阅读说明：本技术 有机电子材料及电荷传输性聚合物的制造方法 (Organic electronic material and method for producing charge-transporting polymer ) 是由 加茂和幸 福岛伊织 石塚健一 宫贵纪 于 2019-04-26 设计创作，主要内容包括：一实施方式涉及一种有机电子材料,含有电荷传输性聚合物,所述电荷传输性聚合物包含：下述式(1)所表示的结构单元；选自由下述式(2-1)所表示的结构单元及下述式(2-2)所表示的结构单元所组成的群组中的至少一种结构单元；以及以一价结构单元的总量为基准而为85摩尔％～100摩尔％的下述式(3)所表示的结构单元。(One embodiment relates to an organic electronic material comprising a charge transporting polymer comprising: a structural unit represented by the following formula (1); at least one structural unit selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2); and 85 to 100 mol% of a structural unit represented by the following formula (3) based on the total amount of the monovalent structural units.)

1. An organic electronic material comprising a charge transporting polymer, the charge transporting polymer comprising:

a structural unit represented by the following formula (1);

at least one structural unit selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2); and

85 to 100 mol% of a structural unit represented by the following formula (3) based on the total amount of the monovalent structural units,

[ solution 1]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group, and at least one Ar is an aromatic hydrocarbon group having a substituent comprising at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.)

[ solution 2]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group)

[ solution 3]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group)

[ solution 4]

(in the formula, n represents an integer of 0 to 20).

2. The organic electronic material according to claim 1, wherein the structural unit represented by formula (1) comprises: at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1b), a structural unit represented by the following formula (1c), a structural unit represented by the following formula (1d), and a structural unit represented by the following formula (1e),

[ solution 5]

3. The organic electronic material according to claim 1 or 2, wherein at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2) comprises: at least one structural unit selected from the group consisting of a structural unit represented by the following formula (2-1c), a structural unit represented by the following formula (2-1d), and a structural unit represented by the following formula (2-2b),

[ solution 6]

4. The organic electronic material according to any one of claims 1 to 3, wherein the structural unit represented by formula (3) comprises a structural unit represented by the following formula (3a),

[ solution 7]

5. The organic electronic material according to any one of claims 1 to 4, wherein the charge transporting polymer further comprises: at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2),

[ solution 8]

(wherein R independently represents a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a substituted or unsubstituted sulfonic acid group, or a substituted or unsubstituted sulfinic acid group.)

[ solution 9]

(wherein R independently represents a hydrogen atom or a linear alkyl group, and at least one R is a linear alkyl group).

6. The organic electronic material according to claim 5, wherein at least one structural unit selected from the group consisting of the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2) comprises: at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4-1b) and a structural unit represented by the following formula (4-2b),

[ solution 10]

7. A method for producing a charge transporting polymer used in the organic electronic material according to any one of claims 1 to 6, comprising:

reacting a monomer mixture in a solvent comprising an aromatic ether, the monomer mixture comprising: a bifunctional monomer having a structural unit represented by the formula (1), at least one trifunctional monomer or tetrafunctional monomer selected from the group consisting of a trifunctional monomer having a structural unit represented by the formula (2-1) and a tetrafunctional monomer having a structural unit represented by the formula (2-2), and 85 to 100 mol% of a monofunctional monomer having a structural unit represented by the formula (3) based on the total amount of the monofunctional monomers.

8. A liquid composition comprising: the organic electronic material according to any one of claims 1 to 6; and a solvent.

9. The fluid composition of claim 8, wherein the vehicle comprises an aromatic ether.

10. An organic layer formed using the organic electronic material according to any one of claims 1 to 6 or the liquid composition according to claim 8 or 9.

11. An organic electronic element comprising the organic layer according to claim 10.

12. An organic electroluminescent element comprising the organic layer according to claim 10.

13. An organic electroluminescent element comprising the organic layer according to claim 10 as a hole injection layer or a hole transport layer.

14. A display element comprising the organic electroluminescent element according to claim 12 or 13.

15. A lighting device comprising the organic electroluminescent element according to claim 12 or 13.

16. A display device, comprising: the lighting device of claim 15; and a liquid crystal element as a display member.

Technical Field

Embodiments of the present invention relate to an organic electronic material, a method for producing a charge transporting polymer, a liquid composition, an organic layer, an organic electronic element, an organic Electroluminescence (EL) element, a display element, an illumination device, and a display device.

Background

Organic electronic devices are devices that electrically operate using organic substances, and are expected to exhibit features such as energy saving, low price, and flexibility. Examples of the organic electronic device include an organic EL device, an organic photoelectric conversion device, and an organic transistor.

Regarding the organic EL element, it is desirable to further improve various element characteristics. As one of means for improving the performance of organic EL devices, attempts have been made to form organic layers into a plurality of layers and separate the functions of the respective layers. When multilayering is performed by a wet process, the lower layer is required to have solvent resistance to a solvent of a coating solution used for forming the upper layer.

For example, a method of using a compound having at least one polymerizable group has been studied in order to form a multilayer organic layer (see, for example, patent document 1).

[ Prior art documents ]

[ patent document ]

Patent document 1: japanese patent laid-open No. 2006-279007

Disclosure of Invention

[ problems to be solved by the invention ]

An object of an embodiment of the present invention is to provide an organic electronic material and a liquid composition that can form an organic layer having an appropriate energy level (energy level), excellent solvent resistance, and improved lifetime characteristics of an organic electronic device. Another object of another embodiment of the present invention is to provide a method for producing a charge transporting polymer suitable for a charge transporting polymer used in the organic electronic material. An object of another embodiment of the present invention is to provide an organic layer having an appropriate energy level, excellent solvent resistance, and improved lifetime characteristics of an organic electronic device. It is an object of a further embodiment of the present invention to provide an organic electronic element, an organic EL element, a display element, an illumination device, and a display device, which have improved life characteristics.

[ means for solving problems ]

The following examples of the embodiments are given. The present invention is not limited to the following embodiments.

One embodiment relates to an organic electronic material comprising a charge transporting polymer comprising: a structural unit represented by the following formula (1); at least one structural unit selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2); and 85 to 100 mol% of a structural unit represented by the following formula (3) based on the total amount of the monovalent structural units.

[ solution 1]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group, and at least one Ar is an aromatic hydrocarbon group having a substituent comprising at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.)

[ solution 2]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group)

[ solution 3]

(wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group)

[ solution 4]

(in the formula, n represents an integer of 0 to 20).

Another embodiment relates to a method for producing a charge transporting polymer used in the organic electronic material, including: reacting a monomer mixture in a solvent comprising an aromatic ether, the monomer mixture comprising: a bifunctional monomer having a structural unit represented by the formula (1), at least one trifunctional monomer or tetrafunctional monomer selected from the group consisting of a trifunctional monomer having a structural unit represented by the formula (2-1) and a tetrafunctional monomer having a structural unit represented by the formula (2-2), and 85 to 100 mol% of a monofunctional monomer having a structural unit represented by the formula (3) based on the total amount of the monofunctional monomers.

Still another embodiment relates to a liquid composition containing the organic electronic material and a solvent.

Still another embodiment relates to an organic layer formed using the organic electronic material or the liquid composition.

Yet another embodiment relates to an organic electronic component having at least one of the organic layers.

Still another embodiment relates to an organic electroluminescent element having at least one of the organic layers.

Still another embodiment relates to a display element including the organic electroluminescent element; a lighting device including the organic electroluminescent element; and a display device including the lighting device and a liquid crystal element as a display member.

[ Effect of the invention ]

According to the embodiments of the present invention, an organic electronic material and a liquid composition can be provided, which can form an organic layer having an appropriate energy level, excellent solvent resistance, and improved lifetime characteristics of an organic electronic device. According to another embodiment of the present invention, a method for producing a charge transporting polymer suitable for a charge transporting polymer used in the organic electronic material can be provided. According to still another embodiment of the present invention, an organic layer having an appropriate energy level, excellent solvent resistance, and improved lifetime characteristics of an organic electronic device can be provided. According to still another embodiment of the present invention, an organic electronic element, an organic EL element, a display element, an illumination device, and a display device, which have improved life characteristics, can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element according to an embodiment.

Detailed Description

Embodiments of the present invention will be explained. The present invention is not limited to the following embodiments.

< organic electronic Material >

One embodiment of the present invention relates to an organic electronic material containing at least a charge transporting polymer, the charge transporting polymer including: a structural unit represented by formula (1); at least one structural unit selected from the group consisting of a structural unit represented by formula (2-1) and a structural unit represented by formula (2-2); and a structural unit represented by the formula (3) in an amount of 85 to 100 mol% based on the total amount of the monovalent structural units. The organic electronic material may further contain an optional component such as a dopant or a polymerization initiator.

In the present disclosure, a structural unit represented by "formula (X)" may be referred to as "structural unit (X)". Further, "at least one structural unit selected from the group consisting of the structural unit represented by the formula (Y-1) and the structural unit represented by the formula (Y-2)" may be referred to as a "structural unit (Y)".

[ Charge-transporting Polymer ]

The charge-transporting polymer comprises at least a structural unit (1), a structural unit (2), and a structural unit (3). The content of the structural unit (3) is 85 to 100 mol% based on the total amount of the monovalent structural units. The charge-transporting polymer may further contain an arbitrary structural unit different from the structural units (1) to (3). For example, the charge transporting polymer may further include at least one structural unit selected from the group consisting of the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2).

(structural Unit (1))

The charge transporting polymer comprises a structural unit (1). The structural unit (1) is a divalent structural unit having two bonding sites with other structural units. By including the structural unit (1), an organic layer having an appropriate energy level can be formed. The charge transporting polymer may contain only one kind of the structural unit (1), or may contain two or more kinds of the structural units (1).

[ solution 5]

Wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group, and at least one Ar is an aromatic hydrocarbon group having a substituent comprising at least one selected from the group consisting of a fluoro group and a fluoroalkyl group.

In the present disclosure, "+" in the structural formula represents a bonding site with other structural unit or structure.

The aromatic hydrocarbon group is an atomic group obtained by removing one or two hydrogen atoms from an aromatic hydrocarbon. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon include: benzene, naphthalene, anthracene, naphthacene, fluorene, phenanthrene, 9, 10-dihydrophenanthrene, triphenylene, pyrene,Perylene, triphenylene, condensed pentacene, benzopyrene, and the like.

Ar is preferably independently substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted anthracenyl, more preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl, respectively.

The aromatic hydrocarbon group may have a substituent. As the substituent, for example, there may be mentioned a substituent selected from the group consisting of-R¹、-OR²、-SR³、-OCOR⁴、-COOR⁵、-SiR⁶R⁷R⁸And a halogen atom (hereinafter sometimes referred to as "substituent Ra").

R¹Selected from the group consisting of alkyl, aryl and heteroaryl. R²～R⁸Each independently selected from the group consisting of hydrogen, alkyl, aryl, and heteroaryl. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 22. The number of carbon atoms of the aryl group is preferably 6 to 30. The carbon number of the heteroaryl group is preferably 2 to 30. Alkyl, aryl and heteroaryl groups may be substituted or unsubstituted.

Examples of the substituent in the case where the alkyl group, the aryl group and the heteroaryl group have a substituent include the substituent Ra, preferably-R¹. Examples of the alkyl group having a substituent include an arylalkyl group, a heteroarylalkyl group, and a fluoroalkyl group. Examples of the aryl group having a substituent include an alkylaryl group and a fluoroaryl group. Examples of the heteroaryl group having a substituent include an alkylheteroaryl group and the like.

Examples of the alkyl group include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, 3, 7-dimethyloctyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

In the present disclosure, an aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Heteroaryl is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound. The aromatic hydrocarbon here includes a single ring, a condensed ring, or two or more polycyclic rings selected from among single rings and condensed rings, which are bonded to each other through a direct bond. The aromatic heterocyclic compound here may be a monocyclic ring, a condensed ring, or a polycyclic ring in which two or more rings selected from the monocyclic ring and the condensed ring are bonded to each other via a direct bond.

Examples of aromatic hydrocarbons in the aryl group include: benzene, naphthalene, anthracene, naphthacene, fluorene, phenanthrene, 9, 10-dihydrophenanthrene, triphenylene, pyrene,Perylene, triphenylene, condensed pentacene, benzopyrene, biphenyl, terphenyl, triphenylbenzene, and the like. Examples of the aromatic heterocyclic compound in the heteroaryl group include: pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, carbazole, furan, benzofuran, dibenzofuran, pyrrole, thiophene, benzothiophene, dibenzothiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, benzotriazole, benzothiophene, bithiophene, and the like.

In formula (1), at least one Ar is an aromatic hydrocarbon group having a substituent including at least one selected from the group consisting of a fluoro group and a fluoroalkyl group. The number of carbons in the fluoroalkyl group is preferably 1 to 4, more preferably 1 or 2. The fluoroalkyl group is preferably a perfluoroalkyl group.

For example, in view of having both a deep Highest Occupied Molecular Orbital (HOMO) level and a large energy gap between HOMO-Lowest Unoccupied Molecular Orbitals (LUMOs), it is preferable that in the structural unit (1), at least one Ar is an aromatic hydrocarbon group having a fluorine group, and all Ar are aromatic hydrocarbon groups having no fluorine group.

On the other hand, for example, from the viewpoint of obtaining a deeper HOMO level, it is preferable that in the structural unit (1), at least one Ar is an aromatic hydrocarbon group having a fluoroalkyl group.

The fluorine group or fluoroalkyl group contained in the structural unit (1) is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to three. When the number is the above number, the effect of increasing the HOMO level tends to be easily obtained. In addition, in the case of the above number, the solubility of the charge transport polymer tends to be prevented from being too low.

The structural unit (1) preferably contains the following structural unit (1a), for example.

[ solution 6]

Wherein R independently represents a hydrogen atom or a substituent, and at least one R is a fluoro group or a fluoroalkyl group.

The number of carbons in the fluoroalkyl group is preferably 1 to 4, more preferably 1 or 2. The fluoroalkyl group is preferably a perfluoroalkyl group. In the formula, the number of R which is a fluoro group or a fluoroalkyl group is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 3.

R which is not fluoro or fluoroalkyl is a hydrogen atom or a substituent. Examples of the substituent include the substituent Ra (wherein fluorine group and fluoroalkyl group are excluded here). From the viewpoint of suppressing the influence of the substituent, all R groups of not the fluoro group or the fluoroalkyl group may be hydrogen atoms.

The structural unit (1) preferably contains at least one structural unit selected from the group consisting of the following structural units (1b) to (1e), for example.

[ solution 7]

When the charge transporting polymer includes the structural unit (1b) and/or the structural unit (1c), a deep HOMO level and a large energy gap between HOMO-LUMOs tend to be easily obtained. When the charge transporting polymer includes the structural unit (1d) and/or the structural unit (1e), a deeper HOMO level tends to be easily obtained. When the charge transporting polymer contains the structural unit (1e), good solubility of the charge transporting polymer tends to be easily obtained.

(structural Unit (2))

The charge-transporting polymer comprises at least one structural unit (2) selected from the group consisting of the structural unit (2-1) and the structural unit (2-2). The structural unit (2-1) is a trivalent structural unit having three bonding sites with other structural units. The structural unit (2-2) is a tetravalent structural unit having four bonding sites with other structural units. The structural unit (2) is a trivalent or tetravalent structural unit having three or four bonding sites with other structural units. The charge transporting polymer is a branched polymer having three or more terminals in one molecule, by containing the structural unit (2). The branched polymer can easily increase the molecular weight and tends to exhibit good solubility. The charge transporting polymer may contain only one kind of the structural unit (2), or may contain two or more kinds of the structural units (2).

[ solution 8]

Wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group.

[ solution 9]

Wherein Ar independently represents a substituted or unsubstituted aromatic hydrocarbon group.

For substituted or unsubstituted aromatic hydrocarbon groups, the description about the substituted or unsubstituted aromatic hydrocarbon groups in the structural unit (1) can be applied. Ar is preferably an unsubstituted aromatic hydrocarbon group.

In the structural unit (2-1), Ar is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted anthracenyl group, more preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, and further preferably a substituted or unsubstituted phenyl group, each independently.

In the structural unit (2-2), Ar is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted anthracenyl group, more preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, and further preferably a substituted or unsubstituted phenyl group, each independently.

The structural unit (2) preferably contains at least one structural unit selected from the group consisting of the structural unit (2-1a) described below, the structural unit (2-1b) described below, and the structural unit (2-2a) described below, for example.

[ solution 10]

Wherein R independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituent Ra.

[ solution 11]

Wherein R independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituent Ra.

[ solution 12]

Wherein R independently represents a hydrogen atom or a substituent. Examples of the substituent include the substituent Ra.

The structural unit (2) preferably includes at least one structural unit selected from the group consisting of the structural units (2-1c), (2-1d) and (2-2b) described below, for example.

[ solution 13]

(structural Unit (3))

The charge transporting polymer contains a structural unit (3). The structural unit (3) is a monovalent structural unit having a bonding site with another structural unit. The structural unit (3) is contained at a terminal of a polymer chain of the charge transporting polymer. The content of the structural unit (3) is 85 to 100 mol% based on the total amount of the monovalent structural units forming the terminal portion. By including 85 to 100 mol% of the structural unit (3), an organic layer having excellent solvent resistance can be obtained, and the life characteristics of the organic electronic device can be improved. The charge transporting polymer may contain only one kind of the structural unit (3), or may contain two or more kinds of the structural units (3).

[ solution 14]

Wherein n represents an integer of 0 to 20.

From the viewpoint of improving reactivity and life characteristics, n is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2.

The structural unit (3) is formed by₂-OXT-C_nH_2n+1"structural unit (Ph is phenylene and OXT is oxetanyl; the same applies hereinafter). The structural unit exhibits excellent reactivity by the structure containing an oxetanyl group, and therefore, the curing reaction of the charge transporting polymer can be efficiently performed. In terms of obtaining a charge-transporting polymer having better heat resistance, the structural unit is compared with a structure containing ". about. -Ph-CH₂-Ph-CH₂-O-CH₂The structural unit of- "is more preferable. In terms of obtaining organic electronic components exhibiting better lifetime characteristics, the structural units are compared to those in ". about. -Ph-" and ". about. -OXT-C_nH_2n+1"includes" - (CH) between₂)_nThe structural unit of- (n is an integer of 2 or more) ", is more preferable.

The content of the structural unit (3) is 85 to 100 mol% based on the total amount of the monovalent structural units. When the content is 85 mol% or more, an organic layer having excellent solvent resistance can be obtained, and the life characteristics of the organic electronic device can be improved. The content of the structural unit (3) is preferably 90 mol% or more, and more preferably 95 mol% or more, in terms of the tendency to obtain these higher effects. The upper limit of the content of the structural unit (3) is 100 mol%. In the case where a structural unit having another function is introduced into the terminal portion of the charge transporting polymer, the content of the structural unit (3) may be less than 100 mol%, for example, 95 mol% or less or 90 mol% or less.

The structural unit (3) preferably contains the following structural unit (3a), for example.

[ solution 15]

(structural Unit (4))

The charge transporting polymer may also include at least one structural unit (4) selected from the group consisting of the structural unit (4-1) and the structural unit (4-2). The structural unit (4-1), the structural unit (4-2) and the structural unit (4) are monovalent structural units having a bonding site with other structural units. The structural unit (4) is contained at a terminal of a polymer chain of the charge transporting polymer. The content of the structural unit (4) is preferably 0 to 15 mol% based on the total amount of the monovalent structural units forming the terminal portion. The inclusion of the structural unit (4) tends to improve the solubility of the charge transporting polymer. The charge transporting polymer may contain only one kind of the structural unit (4), or may contain two or more kinds of the structural units (4).

[ solution 16]

Wherein R independently represents a halogen group, a halogen-substituted alkyl group, a nitro group, a cyano group, a substituted or unsubstituted sulfonic acid group (-S (O)₂) -O-R '(R' is a hydrogen atom or a hydrocarbon group)), or a substituted or unsubstituted sulfinic acid group (-s (O) -O-R '(R' is a hydrogen atom or a hydrocarbon group)).

The halogen group is preferably a fluorine group. The number of carbon atoms of the alkyl group substituted with halogen is preferably 1 to 4, more preferably 1 or 2. The halogen-substituted alkyl group is preferably a fluoroalkyl group. The fluoroalkyl group is preferably a perfluoroalkyl group. Each R 'in the sulfonic acid group and sulfinic acid group is preferably a hydrogen atom or an alkyl group, and when each R' is an alkyl group, the number of carbon atoms is preferably 1 to 4.

The two R's may be the same as or different from each other, and are preferably the same as each other. R is independently preferably a fluoro group or a fluoroalkyl group, more preferably a fluoroalkyl group, and further preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

When the charge transporting polymer contains the structural unit (4-1), a deeper HOMO level tends to be easily obtained.

[ solution 17]

Wherein R independently represents a hydrogen atom or a linear alkyl group, and at least one R is a linear alkyl group.

The number of carbon atoms of the linear alkyl group is preferably 4 to 20, more preferably 4 to 16, and still more preferably 4 to 12.

The content of the structural unit (4) is 0 to 15 mol% based on the total amount of the monovalent structural units. That is, the charge transporting polymer does not contain the structural unit (4) (0 mol%), or the content thereof is 15 mol% or less in the case where the structural unit (4) is contained. When the content is 15 mol% or less, the content of the structural unit (3) becomes sufficient, and an organic layer having excellent solvent resistance can be obtained. In addition, an effect of preventing a large energy gap between HOMO-LUMOs from becoming small or an effect of improving the lifetime characteristics of an organic electronic device can be obtained. In order to obtain these higher effects, the content of the structural unit (4) is preferably 10 mol% or less, more preferably 7 mol% or less, and still more preferably 5 mol% or less. The lower limit of the content of the structural unit (4) is 0 mol%. In the case where it is desired to improve the solubility of the charge transporting polymer, the content of the structural unit (4) may be more than 0 mol%, for example, 5 mol% or more or 10 mol% or more.

The structural unit (4) preferably includes at least one structural unit selected from the group consisting of the structural unit (4-1a) and the structural unit (4-2a) described below, for example.

[ solution 18]

Wherein n and m independently represent an integer of 1 to 4. n and m may be the same or different from each other, and are preferably the same.

[ solution 19]

Wherein n represents an integer of 4 to 20. n is more preferably 4 to 16, and still more preferably 4 to 12.

The structural unit (4) preferably includes at least one structural unit selected from the group consisting of the structural units (4-1b) and (4-2b) described below, for example.

[ solution 20]

(optional structural units)

The charge-transporting polymer may further contain another arbitrary structural unit (hereinafter referred to as "arbitrary structural unit") different from the structural units (1) to (3). Examples of the optional structural unit include the structural unit (4).

In addition, any structural unit is selected from, for example, a substituted or unsubstituted aromatic amine structure, a substituted or unsubstituted carbazole structure, a substituted or unsubstituted thiophene structure, a substituted or unsubstituted fluorene structure, a substituted or unsubstituted benzene structure, a substituted or unsubstituted biphenyl structure, a substituted or unsubstituted terphenyl structure, a substituted or unsubstituted naphthalene structure, a substituted or unsubstituted anthracene structure, a substituted or unsubstituted naphthacene structure, a substituted or unsubstituted phenanthrene structure, a substituted or unsubstituted dihydrophenanthrene structure, a substituted or unsubstituted pyridine structure, a substituted or unsubstituted pyrazine structure, a substituted or unsubstituted quinoline structure, a substituted or unsubstituted isoquinoline structure, a substituted or unsubstituted quinoxaline structure, a substituted or unsubstituted acridine structure, Substituted or unsubstituted phenanthroline structures, substituted or unsubstituted furan structures, substituted or unsubstituted pyrrole structures, substituted or unsubstituted oxazole structures, substituted or unsubstituted oxadiazole structures, substituted or unsubstituted thiazole structures, substituted or unsubstituted thiadiazole structures, substituted or unsubstituted triazole structures, substituted or unsubstituted benzothiophene structures, substituted or unsubstituted benzoxazole structures, substituted or unsubstituted benzooxadiazole structures, substituted or unsubstituted benzothiazole structures, substituted or unsubstituted benzothiadiazole structures, substituted or unsubstituted benzotriazole structures, and structures including one or two of these.

Any structural unit may be monovalent or higher, preferably monovalent to hexavalent, more preferably monovalent to pentavalent, and further preferably monovalent to tetravalent.

With respect to the substituent contained in any structural unit, the description of the substituent in the structural unit (1) can be applied.

(content of each structural unit)

The charge transporting polymer may also contain a divalent structural unit in addition to the structural unit (1). From the viewpoint of adjusting the energy level, the content of the structural unit (1) is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more, based on the total amount of the divalent structural units. The upper limit of the content of the structural unit (1) is 100 mol%.

From the viewpoint of obtaining sufficient charge transport properties, the content of the divalent structural unit contained in the charge transport polymer is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more, based on the total structural units. In consideration of the monovalent structural unit and the trivalent or higher structural unit, the content of the divalent structural unit is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

The charge transporting polymer may also contain a trivalent or higher structural unit in addition to the structural unit (2). From the viewpoint of obtaining good charge transport properties, the content of the structural unit (2) is preferably 50 mol% or more, more preferably 75 mol% or more, and even more preferably 90 mol% or more, based on the total amount of the trivalent or higher structural units. The upper limit of the content of the structural unit (2) is 100 mol%.

From the viewpoint of obtaining an organic layer having excellent solvent resistance, the content of the trivalent or higher structural unit contained in the charge transporting polymer is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, based on the whole structural units. From the viewpoint of suppressing an increase in viscosity and favorably synthesizing a charge-transporting polymer or from the viewpoint of obtaining sufficient charge-transporting properties, the content of the trivalent or higher structural unit is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

The charge transporting polymer may also contain a monovalent structural unit (e.g., structural unit (4)) in addition to structural unit (3). From the viewpoint of obtaining a good charge transport property, the content of the structural unit (3) is preferably 85 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more, based on the total amount of the monovalent structural units. The upper limit of the content of the structural unit (3) is 100 mol%.

From the viewpoint of curability and solubility of the charge transporting polymer, and from the viewpoint of improvement in the characteristics of the organic electronic device, the content of the monovalent structural unit contained in the charge transporting polymer is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more, based on the total structural units. From the viewpoint of obtaining sufficient charge transport properties, the content of the monovalent structural unit is preferably 60 mol% or less, more preferably 55 mol% or less, and still more preferably 50 mol% or less.

The charge transporting polymer may contain an arbitrary structural unit. From the viewpoint of obtaining sufficient effects by the structural units (1) to (3), the content of any structural unit is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less or 5 mol% or less, based on the whole structural units. The lower limit of the content of the optional structural unit is 0 mol%. That is, the charge transporting polymer may not contain any structural unit.

The charge transporting polymer may also contain a structural unit having a substituent containing a substituted or unsubstituted saturated hydrocarbon chain. As examples of substituted or unsubstituted saturated hydrocarbon chains, mention may be made of substituted or unsubstituted alkylene chains (— (CH)₂)_n- ("n" is an integer of 2 or more)). Examples of the substituent containing a substituted or unsubstituted alkylene chain include a substituted or unsubstituted linear alkyl group (for example, — C)_nH_2n+1(n is an integer of 2 or more)), a monovalent group containing a substituted or unsubstituted straight chain alkylene group (for example, (. about. -O- (CH))₂)_n-OXT (n is an integer of 2 or more; OXT is an oxetanyl group which may have a substituent), and the like.

From the viewpoint of improving solubility, the charge transporting polymer preferably contains a structural unit having a substituent containing a substituted or unsubstituted saturated hydrocarbon chain (hereinafter sometimes referred to as "structural unit C") "). On the other hand, the content of the structural unit C in the charge transporting polymer is preferably small from the viewpoint of improving the life characteristics. That is, when the charge transporting polymer contains the structural unit C, the content thereof is preferably 50 mol% or less based on the whole structural units. In particular, the charge transporting polymer preferably does not contain a structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 6 or more carbon atoms (for example, having a structure containing a substituted or unsubstituted alkylene chain (— (CH))₂)_nConstituent unit C) of a substituent (0 mol%) or, when the constituent unit C is contained, the content thereof is 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, based on the whole constituent unit. The content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 5 or more carbon atoms is more preferably in the above range, the content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 4 or more carbon atoms is more preferably in the above range, and the content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 3 or more carbon atoms is particularly preferably in the above range, among all the structural units contained in the charge transporting polymer.

In particular, from the viewpoint of obtaining more excellent life characteristics, the charge transporting polymer preferably has a monovalent structural unit that does not include a structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 6 or more carbon atoms (for example, having a structure containing a substituted or unsubstituted alkylene chain (— (CH))₂)_nConstituent unit C) of a substituent (0 mol%) or, when the constituent unit C is contained, the content thereof is 15 mol% or less, more preferably 10 mol% or less, and still more preferably 5 mol% or less, based on the total amount of monovalent constituent units. In the monovalent structural unit, the content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 5 or more carbon atoms is more preferably in the above range, the content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 4 or more carbon atoms is more preferably in the above range, and the content of the structural unit C containing a substituted or unsubstituted saturated hydrocarbon chain having 3 or more carbon atoms is particularly preferably in the above rangeThe content of the structural unit C of the saturated hydrocarbon chain in (b) is within the range.

In view of the balance of the effects of the respective structural units, the content ratio (molar ratio) of the divalent structural unit, the trivalent or higher structural unit, and the monovalent structural unit contained in the charge transporting polymer is preferably 100: 5 to 70: 50 to 150, more preferably 100: 10 to 60: 60 to 135, and still more preferably 100: 15 to 50: 80 to 120, based on the divalent structural unit, the trivalent or higher structural unit, and the monovalent structural unit.

The content of the structural unit can be determined using the amount of the monomer corresponding to each structural unit used for synthesizing the charge transporting polymer. In addition, the proportion of the structural units may be determined by using a charge-transporting polymer¹The integral value of the spectrum derived from each structural unit in the H Nuclear Magnetic Resonance (NMR) spectrum is calculated as an average value. In a simple aspect, when the amount of use is clear, it is preferable to use a value obtained by using the amount of use.

(number average molecular weight)

The number average molecular weight of the charge transporting polymer may be appropriately adjusted in consideration of solubility in a solvent, film-forming property, and the like. From the viewpoint of excellent charge transport properties, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, still more preferably 2,000 or more, and particularly preferably 5,000 or more. In addition, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and particularly preferably 30,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of a liquid composition.

(weight average molecular weight)

The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film-forming properties, and the like. From the viewpoint of excellent charge transport properties, the weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. In addition, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, even more preferably 400,000 or less, and particularly preferably 100,000 or less, from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of a liquid composition.

The number average molecular weight and the weight average molecular weight can be determined by Gel Permeation Chromatography (GPC) using a calibration curve of standard polystyrene. The measurement conditions include, for example, the conditions described in examples.

(example of the Charge-transporting Polymer Structure)

The charge transporting polymer comprises a divalent structural unit containing the structural unit (1), a trivalent or higher structural unit containing the structural unit (2), and a monovalent structural unit containing the structural unit (3). The trivalent or higher structural unit forms a branch portion of the charge transporting polymer, and the monovalent structural unit forms a terminal portion of the charge transporting polymer.

According to a preferred embodiment, the charge transporting polymer comprises a branched structure having at least one structural unit (2) and three or more structural units (1) bonded to the one structural unit (2). Preferably, the charge transporting polymer has a multiple-branched structure having one structural unit (2) and three or more structural units (1) bonded to the one structural unit (2), and further has, for each of the three or more structural units (1), at least one other structural unit (2) bonded to the structural unit (1) and two or more other structural units (1) bonded to the other structural unit (2).

Examples of the structure contained in the charge transporting polymer include the following. In the structure, "L" represents a divalent structural unit, "B" represents a trivalent or higher structural unit, and "T" represents a monovalent structural unit. In the following structure, a plurality of L may be the same structural unit or different structural units. The same applies to B and T. The charge transporting polymer is not limited to one having the following structure.

[ solution 21]

(use of Charge-transporting Polymer, etc.)

The charge-transporting polymer can adjust the HOMO level to an appropriate level by having the structural unit (1), and is excellent in solubility and durability by having the structural unit (2). Further, since the charge transporting polymer has a specific content of the structural unit (3), the curing properties and the life characteristics are also excellent. An organic electronic material containing such a charge-transporting polymer can be preferably used for a hole-transporting layer of an organic EL element, for example. In order to obtain good solubility, the organic electronic material is preferably used by being dissolved in a solvent containing at least one selected from the group consisting of aromatic ethers and aromatic halides.

< method for producing Charge-transporting Polymer >

One embodiment of the present invention relates to a method for producing a charge-transporting polymer used for the organic electronic material, the method including: reacting a monomer mixture in a solvent comprising an aromatic ether, the monomer mixture comprising: a bifunctional monomer having a structural unit represented by the formula (1), at least one trifunctional monomer or tetrafunctional monomer selected from the group consisting of a trifunctional monomer having a structural unit represented by the formula (2-1) and a tetrafunctional monomer having a structural unit represented by the formula (2-2), and 85 to 100 mol% of a monofunctional monomer having a structural unit represented by the formula (3) based on the total amount of the monofunctional monomers. The method for producing the charge transporting polymer may further include any of the steps of preparing monomers, mixing the monomer mixture with a solvent, adding a catalyst, washing the charge transporting polymer, and the like.

In the present disclosure, "a monomer having a structural unit represented by formula (X)" may be referred to as "monomer (X)". Further, "at least one monomer selected from the group consisting of a monomer having a structural unit represented by the formula (Y-1) and a monomer having a structural unit represented by the formula (Y-2)" may be referred to as a "monomer (Y)".

[ monomer mixture ]

The monomer mixture at least comprises a monomer (1), a monomer (2) and a monomer (3). The content of the monomer (3) is 85 to 100 mol% based on the total amount of the monofunctional monomers. The monomer mixture may further contain an arbitrary monomer different from the monomers (1) to (3). For example, the monomer mixture may further include at least one monofunctional monomer selected from the group consisting of a monofunctional monomer having a structural unit represented by the formula (4-1) and a monofunctional monomer having a structural unit represented by the formula (4-2).

(monomer (1))

The monomer (1) contains a structural unit (1) in the molecule. The monomer (1) can be used for introducing the structural unit (1) into the charge transporting polymer. The description about the structural unit (1) can be applied to the structural unit (1) contained in the monomer (1). The monomer (1) is a difunctional monomer having two reactive functional groups.

The monomer (1) is preferably a monomer represented by the following formula (1M), for example.

[ solution 22]

R-L-R

(1M)

Wherein L represents a structural unit (1) and R each independently represents a reactive functional group.

(monomer (2))

The monomer (2-1) is a trifunctional monomer having one structural unit (2-1) in the molecule and having three reactive functional groups. The monomer (2-2) is a tetrafunctional monomer containing one structural unit (2-2) in a molecule and having four reactive functional groups. The monomer (2) is at least one monomer selected from the group consisting of the monomer (2-1) and the monomer (2-2), and is useful for introducing the structural unit (2) into the charge transporting polymer. The description about the structural unit (2) can be applied to the structural unit (2) contained in the monomer (2).

The monomer (2-1) is preferably a monomer represented by the following formula (2-1M), for example.

[ solution 23]

In the formula, B¹Represents a structural unit (2-1), and R's each independently represents a reactive functional group.

The monomer (2-2) is preferably a monomer represented by the following formula (2-2M), for example.

[ solution 24]

In the formula, B²Represents a structural unit (2-2), and R's each independently represents a reactive functional group.

(monomer (3))

The monomer (3) contains a structural unit (3) in the molecule. The monomer (3) can be used for introducing the structural unit (3) into the charge transporting polymer. The description about the structural unit (3) can be applied to the structural unit (3) contained in the monomer (3). The monomer (3) is a monofunctional monomer having one reactive functional group.

The monomer (1) is preferably a monomer represented by the following formula (3M), for example.

[ solution 25]

T-R

(3M)

Wherein T represents a structural unit (3) and R represents a reactive functional group.

(monomer (4))

The monomer (4-1) is a monofunctional monomer having one reactive functional group and containing one structural unit (4-1) in the molecule. The monomer (4-2) is a monofunctional monomer having one structural unit (4-2) in the molecule and having one reactive functional group. The monomer (4) is at least one monomer (4) selected from the group consisting of the monomer (4-1) and the monomer (4-2), and can be used for introducing the structural unit (4) into the charge transporting polymer. The description about the structural unit (4) can be applied to the structural unit (4) contained in the monomer (4).

The monomer (4-1) is preferably a monomer represented by the following formula (4-1M), for example.

[ solution 26]

T¹-R

(4-1M)

In the formula, T¹Represents the structural unit (4-1), and R represents a reactive functional group.

The monomer (4-2) is preferably a monomer represented by the following formula (4-2M), for example.

[ solution 27]

T²-R

(4-2M)

In the formula, T²Represents the structural unit (4-2), and R represents a reactive functional group.

(reactive functional group)

Reactive functional groups are groups that can react with each other to form bonds between structural units. The bond is preferably a direct bond. The reactive functional group may be appropriately selected depending on the target reaction. For example, in the case where the reaction is a suzuki coupling reaction described later, the reactive functional group is preferably selected from the group consisting of a boronic acid group, a boronic ester group and a halogen group.

As examples of monomer mixtures, mention may be made of mixtures comprising the following monomers: a monomer (1) in which all of the reactive functional groups are boronic acid groups or boronic ester groups; a monomer (2) in which all of the reactive functional groups are halogen groups; and a monomer (3) in which the reactive functional group is a halogen group. As another example of the monomer mixture, a mixture containing the following monomers may be mentioned: a monomer (1) in which all of the reactive functional groups are halogen groups; a monomer (2) in which all of the reactive functional groups are boronic acid groups or boronic ester groups; and a monomer (3) in which the reactive functional group is a boronic acid group or a boronic acid ester group. In these examples, in the case where the monomer mixture further contains the monomer (4), the monomer (4) preferably has the same reactive functional group as the monomer (3).

The monomer can be synthesized by a known method. These monomers can be obtained from, for example, tokyo chemical industry gmbh, SIGMA ALDRICH (SIGMA-ALDRICH) japan alliance, and the like.

(composition of monomer mixture)

The content of each monomer in the monomer mixture may be in accordance with the content of the structural unit corresponding to each monomer in the charge transporting polymer. For example, the content of the monomer (3) in the monomer mixture is 85 to 100 mol% based on the monofunctional monomer, as in the content of the structural unit (3) in the charge transporting polymer. For example, the content of the bifunctional monomer in the monomer mixture is preferably 10 mol% or more based on the total monomers, as in the content of the divalent structural unit in the charge transporting polymer. That is, the explanation of the content (numerical range) of the structural unit in the charge transporting polymer can be used as an explanation of the content (numerical range) of the monomer in the monomer mixture by replacing the charge transporting polymer with the monomer mixture and replacing the structural unit with the monomer.

[ reaction of monomer mixture ]

The reaction is preferably a coupling reaction, and examples of the coupling reaction include known reactions such as suzuki coupling, root and shore coupling, Sonogashira coupling (Sonogashira coupling), Stille coupling, and Buchwald-hartwich coupling. Suzuki coupling is, for example, one that causes a cross-coupling reaction between an aromatic boronic acid compound or an aromatic boronic ester compound and an aromatic halogen compound using a Pd catalyst. According to the suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings to each other.

In Suzuki coupling, for example, Pd compounds such as Pd (0) compounds and Pd (II) compounds, Ni compounds, Ru compounds, and the like are used as catalysts. Examples of Pd compounds include: pd (t-Bu)₃P)₂(bis (tri-tert-butylphosphine) palladium (0)), Pd (t-Bu)₃P)₄(tetrakis (tri-tert-butylphosphine) palladium (0)), Pd (PPh)₃)₄(tetrakis (triphenylphosphine) palladium (0)), Pd (dppf) Cl₂([1, 1' -bis (diphenylphosphino) ferrocene)]Palladium (II) dichloride), PD (dppe) Cl₂([1, 2-bis (diphenylphosphino) ethane)]Palladium (II) dichloride) and the like, and a Pd compound having a phosphine ligand. In addition, a catalyst species generated by using tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate, or the like as a precursor and mixing the precursor with a phosphine ligand in a reaction system may also be used. As an example of the phosphine ligand in the above case, P (t-Bu) may be mentioned₃(Tri (tert-butyl)) Phosphine), tributylphosphine, P (c-Hex)₃(tricyclohexylphosphine), and the like.

The reaction solvent may be an organic solvent, and a mixed solvent of water and an organic solvent is preferably used. Examples of the organic solvent include: aromatic ethers such as 1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2, 3-dimethylanisole, 2, 4-dimethylanisole, and diphenyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, and diphenylmethane; tetrahydrofuran, acetone, acetonitrile, N-dimethylformamide, and the like. In the reaction, as the base, there can also be used: na (Na)₂CO₃、K₂CO₃Carbonates of alkali metals; hydroxides of alkali metals such as NaOH and KOH; k₃PO₄Alkali metal phosphates; water-soluble organic bases such as triethylamine, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide (TEAH). In addition, a phase transfer catalyst may be added to promote the reaction. Examples of phase transfer catalysts include: tetrabutylammonium bromide (TBAB), Aliquat (Aliquat)336 (registered trademark, manufactured by SIGMA ALDRICH (SIGMA-ALDRICH), a mixture of trioctylmethylammonium chloride (tricaprylmethylammonium chloride) and tricaprylylmethylammonium chloride (tricaprylmethyllammonium chloride)), and the like.

In order to obtain the target charge transporting polymer, a preferable reaction solvent includes at least one solvent selected from the group consisting of aromatic ethers and aromatic halides.

The aromatic ether preferably contains an aromatic ether represented by the following formula (a). When the reaction solvent contains an aromatic ether, the reaction solvent is preferably a mixed solvent containing water and an aromatic ether. Specifically, anisole and/or phenetole are preferred as the aromatic ether, and anisole is more preferred. In the case of using a solvent containing an aromatic ether, the charge transporting polymer can be obtained efficiently and easily.

[ solution 28]

Wherein Ar represents an aromatic hydrocarbon group, R represents a hydrocarbon group, and n represents an integer of 1 or more.

As for the aromatic hydrocarbon group, the description about the aromatic hydrocarbon group in the structural unit (1) can be applied. Ar is preferably phenyl or naphthyl, more preferably phenyl. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. Specific examples of the hydrocarbon group include an alkyl group, an ethyl group, and a propyl group. When Ar is phenyl, n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

When the reaction solvent is a mixed solvent containing an aromatic ether, the content of the aromatic ether is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of the reaction solvent. On the other hand, the content of the aromatic ether is preferably less than 100% by mass, more preferably 95% by mass or less, and still more preferably 90% by mass or less, based on the total amount of the reaction solvent.

The aromatic halide preferably contains an aromatic halide represented by the following formula (B). When the reaction solvent contains an aromatic halide, the reaction solvent is preferably a mixed solvent containing water and an aromatic halide. Specifically, chlorobenzene, dichlorobenzene, and/or chloronaphthalene are preferable as the aromatic halide. When a solvent containing chlorobenzene is used, the charge transporting polymer can be obtained efficiently and easily.

[ solution 29]

Wherein Ar represents an aromatic hydrocarbon group, R represents a halogen atom, and n represents an integer of 1 or more.

As for the aromatic hydrocarbon group, the description about the aromatic hydrocarbon group in the structural unit (1) can be applied. Ar is preferably phenyl or naphthyl, more preferably phenyl. The halogen atom is preferably a chlorine atom. When Ar is phenyl, n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

When the reaction solvent is a mixed solvent containing an aromatic halide, the content of the aromatic halide is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of the reaction solvent. On the other hand, the content of the aromatic halide is preferably less than 100% by mass, more preferably 95% by mass or less, and still more preferably 90% by mass or less, based on the total amount of the reaction solvent.

[ dopant ]

The organic electronic material may comprise any additive, for example, may further comprise a dopant. The dopant is not particularly limited as long as it exhibits a doping effect when added to the organic electronic material and can improve charge transport properties. It is preferable to perform p-type doping for improving the hole transporting property, and n-type doping for improving the electron transporting property. In addition, one kind of dopant may be added alone, or a plurality of kinds of dopants may be added in combination.

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, pi-conjugated compounds, and the like. Specifically, as the lewis acid, there can be mentioned: FeCl₃、PF₅、AsF₅、SbF₅、BF₅、BCl₃、BBr₃Etc.; as the protonic acid, there can be mentioned: HF. HCl, HBr, HNO₃、H₂SO₄、HClO₄Inorganic acids such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid, camphorsulfonic acid, and the like; as the transition metal compound, there can be mentioned: FeOCl, TiCl₄、ZrCl₄、HfCl₄、NbF₅、AlCl₃、NBCl₅、TaCl₅、MoF₅(ii) a As the ionic compound, there can be mentioned: tetrakis (pentafluorophenyl) borate ion, tris (trifluoromethanesulfonyl) methide ion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF₆ ^-(hexafluoroarsenate ion), BF₄ ^-(tetrafluoroborate ion) PF₆ ^-Salts having a perfluoroanion such as (hexafluorophosphate ion) and salts having a conjugate base of the protonic acid as an anion; examples of the halogen compound include: cl₂、Br₂、I₂、ICl、ICl₃IBr, IF, etc.; examples of the pi-conjugated compound include TCNE (tetracyanoethylene) and TCNQ (tetracyanoquinodimethane).

The dopant used for n-type doping is an electron-donating compound, and examples thereof include: alkali metals such as Li and Cs; alkaline earth metals such as Mg and Ca; LiF, Cs₂CO₃Salts of alkali metals and/or alkaline earth metals; a metal complex; electron-donating organic compounds, and the like.

In order to improve the solvent resistance of the organic layer, a compound that can act as a polymerization initiator for the polymerizable functional group may be used as the dopant.

[ other optional Components ]

The organic electronic material may further contain a charge-transporting low-molecular compound, another polymer, or the like.

[ contents ]

From the viewpoint of obtaining good charge transport properties, the content of the charge transport polymer in the organic electronic material is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more, with respect to the total mass of the organic electronic material. The upper limit of the content of the charge transporting polymer is not particularly limited, and may be set to 100 mass%. The content of the charge transporting polymer may be, for example, 95 mass% or less or 90 mass% or less, considering that an additive such as a dopant is contained.

When the dopant is contained, the content of the dopant is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, with respect to the total mass of the organic electronic material, from the viewpoint of improving the charge transporting property of the organic electronic material. From the viewpoint of maintaining the film forming property well, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the total mass of the organic electronic material.

< liquid composition >

The liquid composition according to the embodiment of the present invention contains the organic electronic material and a solvent. The organic layer can be easily formed by a coating method using a liquid composition containing a solvent. The liquid composition can be used as an ink composition.

[ solvent ]

As the solvent, any solvent such as water, an organic solvent, or a mixed solvent thereof can be used. Examples of the organic solvent include: alcohols such as methanol, ethanol, and isopropanol; alkanes such as pentane, hexane, octane and the like; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetrahydronaphthalene, and diphenylmethane; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate; aromatic ethers such as 1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2, 3-dimethylanisole, 2, 4-dimethylanisole, etc.; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; aromatic halides such as chlorobenzene, o-dichlorobenzene, 1-chloronaphthalene, and the like; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, dichloromethane, and the like. The liquid composition may contain one kind of solvent alone, or may contain two or more kinds of solvents.

From the viewpoint of obtaining excellent solubility of the charge transporting polymer, the liquid composition preferably contains a solvent containing at least one selected from the group consisting of aromatic ethers and aromatic halides. In the case where the liquid composition contains a solvent containing an aromatic ether and/or an aromatic halide, the charge transporting polymer can be easily dissolved in the solvent without introducing a large amount of a linear alkylene group or a linear alkyl group which may be introduced into the charge transporting polymer for improving the solubility. In order to improve the life characteristics of the organic electronic device, it is preferable that the charge transporting polymer has a small content of the linear alkylene group and the linear alkyl group. When the structural unit (1) is introduced into the charge transporting polymer, the solubility of the charge transporting polymer in a general solvent such as an aromatic hydrocarbon tends to be lowered. However, in the case where the liquid composition contains a solvent containing an aromatic ether and/or an aromatic halide, good solubility can be easily obtained even in the case where the charge transporting polymer contains the structural unit (1).

In a preferred embodiment, the liquid composition preferably contains a solvent containing an aromatic ether. The aromatic ether is preferably an aromatic ether represented by the formula (a). Specifically, the aromatic ether is preferably anisole and/or phenetole, and more preferably anisole. In the case of using a solvent containing an aromatic ether, the charge transporting polymer can be dissolved efficiently and easily. When the solvent containing an aromatic ether is a mixed solvent, the content of the aromatic ether in the mixed solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the total amount of the solvent. The vehicle may be an aromatic ether-only vehicle.

In another preferred embodiment, the liquid composition preferably contains a solvent containing an aromatic halide. The aromatic ether is preferably an aromatic ether represented by the formula (B). Specifically, the aromatic halide is preferably chlorobenzene and/or dichlorobenzene, and more preferably chlorobenzene. When a solvent containing an aromatic halide is used, the charge transporting polymer can be dissolved efficiently and easily. When the solvent containing the aromatic halide is a mixed solvent, the content of the aromatic halide in the mixed solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on the total amount of the solvent. The vehicle may be a vehicle containing only aromatic halide.

[ polymerization initiator ]

The liquid composition preferably contains a polymerization initiator in order to react the oxetanyl group contained in the charge transporting polymer. As the polymerization initiator, a known radical polymerization initiator, cationic polymerization initiator, anionic polymerization initiator, or the like can be used. From the viewpoint of easily preparing a liquid composition, it is preferable to use a substance having both a function as a dopant and a function as a polymerization initiator. Examples of such a substance include the above-mentioned ionic compounds.

[ additives ]

The liquid composition may further contain an additive as an optional component. Examples of additives include: polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reduction inhibitors, oxidizing agents, reducing agents, surface modifiers, emulsifiers, defoamers, dispersants, surfactants, and the like.

[ contents ]

The content of the solvent in the liquid composition may be determined in consideration of the application to various coating methods. For example, the content of the solvent is preferably an amount of 0.1% by mass or more, more preferably an amount of 0.2% by mass or more, and still more preferably an amount of 0.5% by mass or more of the charge transporting polymer relative to the solvent. The content of the solvent is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less of the charge transport polymer relative to the solvent.

< organic layer >

The organic layer according to an embodiment of the present invention is a layer formed using the organic electronic material or the liquid composition. The organic layer exhibits good charge transport properties. By using the liquid composition, the organic layer can be formed well and easily by a coating method. Examples of the coating method include: spin coating; tape casting; an impregnation method; plate printing methods such as relief printing, gravure printing, offset printing, relief reversal offset printing, screen printing, and gravure (gravure) printing; a known method such as a plateless printing method such as an ink jet method. In the case of forming an organic layer by a coating method, a layer of a liquid composition obtained after coating may be dried using a hot plate or an oven, and the solvent may be removed.

Since the charge-transporting polymer contains the structural unit (3) having a polymerizable functional group, the polymerization reaction of the charge-transporting polymer can be carried out by light irradiation, heat treatment, or the like, to obtain a cured organic layer. By stacking the cured organic layers, multilayering of the organic electronic device can be easily achieved.

From the viewpoint of improving the efficiency of charge transport, the thickness of the organic layer after drying or curing is preferably 0.1nm or more, more preferably 1nm or more, and even more preferably 3nm or more. In addition, the thickness of the organic layer is preferably 300nm or less, more preferably 200nm or less, and further preferably 100nm or less, from the viewpoint of reducing the resistance.

< organic electronic component >

The organic electronic element as an embodiment of the present invention has at least one of the organic layers. Examples of the organic electronic element include an organic EL element such as an Organic Light Emitting Diode (OLED), an organic photoelectric conversion element, and an organic transistor. The organic electronic element preferably has a structure in which an organic layer is disposed between at least one pair of electrodes.

< organic electroluminescent element (organic EL element) >

An organic EL element according to an embodiment of the present invention has at least one organic layer. The organic EL element generally includes a light-emitting layer, an anode, a cathode, and a substrate, and if necessary, includes other functional layers such as a hole-transporting layer such as a hole-injecting layer and a hole-transporting layer, and an electron-transporting layer such as an electron-injecting layer and an electron-transporting layer. Each layer may be formed by an evaporation method or a coating method. The organic EL element preferably has the organic layer as a light-emitting layer or another functional layer, more preferably has the organic layer as another functional layer, and even more preferably has the organic layer as at least one of a hole injection layer and a hole transport layer.

Fig. 1 is a schematic cross-sectional view showing an embodiment of an organic EL element. The organic EL element of fig. 1 is an element of a multilayer structure, sequentially including: 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.

[ luminescent layer ]

As a material used for the light-emitting layer, a light-emitting material such as a low molecular compound, a polymer, or a dendrimer (dendrimer) can be used. The polymer is preferably high in solubility in a solvent and suitable for a coating method. Examples of the light-emitting material include a fluorescent material, a phosphorescent material, and a Thermally Activated Delayed Fluorescence (TADF).

[ hole-transporting layer ]

The organic EL element preferably includes the organic layer as a hole-transporting layer, and more preferably includes the organic layer as at least one of a hole-injecting layer and a hole-transporting layer. As described above, these layers can be easily formed by using a liquid composition containing an organic electronic material.

In the case where the organic EL element has the organic layer as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer. In the case where the organic EL element has the organic layer as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. The hole injection layer and the hole transport layer may be the organic layer.

In the case where the hole transport layer is a hardened organic layer, a light emitting layer can be easily formed thereon using an ink composition. In this case, the polymerization initiator may be contained in the organic layer as the hole transport layer, or may be contained in the organic layer located under the hole transport layer.

[ Electron transporting layer ]

Examples of the material used for the electron-transporting layer such as the electron-transporting layer and the electron-injecting layer include: phenanthroline (phenanthroline) derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, fused ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes, and the like. In addition, the organic electronic material may also be used.

[ cathode ]

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

[ Anode ]

As the anode material, for example, a metal (e.g., Au) or another material having conductivity can be used. Examples of the other material include an oxide (e.g., ITO: indium oxide/tin oxide) and a conductive polymer (e.g., a polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[ base plate ]

As the substrate, glass, plastic, or the like can be used. The substrate is preferably transparent and preferably flexible. Quartz glass, resin films, and the like can be preferably used.

The resin film is preferably a light-transmitting resin film. 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 the transmission of water vapor or oxygen.

[ sealing ]

In order to reduce the influence of the external gas to extend the life, the organic EL element may be sealed. As a material used for sealing, glass, a plastic film, or an inorganic substance such as silicon oxide or silicon nitride can be used, but the material is not limited thereto.

[ luminescent colors ]

The emission color of the organic EL element is not particularly limited. A white organic EL element is preferably used for various lighting devices such as home lighting, interior lighting, clocks, and a backlight for liquid crystal.

< display element, illumination device, and display device >

The display element as an embodiment of the present invention includes the organic EL element. For example, by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB), a color display element can be obtained.

In addition, the lighting device as an embodiment of the present invention includes the organic EL element. Further, a display device according to an embodiment of the present invention includes a lighting device and a liquid crystal element as a display member. For example, a display device using the lighting device as a backlight and a known liquid crystal element as a display member, that is, a liquid crystal display device can be used as the display device.

< example of embodiment >

The following is an example of a preferred embodiment of the present invention. The embodiments of the present invention are not limited to the following examples.

[1] An organic electronic material comprising a charge transporting polymer, the charge transporting polymer comprising:

a structural unit represented by the formula (1);

at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2); and

and a structural unit represented by the formula (3) in an amount of 85 to 100 mol% based on the total amount of the monovalent structural units.

[2] The organic electronic material according to [1], wherein the structural unit represented by the formula (1) comprises: at least one structural unit selected from the group consisting of the structural unit represented by the formula (1b), the structural unit represented by the formula (1c), the structural unit represented by the formula (1d), and the structural unit represented by the formula (1 e).

[3] The organic electronic material according to [1] or [2], wherein at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-1) and the structural unit represented by the formula (2-2) comprises: at least one structural unit selected from the group consisting of the structural unit represented by the formula (2-1c), the structural unit represented by the formula (2-1d), and the structural unit represented by the formula (2-2 b).

[4] The organic electronic material according to any one of [1] to [3], wherein the structural unit represented by the formula (3) includes a structural unit represented by the formula (3 a).

[5] The organic electronic material according to any one of [1] to [4], wherein the charge transporting polymer further comprises: at least one structural unit selected from the group consisting of the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2).

[6] The organic electronic material according to [5], wherein at least one structural unit selected from the group consisting of the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2) comprises: at least one structural unit selected from the group consisting of the structural unit represented by the formula (4-1b) and the structural unit represented by the formula (4-2 b).

[7] A method for producing a charge-transporting polymer used for the organic electronic material according to any one of [1] to [6], the method comprising:

reacting a monomer mixture in a solvent comprising an aromatic ether, the monomer mixture comprising: a bifunctional monomer having a structural unit represented by the formula (1), at least one trifunctional monomer or tetrafunctional monomer selected from the group consisting of a trifunctional monomer having a structural unit represented by the formula (2-1) and a tetrafunctional monomer having a structural unit represented by the formula (2-2), and 85 to 100 mol% of a monofunctional monomer having a structural unit represented by the formula (3) based on the total amount of the monofunctional monomers.

[8] A liquid composition comprising: the organic electronic material according to any one of the above [1] to [6 ]; and a solvent.

[9] The liquid composition according to [8], wherein the solvent contains an aromatic ether.

[10] An organic layer formed using the organic electronic material according to any one of the above [1] to [6], or the liquid composition according to the above [8] or [9 ].

[11] An organic electronic element comprising the organic layer according to [10 ].

[12] An organic electroluminescent element comprising the organic layer according to [10 ].

[13] An organic electroluminescent element comprising the organic layer according to [10] as a hole injection layer or a hole transport layer.

[14] A display element comprising the organic electroluminescent element according to [12] or [13 ].

[15] A lighting device comprising the organic electroluminescent element according to [12] or [13 ].

[16] A display device, comprising: the lighting device according to [15 ]; and a liquid crystal element as a display member.

[ examples ]

Embodiments of the present invention will be described more specifically with reference to examples. The embodiments of the present invention are not limited to the following examples.

< preparation of Charge transporting Polymer >

[ preparation of Pd catalyst ]

Tris (dibenzylideneacetone) dipalladium (73.2mg, 80 μmol) was weighed into a sample tube at room temperature in a glove box (glove box) under a nitrogen atmosphere, and anisole (15mL) was added thereto and stirred for 30 minutes. Similarly, tris (tert-butyl) phosphine (129.6mg, 640. mu. mol) was weighed into a sample tube, and anisole (5mL) was added thereto and stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to obtain a solution of the catalyst (hereinafter referred to as "Pd catalyst solution"). In the preparation of the Pd catalyst, all solvents were used after degassing for 30 minutes or more by bubbling nitrogen.

[ preparation of Charge-transporting Polymer ]

The charge-transporting polymers 1 to 22 were prepared in the following manner. The monomers used are shown in table 1.

[ tables 1-1]

(Charge-transporting Polymer 1)

Into a three-necked round-bottomed flask were charged monomer (1b) (5.0mmol), monomer (2-1c) (2.0mmol), monomer (3a) (2.0mmol), monomer (4-1b) (2.0mmol), methyl tri-n-octylammonium chloride ("Aliquat) 336" manufactured by Alfa Aesar corporation (0.04g), a 3M aqueous potassium hydroxide solution (7.79g), and anisole (53mL), and the mixture was further charged and mixed with the Pd catalyst solution (1.0 mL). The resulting mixture was heated under reflux for 2 hours. All operations up to now were carried out under a nitrogen flow. All solvents were used after being degassed by bubbling nitrogen gas for 30 minutes or more.

After the reaction was completed, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was recovered by suction filtration and washed with methanol-water (9: 1). The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The resulting precipitate was recovered by suction filtration, dissolved in toluene, added with a metal adsorbent ("Triphenylphosphine" manufactured by Strem Chemicals, Inc., polymer-bound on styrene-divinylbenzene copolymer (200 mg) to 100mg of the precipitate), and stirred at 80 ℃ for 2 hours. After completion of the stirring, the metal adsorbent and insoluble matter were removed by filtration, and reprecipitation from methanol was performed. The resulting precipitate was recovered by suction filtration and washed with methanol. The resulting precipitate was vacuum-dried to obtain a charge transporting polymer 1. The charge transporting polymer 1 had a number average molecular weight of 15,092 and a weight average molecular weight of 56,449.

The number average molecular weight and the weight average molecular weight are measured by GPC (polystyrene equivalent) using Tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.

The device comprises the following steps: promin Shimadzu corporation of high performance liquid chromatography

Liquid sending pump (LC-20AD)

Degassing unit (DGU-20A)

Automatic sampler (SIL-20AHT)

Tubular column oven (CTO-20A)

Photodiode array (PDA) detector (SPD-M20A)

Differential refractive index detector (RID-20A)

Pipe column: gelpack (registered trademark)

GL-A160S (manufacturing number: 686-1J27)

GL-A150S (production number: 685-1J27) Hitachi chemical Co., Ltd

Eluent: tetrahydrofuran (THF) (for High Performance Liquid Chromatography (HPLC), containing a stabilizer) Fuji film and Wako pure chemical industries, Ltd

Flow rate: 1mL/min

Temperature of the pipe column: 40 deg.C

Detection wavelength: 254nm

Molecular weight standard substance: PStQuick A/B/C Tosoh Co Ltd

(Charge-transporting Polymer 2 to Charge-transporting Polymer 22)

Charge-transporting polymers 2 to 22 were prepared in the same manner as for the charge-transporting polymer 1, except that the monomers used were changed to those shown in table 2.

Table 2 shows the monomer ratios of the charge-transporting polymers 1 to 22, the contents of the monomer (3), the number average molecular weights, and the weight average molecular weights.

[ Table 2]

TABLE 2

In table 2, the values given below the respective monomer numbers are the monomer ratios used in the synthesis. The content (mol%) of the monomer (3) based on the total amount of the monofunctional monomers is described in the column "(3)/(monofunctional monomer)".

< evaluation >

[ evaluation of solvent resistance ]

The organic layers a1 to a22 were formed using the charge-transporting polymers 1 to 22, and the solvent resistance (i.e., the curability of the charge-transporting polymer) was evaluated by the residual film ratio measurement in the following manner. The results are shown in table 3.

(measurement of residual film ratio)

The following polymerization initiator (10mg) was weighed out into a 20mL spiral tube, and chlorobenzene (10mL) was added and stirred to obtain a polymerization initiator solution. Then, a charge transporting polymer (10mg) and chlorobenzene (792. mu.L) were added to the 9mL spiral tube to dissolve the charge transporting polymer. Thereafter, 101. mu.L of the polymerization initiator solution was added to the 9mL spiral tube, and stirred to prepare an ink composition. The ink composition was filtered through a Polytetrafluoroethylene (PTFE) filter (pore size 0.2 μm), and then dropped onto a quartz substrate (22 mm in length x 29mm in width x 0.7mm in thickness) to form a coating film by a spin coater. Next, the mixture was cured by heating at 200 ℃ for 30 minutes in a nitrogen atmosphere to form an organic layer having a thickness of 30nm on the quartz substrate.

[ solution 30]

The absorbance a of the organic layer formed on the quartz substrate was measured using a spectrophotometer ("UV-2700" manufactured by shimadzu corporation). Next, the substrate was immersed in anisole (10mL, 25 ℃) for 10 minutes at 25 ℃ so that the measured organic layer was the top surface. The absorbance B of the organic layer after the anisole impregnation was measured, and the residual film ratio was calculated from the absorbance a of the formed organic layer and the absorbance B of the organic layer after the anisole impregnation using the following formula. The absorbance value was measured at the maximum absorption wavelength of the organic layer. The higher the residual film ratio, the more excellent the solvent resistance.

[ numerical formula 1]

Residual film ratio (%) (absorbance B/absorbance a) × 100

[ HOMO energy level evaluation ]

In the same manner as in the (residual film ratio measurement), the charge-transporting polymers 1 to 22 were used to form the organic layers B1 to B22, and the HOMO levels were measured.

For the measurement of the HOMO level, a photoelectron spectrometer ("AC-5" manufactured by Racto research instruments Co., Ltd.) was used. The results are shown in table 3.

[ evaluation of Charge transport Properties and Heat resistance ]

HOD (hole-only device) a1 to HOD B22 were produced using the charge-transporting polymers 1 to 22 in the following manner, and conductivity and heat resistance were evaluated. The results are shown in table 3.

The polymerization initiator (10mg) was weighed into a 20mL spiral tube, and chlorobenzene (1mL) was added and stirred to obtain a polymerization initiator solution. Then, a charge-transporting polymer (30mg) and chlorobenzene (782. mu.L) were added to a 9mL spiral tube to dissolve the charge-transporting polymer. Thereafter, 93. mu.L of the polymerization initiator solution was added to the 9mL spiral tube, and stirred to prepare an ink composition. The ink composition was filtered through a Polytetrafluoroethylene (PTFE) filter (pore size: 0.2 μm), and then dropped onto a glass substrate (22 mm in the longitudinal direction: 29mm in the transverse direction: 0.7mm in thickness) patterned with ITO to have a width of 1.6mm, and a coating film was formed by a spin coater. Next, the mixture was cured by heating at 200 ℃ for 30 minutes in a nitrogen atmosphere to form an organic layer having a thickness of 100nm on the quartz substrate. The glass substrate was transferred to a vacuum evaporator, and Al (100nm) was formed on the organic layer by an evaporation method, followed by sealing treatment to produce HOD a.

In the same manner as in the production of HOD A, ITO was patterned into a 1.6mm wide glass substrate at a rotational speed of 3,000min^-1The ink composition is spin-coated to form a coating film. Subsequently, the cured product was heated and cured at 200 ℃ for 30 minutes under a nitrogen atmosphere, and further additionally heated at 230 ℃ for 30 minutes under a nitrogen atmosphere. Thereafter, HOD B is produced in the same manner as the production of HODA.

Voltages were applied to HODA and HOD B, respectively, and the current density was measured at 300mA/cm²Voltage a and voltage B. The smaller the values of voltage a and voltage B are, the more excellent the hole injection function is. Further, a voltage difference (a voltage rise) between the voltage a and the voltage B is obtained. The smaller the voltage difference, the more excellent the heat resistance. The results are shown in table 3.

Voltage A: for HOD A (heated at 200 ℃ for 30 minutes under nitrogen) at a current density of 300mA/cm²The value measured.

Voltage B: HOD B (heated at 200 ℃ for 30 minutes under nitrogen atmosphere, and further at 230 ℃ for 30 minutes under nitrogen atmosphere) was heated at a current density of 300mA/cm²The value measured.

Difference in voltage: voltage b (v) -value of voltage a (v).

[ evaluation of element characteristics ]

The organic EL devices 1 to 22 were produced using the charge-transporting polymers 1 to 22 in the following manner, and the driving voltage, the light emission efficiency, and the light emission life were evaluated. The results are shown in table 3.

(preparation of organic EL element)

The polymerization initiator (10mg) was weighed into a 20mL spiral tube, and chlorobenzene (10mL) was added and stirred to obtain a polymerization initiator solution. Then, a 9mL spiral tube was charged with the charge transporting polymer (10mg) and chlorobenzene (583. mu.L) to dissolve the charge transporting polymer. Thereafter, 309. mu.L of the polymerization initiator solution was added to the 9mL spiral tube, and stirred to prepare an ink composition. The ink composition was filtered through a Polytetrafluoroethylene (PTFE) filter (pore size: 0.2 μm), and then dropped onto a glass substrate (22 mm in the longitudinal direction: 29mm in the transverse direction: 0.7mm in thickness) patterned with ITO to have a width of 1.6mm, and a coating film was formed by a spin coater. Subsequently, the mixture was heated on a hot plate at 200 ℃ for 30 minutes in a nitrogen atmosphere to form a hole injection layer (30 nm).

Poly-TPD (Poly [ N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) -benzidine ] (10mg) and chlorobenzene (1794. mu.L) were added to a 9mL spiral tube as a material for a hole transport layer, and stirred. The ink composition was filtered through a Polytetrafluoroethylene (PTFE) filter (pore size 0.2 μm), and then dropped onto the hole injection layer to form a coating film by a spin coater. Subsequently, the mixture was heated on a hot plate at 200 ℃ for 30 minutes in a nitrogen atmosphere to form a hole transport layer (40 nm).

Transferring the glass substrate having the hole injection layer and the hole transport layer to a vacuum evaporation machine, and evaporating CBP, Ir (ppy)₃(94: 6, 30nm), BALq (10nm), TPBi (30nm), LiF (0.8nm) and Al (100nm) were formed in the stated order. Thereafter, a sealing treatment was performed to fabricate an organic EL element.

(evaluation of organic EL element)

As a result of applying a voltage to each organic EL element, green emission was observed. Measurement of light-emission luminance 5,000cd/m²Driving voltage, luminous efficiency and initial luminous brightness of 5,000cd/m²Luminescence lifetime (brightness halved time). The measurement results are shown in table 3.

[ Table 3-1]

As shown in table 3, the organic layer according to the embodiment of the present invention has an appropriate energy level, is excellent in solvent resistance, and can improve the life characteristics of the organic electronic device.

[ description of symbols ]

1: luminescent layer

2: anode

3: hole injection layer

4: cathode electrode

5: electron injection layer

6: hole transport layer

7: electron transport layer

8: substrate