl group bonded to the aromatic ring structure directly or through a divalent linking group. It may be. In the latter case, the vinyl group-containing group has a binding site to another structure on the aromatic ring structure. Examples of the divalent linking group include a substituted or unsubstituted alkylene group, an ether bond, a carbonyl bond, a substituted or unsubstituted aromatic ring group, or a group formed by combining two or more selected from these. . The aromatic ring structure, the alkylene group and the substituent which the aromatic ring group may have are, for example, -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ A halogen atom, and a substituent selected from the group consisting of a vinyl group-containing group (this substituent may be referred to as “substituent R ^C ”).

  An example of the vinyl group-containing group is as follows. The vinyl group-containing group is not limited to the following examples.

Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. l to m represent an integer, l is 0 or 1, n is 0 or 1, and m is 1 or more. The upper limit of m is determined according to the structure of Ar and the number of l.
Examples of the substituent which the aromatic ring may have include the above-mentioned substituent R ^C , and examples of the substituent when at least one of R ^{a to} R ^c is a substituent, the above-mentioned substituent R ^A Can be mentioned.

  An example of the group represented by Formula (9) is given below. The vinyl group-containing group is not limited to the following examples.

Ar represents a substituted or unsubstituted aromatic ring, and R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. l and m represent an integer, l is 0 or 1, and m is 1 or more. The upper limit of m is determined according to the structure of Ar and the number of l. a to g represent integers, a is 0 to 20, b is 0 to 1, c is 0 to 20, d is 0 to 1, e is 0 to 1, f is 0 to 5, g is 0 to 1 is there.
Examples of the substituent which the aromatic ring may have include the above-mentioned substituent R ^C , and examples of the substituent when at least one of R ^{a to} R ^c is a substituent, the above-mentioned substituent R ^A Can be mentioned.

  An example of the group represented by Formula (10) is shown below. The vinyl group-containing group is not limited to the following examples.

R ^{a to} R ^c each independently represent a hydrogen atom or a substituent.
When at least one of R ^{a to} R ^c is a substituent, examples of the substituent include the above-mentioned substituent R ^A.

  An example of the group represented by Formula (10) is shown below. The vinyl group-containing group is not limited to the following examples.

R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. m is an integer of 1 to 5; a to g represent integers, a is 0 to 20, b is 0 to 1, c is 0 to 20, d is 0 to 1, e is 0 to 1, f is 0 to 5, g is 0 to 1 is there.
When at least one of R ^{a to} R ^c is a substituent, examples of the substituent include the above-mentioned substituent R ^A.

  Although the specific example of a vinyl group containing group is shown below, it is not limited to the following specific examples.

(Structure of charge transporting polymer)
The term “charge transporting polymer” described in the following description is a first charge transporting polymer having a benzocyclobutenyl group-containing group, and a second charge having a carbon-carbon unsaturated bond group-containing group Means each of the transportable polymer. Further, the term "polymerizable functional group" refers to the benzocyclobutenyl group-containing group possessed by the first charge transporting polymer and the carbon-carbon unsaturated bond group-containing group possessed by the second charge transporting polymer. I mean each.

  From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the generation of the polymerization reaction, the main skeleton of the charge transporting polymer and the polymerizable functional group are, for example, linear C 1-8 alkylene chains. Although it is preferable that it is connected, it does not specifically limit. Also, for example, when forming an organic layer on an electrode, from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO, the main skeleton of the charge transporting polymer and the polymerizable functional group are ethylene glycol chains, It is preferable that they are linked by a hydrophilic chain such as diethylene glycol chain. Furthermore, from the viewpoint of facilitating the preparation of the monomer used to introduce the polymerizable functional group, the charge transporting polymer is preferably polymerized with the end of the alkylene chain and / or the hydrophilic chain, ie, these chains The bond with the sexual functional group and / or the bond between these chain and the skeleton of the charge transport polymer may have an ether bond or an ester bond.

  The polymerizable functional group is preferably contained in large amounts in the charge transporting polymer from the viewpoint of contributing to the change in solubility. On the other hand, from the viewpoint of not interfering with the charge transportability, it is preferable that the amount contained in the charge transportable polymer is small. The content of the polymerizable functional group can be appropriately set in consideration of these.

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

The number of polymerizable functional groups per molecule of charge transportable polymer is the charge of the polymerizable functional group used to synthesize the charge transport polymer (for example, the charge of the monomer having the polymerizable functional group), each structure It can be determined as an average value using the charged amount of the monomer corresponding to the unit, the weight average molecular weight of the charge transporting polymer and the like. Further, the number of polymerizable functional groups is the ratio of the integral value of the signal derived from the polymerizable functional group in the ¹ H-NMR (nuclear magnetic resonance) spectrum of the charge transporting polymer to the integral value of the entire spectrum, charge transportability It can be calculated as an average value using the weight average molecular weight of the polymer and the like. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

  The charge transporting polymer may be linear or branched. The branched charge transporting polymer has a structure branched in three or more directions. According to one embodiment, the charge transporting polymer preferably includes at least a divalent structural unit L having charge transporting properties and a structural unit T constituting an end, and a trivalent or higher constituting a branch. The structural unit B may be further included. Further, according to one embodiment, the charge transporting polymer preferably contains at least a trivalent structural unit B having charge transporting property and a monovalent structural unit T constituting an end, and has a divalent structure. The unit L may further be included. The charge transporting polymer may contain only one type of each structural unit, or may contain multiple types of each. In the charge transporting polymer, each structural unit is bonded to each other at a “monovalent” to “trivalent or higher” bonding site.

  The following is mentioned as an example of the partial structure contained in a charge transportable polymer. The charge transporting polymer is not limited to one having the following partial structure. In the partial structure, “B” represents a structural unit B, “L” represents a structural unit L, and “T” represents a structural unit T. In the following, "*" represents a binding site to another structural unit. In the following partial structures, a plurality of L may be the same structural unit as one another or structural units different from one another. The same applies to T and B.

Examples of linear charge transporting polymers

Example of branched charge transporting polymer

  In the charge transporting polymer, the polymerizable functional group is introduced into the non-terminal portion (that is, the structural unit L or B) even though it is introduced to the terminal portion (that is, the structural unit T) of the charge transporting polymer Alternatively, they may be introduced into both the end and non-end portions. From the viewpoint of curability, it is preferably introduced to at least the terminal part, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced to only the terminal part. When the charge transporting polymer is branched, the polymerizable functional group may be introduced into the main chain of the charge transporting polymer or may be introduced into the side chain, and both the main chain and the side chain May be introduced in According to one embodiment, from the viewpoint of reactivity of charge transporting polymers, at least one of the first charge transporting polymer and the second charge transporting polymer has at least one polymerizable functional group at an end. Is preferred. Also, according to one embodiment, at least one of the benzocyclobutenyl group-containing groups is present at the end of the first charge transporting polymer, and at least one of the carbon-carbon unsaturated bond group-containing groups is the second. It is preferably present at the end of the charge transporting polymer of Each structural unit will be specifically described below.

(Structural unit L)
The structural unit L is a divalent structural unit having charge transportability. The structural unit L should just contain the atomic group which has the ability to transport an electric charge, and it is not specifically limited. For example, the structural unit L may be substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, bithiophene structure, fluorene structure, benbenzocyclobutene structure, biphenyl structure, terphenyl structure, naphthalene structure, anthracene structure, tetracene Structure, phenanthrene structure, dihydrophenanthrene structure, pyridine structure, pyrazine structure, quinoline structure, isoquinoline structure, quinoxaline structure, acridine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxadiazole structure, thiazole structure, thiadiazole Structure, triazole structure, benzothiophene structure, benzoxazole structure, benzoxadiazole structure, benzothiazole structure, benzothiadiazole structure, benzotriazole Concrete, and are selected from the structure containing one or two or more of these. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure. In addition, the benbenzocyclobutene structure is preferably a p-phenylene structure or an m-phenylene structure.

  In one embodiment, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, bithiophene structure, fluorene structure, benbenzocyclobutene structure, from the viewpoint of obtaining excellent hole transportability. And one or more structures selected from pyrrole structures, and more preferably one or more structures selected from substituted or unsubstituted aromatic amine structures, carbazole structures, thiophene structures, and fluorene structures It is further preferred to have one or more structures preferably selected from a substituted or unsubstituted aromatic amine structure and a carbazole structure.

  In another embodiment, the structural unit L is selected from a substituted or unsubstituted fluorene structure, a benbenzocyclobutene structure, a phenanthrene structure, a pyridine structure, and a quinoline structure from the viewpoint of obtaining excellent electron transportability. It is preferable to have the above structure.

  The specific structure of the structural unit L is not particularly limited, and examples thereof include the structures described in paragraph 0097 of WO 2010/140553.

(Structural unit T)
The structural unit T is a structural unit that constitutes an end of the charge transporting polymer. The structural unit T is not particularly limited, and is selected, for example, from a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure, and a structure containing one or more of them. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without reducing charge transportability. As to valences, the structural unit T may have the same structure as at least one of the structural units L and B or may have a different structure.

  In a preferred embodiment, the structural unit T preferably contains a structural unit having a polymerizable functional group. For example, the first charge transporting polymer has a structural unit T1 having a benzocyclobutenyl group-containing group. In addition, the second charge transporting polymer has a structural unit T2 having a carbon-carbon unsaturated bond group-containing group. Each of the first charge transporting polymer and the second charge transporting polymer may further have a structural unit T3 having no benzocyclobutenyl group-containing group and no carbon-carbon unsaturated bond group-containing group .

  The structural unit T1 can be represented by the following formula (3).

  T1 is a structure containing a benzocyclobutenyl group-containing group. The benzocyclobutenyl group-containing group described above may be T1, and as an example of T1, a group represented by the formula (4), a group represented by the formula (5), a table by the formula (6) And a group represented by Formula (7).

  The structural unit T2 can be represented by the following formula (8).

  T2 is a structure containing a carbon-carbon unsaturated bond group-containing group. The carbon-carbon unsaturated bond group-containing group described above may be T2, and as an example of T2, a group represented by Formula (9), a group represented by Formula (10), Formula (11) And groups represented by formula (12).

  The following is mentioned as a specific example of structural unit T3. However, structural unit T3 is not limited to the following.

R is each independently a hydrogen atom or a substituent, and the substituent is, for example, a substituent R ^A.

(Structural unit B)
The structural unit B is a trivalent or higher structural unit constituting a branched portion when the charge transporting polymer or oligomer has a structure branched in three or more directions. The structural unit B is preferably hexavalent or less, more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic device. The structural unit B is preferably a unit having charge transportability. For example, the structural unit B may be a substituted or unsubstituted aromatic amine structure, a carbazole structure, a fused polycyclic aromatic hydrocarbon structure, and one or two of them from the viewpoint of improving the durability of the organic electronic device. It is selected from structures containing more than species. With respect to other than valence, the structural unit B may have the same structure as the structural unit L or may have a different structure, and even if it has the same structure as the structural unit T, Or you may have a different structure.

  Although there are no particular limitations on the specific structure of the structural unit B, for example, the structure described in paragraph 0091 of WO 2010/140553 can be mentioned.

(Number average molecular weight)
The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of the solubility in a solvent, the film forming property and the like. From the viewpoint of excellent charge transportability, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. In one embodiment, the number average molecular weight is preferably 18,000 or more, more preferably 20,000 or more, and still more preferably 25,000 or more. On the other hand, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. 000 or less is more preferable.

(Weight average molecular weight)
The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of the solubility in a solvent, the film forming property and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more from the viewpoint of excellent charge transportability. On the other hand, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. 000 or less is more preferable, and 300,000 or less is especially preferable. In one embodiment, the weight average molecular weight of the charge transporting polymer is preferably 200,000 or less.

  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.

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 under the following conditions.
Liquid delivery pump: L-6050 Hitachi High-Technologies Corporation UV-Vis detector: L-3000 Hitachi High-Technologies Corporation column: Gelpack (registered trademark) GL-A 160 S / GL-A 150 S Hitachi Chemical Co., Ltd. Eluent: THF (HPLC For use, stabilizer not included) Wako Pure Chemical Industries, Ltd. Flow rate: 1 mL / min
Column temperature: Room temperature molecular weight standard substance: Standard polystyrene

(Proportion of structural unit)
When the charge transporting polymer contains the structural unit L, the proportion of the structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more, based on all structural units, from the viewpoint of obtaining sufficient charge transportability. And 30 mol% or more is more preferable. Further, the ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less, in consideration of the structural unit T and the structural unit B introduced as necessary.

  The ratio of the structural unit T contained in the charge transportable polymer is based on all structural units from the viewpoint of improving the properties of the organic electronic device, or from the viewpoint of suppressing the increase in viscosity and favorably synthesizing the charge transportable polymer. 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is still more preferable. The proportion of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and still more preferably 50 mol% or less from the viewpoint of obtaining sufficient charge transportability.

  When the charge transporting polymer contains the structural unit B, the proportion of the structural unit B is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total structural units, from the viewpoint of improving the durability of the organic electronic device. Preferably, 10 mol% or more is more preferable. Further, the proportion of the structural unit B is preferably 50 mol% or less, and 40 mol% or less, from the viewpoint of suppressing the increase in viscosity and performing synthesis of the charge transporting polymer favorably, or from the viewpoint of obtaining sufficient charge transporting properties. Is more preferable, and 30 mol% or less is more preferable.

  From the viewpoint of efficiently curing the charge transporting polymer, the proportion of the polymerizable functional group is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and 1 mol%, based on the total structural units. The above is more preferable. The proportion of the polymerizable functional group is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, particularly preferably 5 mol% or less, from the viewpoint of obtaining good charge transportability. Preferably, 2.5 mol% or less is very preferable. In addition, "the ratio of a polymerizable functional group" here means the ratio of the structural unit which has a polymerizable functional group. By combining the first charge transporting polymer and the second charge transporting polymer, sufficient insolubilization is achieved even when the proportion of the polymerizable functional group contained in each charge transporting polymer is small. it can.

  When the charge transporting polymer has a polymerizable functional group at the end, the ratio of the structural unit (structural unit T1 or structural unit T2) having the polymerizable functional group is all from the viewpoint of efficiently curing the charge transporting polymer. 1 mol% or more is preferable on the basis of the structural unit T of a terminal, 1.5 mol% or more is more preferable, and 2 mol% or more is still more preferable. Further, the proportion of the structural unit having a polymerizable functional group (structural unit T1 or structural unit T2) is preferably 30 mol% or less, more preferably 20 mol% or less, from the viewpoint of obtaining good charge transportability. It is more preferable that it is mol% or less.

  Considering the balance of charge transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit L and the structural unit T is preferably L: T = 100: 1 to 70, more preferably 100: 3 to 50. Preferably, 100: 5 to 30 is more preferable. When the charge transporting polymer further contains the structural unit B, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is L: T: B = 100: 10 to 200: 10 to 100. 100: 20 to 180: 20 to 90 are more preferable, and 100: 40 to 160: 30 to 80 are more preferable.

The proportion of structural units can be determined using the amount of monomer corresponding to each structural unit used to synthesize the charge transporting polymer. The proportion of structural units can be calculated as an average value using the integral value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

(Degree of polymerization)
The polymerization degree (number of units of structural units) of the charge transporting polymer is preferably 5 or more, more preferably 10 or more, and still 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 still 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 weight average molecular weight of the charge transporting polymer, the molecular weight of the structural unit, and the ratio of the structural unit.

  In a preferred embodiment, the charge transporting polymer comprises a substituted or unsubstituted aromatic amine structure, a carbazole structure, a thiophene structure, and a fluorene structure from the viewpoint of having high hole injecting property, hole transporting property and the like. It is preferred to have one or more structures selected from the group. Further, in a particularly preferred embodiment, the charge transporting polymer is mainly composed of a structural unit having an aromatic amine structure and / or a structural unit having a carbazole structure, from the viewpoint of having high hole injection property, hole transport property and the like. It is preferable that it is a compound made into this structural unit (main frame). For example, the proportion of the structural unit having an aromatic amine structure and the structural unit having a carbazole structure is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more. The upper limit is 100 mol%. The ratio here is the structural unit of the sum of structural unit L and structural unit B (in the case where only one of the charge transporting polymers is contained, the structural unit of the one concerned). The ratio of the total of structural units having an aromatic amine structure contained in the structural unit L and structural unit B and structural units having a carbazole structure, based on

(Production method)
The charge transporting polymer can be produced by various synthesis methods and is not particularly limited. For example, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Stille coupling, Buchwald-Heartwig coupling can be used. Suzuki coupling causes a Pd-catalyzed cross coupling reaction to occur between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings.

  In the coupling reaction, for example, a Pd (0) compound, a Pd (II) compound, a Ni compound or the like is used as a catalyst. Alternatively, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like as a precursor with a phosphine ligand can also be used. For the synthesis method of the charge transporting polymer, for example, the description of WO 2010/140553 can be referred to.

[Dopant]
The charge transportable material may contain any additive, and may further contain, for example, a dopant. The dopant exerts a doping effect by being added to the charge transportable material to improve charge transportability. There is no particular limitation as long as it can be obtained. For doping, there are p-type doping and n-type doping, and in p-type doping, a substance that functions as an electron acceptor is used as a dopant, and in n-type doping, a substance that functions as an electron donor as a dopant is used. It is preferable to perform p-type doping to improve hole transportability and n-type doping to improve electron transportability. The dopant used for the charge transportable material may be a dopant that exhibits either p-type doping or n-type doping effect. Also, one dopant may be added alone, or a plurality of dopants may be mixed and added.

The dopant used for p-type doping is an electron accepting compound, and examples thereof include Lewis acids, protonic acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, as a Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SfF ₅ , BF ₅ , BCl ₃ , BBr ₃ etc .; As a protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , Inorganic acids such as HClO ₄ , benbenzocyclobutenesulfonic acid, p-toluenesulfonic acid, dodecylbenbenzocyclobutenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfone Organic acids such as acid, vinyl phenyl sulfonic acid, camphor sulfonic acid; transition metal compounds such as FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; as ionic compounds Is tetrakis (pentafluorophenyl) borate Ion, tris (trifluoromethanesulfonyl) Mechidoion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF ₆ ^- (hexafluoro arsenic acid ions), BF ₄ ^- (tetrafluoroborate), PF ₆ ^- (hexa A salt having a perfluoro anion such as fluorophosphate ion), a salt having a conjugated base of the protonic acid as an anion; a halogen compound such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF, etc. Examples of the π-conjugated compound include TCNE (tetracyanoethylene) and TCNQ (tetracyanoquinodimethane). Moreover, it is also possible to use the electron-accepting compound as described in JP-A-2000-36390, JP-A-2005-75948, JP-A-2003-213002, and the like. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like.

The dopant used for n-type doping is an electron donative compound, for example, alkali metals such as Li and Cs, alkaline earth metals such as Mg and Ca, alkali metals such as LiF and Cs ₂ CO ₃ , and / or Or salts of alkaline earth metals, metal complexes, electron donating organic compounds and the like.

  In the dopant, the ionic compound also functions as a polymerization initiator. The charge transportable material containing the first charge transportable polymer and the second charge transportable polymer can be insolubilized without using a polymerization initiator, but if necessary, it can be charge transportable. Ion compounds may be included for the purpose of improvement.

[Other optional ingredients]
The charge transporting material may further contain a charge transporting low molecular weight compound, another polymer and the like.

[Content]
The total content of the first charge transportable polymer and the second charge transportable polymer in the charge transportable material is 50% by mass relative to the total mass of the charge transportable material from the viewpoint of obtaining good charge transportability. % Or more is preferable, 70% by mass or more is more preferable, and 80% by mass or more is more preferable. The upper limit of the total content of the first charge transporting polymer and the second charge transporting polymer is not particularly limited, and may be 100% by mass. In consideration of including an additive such as a dopant, the content of the charge transporting polymer may be, for example, 95% by mass or less and 90% by mass or less.

  When the dopant is contained, its content is preferably 0.01% by mass or more with respect to the total mass of the charge transportable material from the viewpoint of improving the charge transportability of the charge transportable material, 0.1% by mass The above is more preferable, and 0.5 mass% or more is more preferable. On the other hand, the content of the dopant is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less from the viewpoint of preventing roughness of the film surface, unevenness in film thickness and the like.

<Ink composition>
In one embodiment, the ink composition contains the charge transporting material and a solvent capable of dissolving or dispersing the material. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

[solvent]
As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. Examples of organic solvents include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; and aromatic hydrocarbons such as benbenzocyclobutene, toluene, xylene, mesitylene, tetralin and diphenylmethane Aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenbenzocyclobutene, 1,3-dimethoxybenbenzocyclobutene, anisole, phenetole, 2 -Aromatic ethers such as methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole; ethyl acetate, Aliphatic esters such as n-butyl acid, ethyl lactate and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, aromatic esters such as n-butyl benzoate; N, Amide solvents such as N-dimethylformamide, N, N-dimethylacetamide and the like; dimethylsulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like.

[Additive]
The ink composition may further contain an additive as an optional component. As the additive, for example, a polymerization inhibitor, a stabilizer, a thickener, a gelling agent, a flame retardant, an antioxidant, a reduction inhibitor, an oxidizing agent, a reducing agent, a surface modifier, an emulsifier, an antifoamer, Dispersants, surfactants and the like can be mentioned.

[Content]
The content of the solvent in the 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 transporting polymer to the solvent is 0.1% by mass or more, and more preferably 0.2% by mass or more. More preferably, In addition, the content of the solvent 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 still more preferably 10% by mass or less .

<Organic layer>
In one embodiment, the organic layer is a layer formed using the charge transporting material or the ink composition. By using the ink composition, the organic layer can be formed favorably and simply by a coating method. Coating methods include, for example, spin coating method; cast method; immersion method; plate printing method such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing, gravure printing, etc .; Known methods such as plateless printing can be mentioned. When forming an organic layer by the apply | coating method, the organic layer (application layer) obtained after application may be dried using a hotplate or oven, and a solvent may be removed.

  Since the charge transporting polymer has a polymerizable functional group, the polymerization reaction of the charge transporting polymer can be advanced by light irradiation, heat treatment or the like to change the solubility of the organic layer. By laminating the organic layer whose solubility is changed, it is possible to easily make the organic electronic device multilayer. For the method of forming the organic layer, for example, the description of International Publication WO 2010/140553 can be referred to.

  The charge transporting material or the ink composition used to form an organic layer has a first charge transporting polymer having a benzocyclobutenyl group-containing group and a carbon-carbon unsaturated bond group-containing group And a second charge transporting polymer. Therefore, the Diels-Alder reaction between the first charge transporting polymer and the second charge transporting polymer proceeds by performing heat treatment after the application of the charge transporting material or the ink composition, as compared with the prior art, The organic layer can be sufficiently insolubilized (cured). For example, after the charge transporting material or the ink composition is applied, the organic layer can be sufficiently cured by heating at 120 ° C. or higher. In one embodiment, the heating temperature at the time of curing is preferably 160 ° C. or more, more preferably 180 ° C. or more. It is also possible to heat at a higher temperature, for example, 200 ° C. or more is preferable, 215 ° C. or more is more preferable, and 230 ° C. or more is more preferable. The heating temperature is preferably 350 ° C. or less, more preferably 250 ° C. or less, and still more preferably 200 ° C. or less, in consideration of the influence of heating on the organic layer, the substrate, and the like. The heating time is not particularly limited, but it is preferable to adjust within 60 minutes, and more preferably within 30 minutes, from the viewpoint of suppressing the performance decrease of the organic layer due to heating.

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

<Organic electronics device>
In one embodiment, the organic electronic device comprises at least one or more of the organic layers. As an organic electronics element, an organic EL element, an organic photoelectric conversion element, an organic transistor etc. are mentioned, for example. The organic electronic device preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

<Organic EL element>
In one embodiment, an organic EL element has at least one or more of the organic layers. The organic EL device generally comprises a light emitting layer, an anode, a cathode, and a substrate, and as necessary, other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, etc. Have. Each layer may be formed by a vapor deposition method or may be formed by a coating method. The organic EL device preferably has the organic layer as a light emitting layer or a functional layer, more preferably as a functional layer, and still more preferably as at least one of a hole injecting layer and a hole transporting layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the organic EL element. The organic EL device of FIG. 1 is a device having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6, a light emitting layer 1, an electron transport layer 7, an electron injection layer 5 and a cathode 4. In this order. Each layer will be described below.

[Emitting layer]
As materials used for the light emitting layer, light emitting materials such as low molecular weight compounds, polymers, and dendrimers can be used. The polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. As the light emitting material, a fluorescent material, a phosphorescent material, a heat activated delayed fluorescent material (TADF) and the like can be mentioned.

  Fluorescent materials such as perylene, coumarin, rubrene, quinacdoline, stilbene, dyes for dye laser, aluminum complexes, low molecular weight compounds such as derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer And polymers such as fluorene-triphenylamine copolymer and derivatives thereof; and mixtures thereof.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. As the Ir complex, for example, FIrpic (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate which emits blue light, Ir (ppy) ₃ (Fac tris) which emits green light (2-phenylpyridine) iridium), and red emission _(btp) 2 Ir (acac) (bis [2- (2'-benzo [4,5-α] thienyl) pyridinato -N, ^{C 3]} iridium (acetyl -Acetonate)), Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium) and the like. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 13, 17, 18-octaethyl-21H, 23H-phorphine platinum) which emits red light.

  When the light emitting layer contains a phosphorescent material, it is preferable to further contain a host material in addition to the phosphorescent material. As a host material, a low molecular weight compound, a polymer or a dendrimer can be used. As low molecular weight compounds, for example, CBP (4,4′-bis (9H-carbazol-9-yl) biphenyl), mCP (1,3-bis (9-carbazolyl) benbenzocyclobutene), CDBP (4,4, 4'-bis (carbazol-9-yl) -2,2'-dimethylbiphenyl), derivatives thereof and the like, and as the polymer, the charge transporting material, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof It can be mentioned.

  As a heat activation delayed fluorescence material, for example, Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012) Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012). Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014) and the like.

[Hole injection layer, hole transport layer]
In FIG. 1, at least one of the hole injection layer 3 and the hole transport layer 6 may be an organic layer formed using the charge transporting material or the ink composition, but the organic EL device The structure is not limited to this. Organic layers other than the hole injection layer and the hole transport layer may be formed using the charge transport material.

  The charge transporting material is preferably used as a hole injecting material and / or a hole transporting material. For example, the charge transporting material is preferably used as a material constituting at least one of a hole injecting layer and a hole transporting layer, and more preferably used as a material of at least a hole transporting layer. As described above, these layers can be easily formed by using the ink composition containing the charge transporting material.

  For example, when the organic EL element has an organic layer formed by using the charge transporting material as a hole transporting layer and further has a hole injecting layer, known materials can be used for the hole injecting layer. . When the organic EL element has an organic layer formed using the charge transporting material as a hole injecting layer and further has a hole transporting layer, known materials can be used for the hole transporting layer. .

  Materials usable for the hole injection layer and the hole transport layer include aromatic amine compounds (N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (α-NPD) And aromatic diamines), phthalocyanine compounds, and thiophene compounds.

[Electron transport layer, electron injection layer]
Materials used for the electron transport layer and the electron injection layer include, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, fused ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides And fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. Further, the charge transporting material can also be used.

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

[anode]
As the anode material, for example, a metal (for example, Au) or another conductive material is used. Other materials include, for example, oxides (eg, ITO: indium oxide / tin oxide), conductive polymers (eg, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[substrate]
A glass substrate, a resin substrate, etc. can be used as a board | substrate, A resin substrate is used preferably. The substrate is preferably transparent and is preferably a flexible substrate having flexibility. Quartz glass, a light transmitting resin film, etc. are preferably used.

  As the resin film, for example, a film composed of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc. It can be mentioned.

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

[Sealing]
The organic EL element may be sealed in order to reduce the influence of external air and prolong its life. As a material used for sealing, plastic films such as glass, epoxy resin, acrylic resin, polyethylene terephthalate, polyethylene naphthalate and the like or inorganic substances such as silicon oxide and silicon nitride can be used, but it is not limited thereto Absent. The method of sealing is also not particularly limited, and can be performed by a known method.

[Emitting color]
The luminescent color of 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, in-car lighting, clocks, backlights of liquid crystals, and the like.

  As a method of forming a white organic EL element, it is possible to use a method in which a plurality of light emitting materials are used to simultaneously emit light of a plurality of light emitting colors for color mixing. The combination of plural emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths such as blue and yellow, yellow green and orange, etc. Can be mentioned. Control of the luminescent color can be performed by adjusting the type and amount of the luminescent material.

<Display element, lighting device, display device>
In one embodiment, the display element includes the organic EL element. For example, a color display element can be obtained by using an organic EL element as an element corresponding to each pixel of red, green and blue (RGB). Image forming methods include a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged and driven in each element.

In one embodiment, the lighting device includes the organic EL element.
Furthermore, in one embodiment, the display device includes the lighting device and a liquid crystal element as a display unit. For example, the display device can be a display device using the lighting device as a backlight and a known liquid crystal element as a display means, that is, a liquid crystal display device.

  Embodiments of the present invention will be specifically described by way of examples. Embodiments of the present invention are not limited to the following examples.

Synthesis Example of Monomer
Although the synthesis example of a monomer is shown below, this invention is not limited to the following synthesis examples.

Synthesis Example 1
Monomer T1-2 having the following structure was synthesized by the following method. In detail, it synthesize | combined by the following route.

  Under nitrogen atmosphere, 5-bromo-1-pentene (7.45 g, 50 mmol) and tetrahydrofuran (20 mL) were mixed in a 300 mL three-necked flask to obtain a solution. To the resulting solution was added dropwise 0.5 M of 9-BBN / THF solution (9-borabicyclo [3.3.1] nonane tetrahydrofuran solution) (100 mL) over 1 hour, and then stirred at room temperature for 12 hours. Monomer T1-1 (3.66 g, 20 mmol), (diphenylphosphinoferrocene) palladium dichloride (0.82 g), tetrahydrofuran (32 mL), and 3 M aqueous solution of sodium hydroxide (27 mL) were added to the reaction solution obtained. Mix and reflux for 4 hours. After completion of the reaction, the obtained solution was cooled to room temperature, hexane (40 mL) was added, hydrogen peroxide water (6 mL) was slowly added dropwise with ice cooling, and the mixture was stirred for 1 hour. After separation of the reaction solution, the organic layer was washed 5 times with ion-exchanged water (50 mL). The obtained organic layer was dried over sodium sulfate and then purified by column chromatography using hexane as a developing solvent and silica gel as a filler to obtain Intermediate A (3.80 g, 15 mmol).

  Intermediate A (3.80 g, 15 mmol), 4-bromophenol (3.89 g, 22.5 mmol), tetrabutylammonium bromide (0.16 g, 0.5 mmol) in a 50 mL two-necked flask under a nitrogen atmosphere 50% aqueous potassium hydroxide solution (6.7 g) and toluene (20 mL) were mixed and refluxed for 6 hours. After completion of the reaction, the obtained solution was washed three times with ion exchanged water (10 mL). After drying the obtained organic layer with sodium sulfate, the monomer T1-2 is purified by column chromatography using a hexane / ethyl acetate (95/5) mixed solvent as a developing solvent and silica gel as a filler. (4.14 g, 12 mmol).

(Composition example 2)
Monomer T2-4 having the following structure was synthesized by the following method. In detail, it synthesize | combined by the following route.

  Under a nitrogen atmosphere, magnesium (0.53 g, 22 mmol) and tetrahydrofuran (10 mL) were charged into a 100 mL three-necked flask. 8-bromo-1-octene (3.82 g, 20 mmol) dissolved in tetrahydrofuran (20 mL) was added dropwise over 20 minutes. To the resulting solution was added 4-bromobenzyl bromide (5.50 g, 22 mmol), and the mixture was stirred at room temperature for 1 hour and then heated to reflux for 3 hours. The resulting reaction solution was washed three times with ion-exchanged water (10 mL). After drying over sodium sulfate, the sodium sulfate was filtered and the solvent was evaporated. Purification by column chromatography gave monomer T2-4 (2.81 g, 10 mmol).

Synthesis Example of Charge-Transporting Polymer
(Preparation of Pd catalyst)
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature and anisole (15 mL) was added and stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, anisole (5 mL) was added and stirred for 5 minutes. The solutions were mixed and stirred at room temperature for 30 minutes to become catalyst. All solvents were used after degassing with nitrogen bubbles for over 30 minutes.

(Synthesis of Charge Transport Polymer A)
In a three-necked round bottom flask, the following monomer L1 (10.0 mmol), the following monomer B1 (5.0 mmol), the following monomer T1-2 (0.125 mmol), the following monomer T3 (4.875 mmol), toluene (42.8 mL) And methyltri-n-octyl ammonium chloride (67.2 mg) were added, and further, the prepared Pd catalyst solution (15.0 mL) was added. After stirring for 30 minutes, 3 M aqueous potassium hydroxide solution (13.5 mL) was added. All solvents were used after degassing with nitrogen bubbles for over 30 minutes. The mixture was heated to reflux for 2 hours. All operations up to this point were performed under a nitrogen stream.

  After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with butyl acetate to obtain a precipitate. The obtained precipitate is collected by suction filtration, dissolved in toluene, a metal adsorbent ("Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer" manufactured by Strem Chemicals, 200 mg per 100 mg of precipitate) is added, Stir overnight. After completion of the stirring, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was concentrated by a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The resulting precipitate was dried under vacuum to obtain charge transporting polymer A.

  The number average molecular weight of the obtained charge transporting polymer A was 30,799, and the weight average molecular weight was 97,707. The charge transporting polymer A has a structural unit L1, a structural unit B1, a structural unit T1-2, and a structural unit T-3, and the ratio (molar ratio) of each structural unit is 50.0%, 25. 0%, 0.63% and 24.38%.

(Synthesis of charge transporting polymer B)
In a three-necked round bottom flask, the monomer L1 (10.0 mmol), the monomer B1 (5.0 mmol), the following monomer T2-4 (0.125 mmol), the monomer T3 (4.875 mmol), toluene (42.8 mL) And methyltri-n-octyl ammonium chloride (67.2 mg) were added, and further, the prepared Pd catalyst solution (15.0 mL) was added. Thereafter, in the same manner as in the synthesis of the charge transporting polymer A, a charge transporting polymer B was obtained.

  The number average molecular weight of the obtained charge transporting polymer B was 29,012, and the weight average molecular weight was 91,952. The charge transporting polymer B has the structural unit L1, the structural unit B1, the structural unit T2-4, and the structural unit T3, and the ratio (molar ratio) of each structural unit is 50.0%, 25.0% , 0.63% and 24.38%.

(Synthesis of Charge Transport Polymer C)
In a three-necked round bottom flask, the monomer L1 (10.0 mmol), the monomer B1 (5.0 mmol), the monomer T1-2 (0.25 mmol), the monomer T3 (4.75 mmol), and toluene (42.7 mL) ), Methyltri-n-octyl ammonium chloride (67.2 mg) was added, and further, the prepared Pd catalyst solution (15.0 mL) was added. Thereafter, in the same manner as in the synthesis of the charge transporting polymer A, a charge transporting polymer C was obtained.

  The number average molecular weight of the obtained charge transporting polymer C was 56, 144, and the weight average molecular weight was 112, 751. The charge transporting polymer C has a structural unit L1, a structural unit B1, a structural unit T1-2, and a structural unit T3, and the ratio (molar ratio) of each structural unit is 50.0%, 25.0% , 1.25% and 23.75%.

(Synthesis of charge transporting polymer D)
In a three-necked round-bottom flask, the monomer L1 (10.0 mmol), the monomer B1 (5.0 mmol), the monomer T2-4 (0.25 mmol), the monomer T3 (4.75 mmol), and toluene (80.1 mL) ), Methyltri-n-octyl ammonium chloride (67.2 mg) was added, and further, the prepared Pd catalyst solution (15.0 mL) was added. Thereafter, charge transportable polymer D was obtained in the same manner as in the synthesis of charge transportable polymer A.

  The number average molecular weight of the obtained charge transporting polymer D was 55,718, and the weight average molecular weight was 112,656. The charge transporting polymer 4 has a structural unit L1, a structural unit B1, a structural unit T2-4, and a structural unit T3, and the ratio (molar ratio) of each structural unit is 25.0%, 50.0% , 1.25% and 23.75%.

<Evaluation of solvent resistance>
An ink composition containing charge transport polymer A and charge transport polymer B, and an ink composition containing charge transport polymer C and charge transport polymer D, so that the film thickness becomes 60 to 80 nm An organic layer was formed. The solvent resistance (insolubilizing effect) of the organic layer was evaluated by determining the effect of improving the residual film rate by the compounding.

Comparative Example 1
Charge transport polymer A (10.0 mg) was dissolved in toluene (2,000 μL) to obtain a coating solution (ink composition). The coating solution was spin coated on a quartz substrate at 3,000 rpm. Next, on a hot plate, the quartz substrate was heated at 220 ° C. for 30 minutes to polymerize the charge transporting polymer A to form an organic layer. Thereafter, the quartz substrate having the organic layer formed on the surface was immersed in toluene (25 ° C.) for 1 minute. From the ratio of the absorbance (Abs) of the absorption maximum (λmax) in the UV-vis spectrum of the organic layer before and after the immersion, the residual film ratio was 74.7%. The UV-vis spectrum was measured using a spectrophotometer ("U-3900H" manufactured by Hitachi High-Technologies Corporation) in a wavelength range of 300 to 500 nm.

Comparative Example 2
A polymer layer was formed in the same manner as in Comparative Example 1 except that the charge transporting polymer B (10.0 mg) was used instead of the charge transporting polymer A, and the residual film ratio was measured. The residual film rate was 40.2%.

Example 1
Charge transport polymer A (1.0 mg) and charge transport polymer B (9.0 mg) were dissolved in toluene (2,000 μL) to obtain a coating solution (ink composition). The coating solution was spin coated on a quartz substrate at 3,000 rpm. Next, on a hot plate, the quartz substrate was heated at 220 ° C. for 30 minutes to polymerize the charge transporting polymer A and the charge transporting polymer B to form an organic layer. It was 21.8% when the effect by the mixing | blending of the organic layer was evaluated by the following method.

(1) The "remaining film rate (%) contributed by the charge transporting polymer A" corresponds to the remaining film rate of the organic layer formed using the solution containing only the charge transporting polymer A, the charge in the coating solution It was calculated as a value obtained by multiplying the ratio of the mass of charge transport polymer A to the total mass of transport polymer A and charge transport polymer B.

(2) In the same manner as in the above (1), "the residual film ratio (%) contributed by the charge transporting polymer B" was determined. That is, the residual film ratio to which the charge transporting polymer (B) contributes was calculated by the same method as the above (1) except that the charge transporting polymer A was replaced with the charge transporting polymer B.

(3) The "presumed residual film ratio (%)" was calculated by adding the residual film ratio to which the charge transporting polymer A contributes and the residual film ratio to which the charge transporting polymer B contributes. When the charge transport polymer A and the charge transport polymer B are blended to prepare a coating solution, the charge transport polymer A and the charge transport polymer B do not interact with each other when heating and curing the coating solution. If it exists, the residual film ratio of the organic layer after curing is considered to be assumed as a value obtained by adding the residual film ratio to which the charge transporting polymer A contributes and the residual film ratio to which the charge transporting polymer B contributes.

(4) It calculated by taking the difference of the residual film rate which measured "the effect (%) by mixing | blending", and the residual film rate assumed.

[Examples 2 to 5]
An organic layer was formed in the same manner as in Example 1 except that the charge transport polymers A and B were used so that the total amount would be 10.0 mg in the compounding ratio shown in Table 1, and the effect of the compounding was evaluated. .

Comparative Example 3
An organic layer was formed in the same manner as in Comparative Example 1 except that the charge transporting polymer C (10.0 mg) was used instead of the charge transporting polymer A, and the residual film ratio was measured. The residual film rate was 87.6%.

Comparative Example 4
An organic layer was formed in the same manner as in Comparative Example 1 except that the charge transporting polymer D (10.0 mg) was used instead of the charge transporting polymer A, and the residual film ratio was measured. The residual film rate was 72.8%.

[Examples 6 to 10]
An organic layer is formed in the same manner as in Example 1 except that the charge transporting polymers C and D are used so that the total amount is 10.0 mg at the compounding ratio shown in Table 2, and the residual film rate is improved. The effect was evaluated.

The evaluation results of the effects of the formulation are shown in Tables 1 and 2 below.

  The effect by the combination was obtained for all the organic layers of Examples 1 to 5 and Examples 6 to 10. From this, it is understood that the solvent resistance of the organic layer can be enhanced by using the charge transporting material containing the first charge transporting polymer and the second charge transporting polymer.

<Evaluation of fluorescence spectrum>
With respect to the organic layer formed using the ink composition containing the charge transporting polymer C and the charge transporting polymer D, the change of the fluorescence spectrum upon curing was evaluated.

[Reference Examples 1 to 7]
An organic layer was formed in the same manner as in Examples 6 to 10 and Comparative Examples 3 and 4 except that the organic layer was left in the atmosphere at room temperature of 25 ° C. for 60 minutes without heating, and the fluorescence spectrum was measured. The fluorescence spectrum was measured under conditions of excitation light of 380 nm and a wavelength range of 400 to 600 nm using a spectrofluorimeter ("F-7000" manufactured by Hitachi High-Technologies Corporation).

  FIG. 2 shows the fluorescence spectrum, and FIG. 3 shows the difference spectrum between the fluorescence spectrum measured in Reference Example 1 and the fluorescence spectrum measured in Reference Example 5. Even when the mixing ratio of the charge transporting polymer C and the charge transporting polymer D was changed, there was almost no change in the fluorescence spectrum.

[Examples 11 to 15 and Comparative Examples 5 and 6]
An organic layer was formed in the same manner as in Examples 6 to 10 and Comparative Examples 3 and 4 except that heating was performed under a nitrogen atmosphere at 230 ° C. for 60 minutes, and a fluorescence spectrum was measured in the same manner as in the reference example. did.

  FIG. 4 shows the fluorescence spectrum, and FIG. 5 shows the difference spectrum between the fluorescence spectrum measured in Example 11 and the fluorescence spectrum measured in Example 15. The fluorescence spectrum changed depending on the compounding ratio of the charge transporting polymer C and the charge transporting polymer D. From the difference spectrum between the fluorescence spectrum measured in Example 11 and the fluorescence spectrum measured in Example 15, a change having a peak at 476 nm was confirmed.

  Table 3 shows the spectral intensity at 475 nm of each organic layer, and further shows the difference between the spectral intensity and the spectral intensity at 475 nm of the organic layers obtained in Reference Examples 1 to 7.

  The result was obtained that the change in the fluorescence spectrum is smaller as the blending ratio of the charge transporting polymer D is higher. From this, it is understood that the change of the fluorescence spectrum can be controlled by adjusting the content of the benzocyclobutenyl group-containing group and the carbon-carbon unsaturated bond group-containing group in the charge transporting material.

  The effects of the embodiment of the present invention have been described above using the examples. In addition to the charge transporting polymer used in the examples, the first charge transporting polymer having a benzocyclobutenyl group-containing group and the second one having a carbon-carbon unsaturated bond group-containing group as described above A charge transportable material containing a charge transportable polymer can exhibit a higher insolubilizing effect than using any of the charge transportable polymers alone.

  According to one embodiment, the charge transport material comprising the first charge transport polymer and the second charge transport polymer is a material suitable for a wet process and the formation of an organic layer using a wet process Can be used preferably. Further, according to one embodiment, the organic layer formed by using the charge transporting material is a layer suitable for the lower layer of the multilayer structure, and can be preferably used for the production of an organic electronic device having a multilayer structure.

REFERENCE SIGNS LIST 1 light emitting layer 2 anode 3 hole injection layer 4 cathode 5 electron injection layer 6 hole transport layer 7 electron transport layer 8 substrate

Claims (15)

  Charge transporting property comprising a first charge transporting polymer having at least one benzocyclobutenyl group-containing group and a second charge transporting polymer having at least one carbon-carbon unsaturated bond group-containing group material.   The charge transportable material according to claim 1, wherein the first charge transportable polymer and the second charge transportable polymer each have a branched structure in three or more directions.   The first charge transporting polymer and the second charge transporting polymer are each one or more selected from the group consisting of substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, and fluorene structure The charge transportable material according to claim 1, having a structure.   At least one of the one or more benzocyclobutenyl group-containing groups is present at the end of the first charge transportable polymer, and at least one of the one or more carbon-carbon unsaturated bond group-containing groups is the first one The charge transportable material according to any one of claims 1 to 3, which is present at an end of the charge transportable polymer of 2. The charge transportable material according to any one of claims 1 to 4, wherein the benzocyclobutenyl group-containing group contains a group represented by the following formula (4).
(Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^g each independently represent a hydrogen atom or a substituent. 1 to m are integers. L is 0 or 1, n is 0 or 1, and m is 1 or more.) The charge transportable material according to any one of claims 1 to 5, wherein the carbon-carbon unsaturated bond group-containing group contains a group represented by the following formula (9).
(Ar represents a substituted or unsubstituted aromatic ring, X represents a divalent linking group, and R ^{a to} R ^c each independently represent a hydrogen atom or a substituent. 1 to m are integers. L is 0 or 1, n is 0 or 1, and m is 1 or more.)   The charge transporting material according to any one of claims 1 to 6, which is a hole injecting material or a hole transporting material.   An ink composition comprising the charge transporting material according to any one of claims 1 to 7 and a solvent.   An organic electronic device having an organic layer formed using the charge transportable material according to any one of claims 1 to 7 or the ink composition according to claim 8.   The organic electroluminescent element which has an organic layer formed using the charge transportable material of any one of Claims 1-7, or the ink composition of Claim 8.   The organic electroluminescent device according to claim 10, further comprising a flexible substrate.   The organic electroluminescent device according to claim 10, further comprising a resin substrate.   The display element provided with the organic electroluminescent element of any one of Claims 10-12.   A lighting device comprising the organic electroluminescent device according to any one of claims 10 to 12.   The display apparatus provided with the illuminating device of Claim 14, and a liquid crystal element as a display means.