JP6953824B2 - Organic electroluminescent device - Google Patents

Description

The present invention relates to an organic electroluminescent device.

A film having charge transport performance (also called hole transport performance) as one of the organic compound layers of electronic devices such as electrophotographic photosensitive members, organic field light emitting devices, organic transistors, and organic solar cells, that is, "charge transport property". "Membrane" is being actively developed.

For example, Patent Document 1 discloses a reactive compound represented by the general formula (I) or a charge transporting membrane containing a structure derived from the reactive compound.
For example, Patent Document 2 discloses a charge-transporting membrane containing a polymer of a compound represented by the general formula (I).
For example, Patent Document 3 discloses a charge-transporting membrane containing a polymer of a compound represented by the general formula (I).
For example, Patent Document 4 discloses a charge-transporting film obtained by curing a composition containing a compound represented by the general formula (I).

Japanese Unexamined Patent Publication No. 2013-38441 Japanese Unexamined Patent Publication No. 2013-44819 Japanese Unexamined Patent Publication No. 2013-60422 Japanese Unexamined Patent Publication No. 2013-6057

By the way, some organic electroluminescent devices include an organic compound layer containing a polymer of a hole transport compound having a polymerizable group, and the organic compound layer may have high resistance.
Therefore, an object of the present invention is to provide an organic electroluminescent element provided with an organic compound layer having a lower resistance than that containing a polymer composed only of a hole transport compound having a polymerizable group.

Specific means for solving the above problems include the following aspects.

The invention according to <1 > is
It has a pair of electrodes, at least one of which is transparent, and one or more organic compound layers, including a light emitting layer sandwiched between the pair of electrodes.
An organic electroluminescent device in which at least one of the organic compound layers contains a polymer of a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group.

The invention according to <2 > is
The organic electroluminescent device according to < 1 > , wherein the hole transport compound having a polymerizable group is a compound represented by the following general formula (1).

In the general formula (1), F represents a hole-transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S. -, One type of linking group selected from a trivalent group obtained by removing 3 hydrogen atoms from methane and a trivalent group obtained by removing 3 hydrogen atoms from ethylene, or a (n + 1) valent linking group consisting of a combination of two or more types. , R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 1 or more and 6 or less, and n represents an integer of 1 or more and 3 or less.

The invention according to <3 > is
The organic electroluminescent device according to < 2 > , wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In the general formula (2), Ar ^{1 to} Ar ⁴ independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group, respectively. k represents 0 or 1, c1 to c5 independently represent integers of 0 or more and 2 or less, but the total of c1 to c5 is 1 or more. D represents a group represented by the general formula (3), and in the general formula (3), L is an alkylene group, −C = C−, −C (= O) −, −N (R) −, −O. -, -S-, one linking group selected from a trivalent group obtained by removing 3 hydrogen atoms from methane, and a trivalent group obtained by removing 3 hydrogen atoms from ethylene, or a combination of two or more (n + 1). It represents a valent linking group, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 1 or more and 3 or less.

The invention according to <4 > is
The organic electroluminescent device according to < 3 > , wherein the group represented by the general formula (3) in the compound represented by the general formula (2) is a group represented by the following general formula (4).

In the general formula (4), X is one or more selected from an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group consisting of a combination of, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and p represents 0 or 1.

The invention according to <5 > is
The group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the group represented by the following general formula (5-1) or the following general formula (5-2). The organic electroluminescent device according to < 3 > , which is a base.

In the general formula (5-1) and the general formula (5-2), X is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group consisting of one or a combination of two or more selected from, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and p represents 0 or 1.

The invention according to <6 > is
The group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the group represented by the following general formula (6-1) or the group represented by the following general formula (6-2). The organic electroluminescent device according to < 3 > , which is a base.

In the general formula (6-1) and the general formula (6-2), X is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group consisting of one or a combination of two or more selected from, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and p represents 0 or 1.

The invention according to <7 > is
The group in which the electron-transporting compound having a polymerizable group consists of a compound represented by the following general formula (7), a compound represented by the following general formula (8), and a compound represented by the following general formula (9). The organic electroluminescent element according to any one of < 1 > to < 6 > , which is a compound selected from the above.

In the general formula (7), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, and aryl groups, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (8), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 21} , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (9), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 31} , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ , the group represented by −Y− (Z) _m is 1 or more and 4 or less.
Among the groups represented by -Y- (Z) _m , Y was obtained by removing 3 hydrogen atoms from the alkylene group, the adamantane group, -C = C-, -C (= O)-, -O- and methane. Represents a (m + 1) valent linking group consisting of one or a combination of two or more selected from trivalent groups, where Z is an acryloyl group, a methacryloyl group or a styrene group, and m is 1 or 2.

The invention according to <8 > is
The organic electroluminescent device according to any one of < 1 > to < 7 > , further containing at least one selected from a thermal radical generator and a derivative thereof and a photoradical generator and a derivative thereof.

The invention according to <9 > is
The mass ratio (C) of the structural unit (C) derived from the hole transporting compound having a polymerizable group and the structural unit (E) derived from the electron transporting compound having a polymerizable group in the polymer: (E) is 10: 1 to a range 1:20 <1> to the organic electroluminescent device according to <8>.

The invention according to <10 > is
The mass ratio (C) of the structural unit (C) derived from the hole transporting compound having a polymerizable group and the structural unit (E) derived from the electron transporting compound having a polymerizable group in the polymer: The organic electroluminescent element according to < 9 > , wherein (E) is in the range of 1: 1 to 1:15.

The invention according to <11 > is
When the volume resistivity of the organic compound layer containing the polymer of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less. The organic electric field light emitting element according to any one of < 1 > to < 10 >.

According to the inventions relating to < 1 > , < 2 > , < 3 > , < 4 > , < 5 > , < 6 > , < 9 > , < 10 > , or < 11 > , holes having a polymerizable group. Provided is an organic electroluminescent element provided with an organic compound layer having a lower resistance than that of a polymer containing only a transport compound.
According to the invention according to < 7 > , an organic compound layer having a small resistance change as compared with the case where a polymer composed only of a hole transport compound having a polymerizable group and a compound 7, 8 or 9 described later is contained is provided. An organic electroluminescent element is provided.
According to the invention according to < 8 > , an organic compound layer having excellent mechanical strength as compared with the case where it does not contain at least one selected from a thermal radical generator and its derivative and a photoradical generator and its derivative. Provided is an organic electroluminescent element.

It is a schematic cross-sectional view of an example of the organic electroluminescent element which concerns on this embodiment. It is a schematic cross-sectional view of an example of the organic electroluminescent element which concerns on this embodiment. It is a schematic cross-sectional view of an example of the organic electroluminescent element which concerns on this embodiment. It is a schematic cross-sectional view of an example of the organic electroluminescent element which concerns on this embodiment.

Hereinafter, embodiments of the invention will be described. These explanations and examples exemplify embodiments and do not limit the scope of the invention.

In the present specification, when the amount of each component in the layer or composition is referred to, when a plurality of substances corresponding to each component are present in the layer or composition, unless otherwise specified, in the layer. Alternatively, it means the total amount of the plurality of substances present in the composition.

<Organic electroluminescent device>
The organic electroluminescent element according to the present embodiment has a pair of electrodes whose at least one is transparent, and one or a plurality of organic compound layers including a light emitting layer sandwiched between the pair of electrodes, and is an organic compound. At least one of the layers contains a polymer of a hole-transporting compound having a polymerizable group and an electron-transporting compound having a polymerizable group.

The present inventors use a polymer obtained by copolymerizing a hole-transporting compound having a polymerizable group and an electron-transporting compound having a polymerizable group to resist the organic compound layer containing the polymer. Was found to be low.
The polymer obtained by copolymerizing a hole-transporting compound having a polymerizable group and an electron-transporting compound having a polymerizable group has both a hole-transporting site and an electron-transporting site in the molecule. As a result, partial charge transfer is likely to occur between the hole transport site and the electron transport site, resulting in a charged molecule. Then, it is presumed that the amount of electric charge in the organic compound layer containing such a polymer increases and the resistance decreases.
Reducing the resistance of the organic compound layer in an organic electroluminescent device is important from the viewpoint of charge injectability from the electrode, adjustment and increase of the amount of charge. Therefore, it can be said that an organic compound layer containing a polymer of a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group is useful as an organic compound layer constituting an organic electric field light emitting element.

Further, the organic electroluminescent element includes an organic compound layer sandwiched between a pair of electrodes, and the organic compound layer is affected by external factors such as heat and a solvent when forming other layers, and the resistance changes. May occur.
The resistance change of the organic compound layer is 1. 2. The components in the organic compound layer (particularly low molecular weight compounds) move out of the layer due to heat (hereinafter referred to as "migration"). It is considered that this is caused by elution of components in the lower organic compound layer due to a solvent or the like used when forming another layer on the organic compound layer.
In particular, in the case of an organic compound layer containing a polymer of a hole transport compound having a polymerizable group but containing an electron transport compound having no polymerizable group, the electron transport compound is in a state of being easily moved. It is considered that the resistance changes due to migration or elution into the solvent.
The organic compound layer in the present embodiment contains a polymer of a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group. It is considered that by including the polymer in such a form in the organic compound layer, migration and elution of the electron transport compound are suppressed, and resistance change is suppressed.

[Polymer-containing organic compound layer]
First, an organic compound layer containing a polymer of a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group constituting the organic electric field light emitting element according to the present embodiment (hereinafter, appropriately "containing a polymer"). "Organic compound layer") will be described.
The polymer-containing organic compound layer is composed of a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group, as described below, as well as a thermal radical generator and a photoradical generator, if necessary. It is obtained by using a radical generator.

(Hole transport compound having a polymerizable group)
The hole-transporting compound having a polymerizable group in the present embodiment may be a compound in which a polymerizable group is directly bonded to a skeleton having a hole-transporting performance or via a linking group.
Examples of the hole transporting compound having a polymerizable group include various compounds having different types of skeletons having hole transporting performance, types of polymerizable groups, number of polymerizable groups, presence or absence of linking groups, and the like. It may be selected according to the performance required for the contained organic compound layer.
The skeleton having the hole transporting performance may be a skeleton derived from a compound having the hole transporting performance, and specific examples thereof include subunits derived from the compound having the hole transporting performance described later.
The polymerizable group is preferably a functional group capable of radical polymerization, and examples thereof include a functional group having a group containing at least a carbon double bond. Specifically, examples of the polymerizable group include a vinyl group, a vinyl ether group, a vinyl thioether group, a styrene group, an acryloyl group, a methacryloyl group, and a group containing at least one selected from derivatives thereof. ..
The linking group may be any group that can link the above-mentioned skeleton having hole transporting performance and the polymerizable group, and may be linear, branched, cyclic, or a structure combining these. good.

As the hole transport compound having a polymerizable group, a compound represented by the following general formula (1) is preferable from the viewpoints of hole transport performance, polymerization performance, solvent resistance, coating suitability and the like.

The compound represented by the following general formula (1) is a compound in which a styrene group, which is a chain-growth group, is bonded to a hole-transporting subunit represented by F via a linking group L.
In general, the hole transport performance of a hole transport compound tends to decrease as the number of crosslinked sites (number of polymerizable groups) of the hole transport compound increases. It is considered that this is because when the number of cross-linked sites (the number of polymerizable groups) of the hole-transporting compound is increased, the hole-transporting subunit is distorted when polymerized.
On the other hand, the compound represented by the general formula (1) has a structure in which a styrene group, which is a chain-growth polymerizable group, is bonded to the hole-transporting subunit F via a linking group L, and thus is linked. Due to the presence of the group L, the hole transporting subunit is less likely to be distorted when polymerized, and both the polymerization performance and the hole transporting performance can be achieved at the same time.
Further, since the polymer of the compound represented by the general formula (1) is excellent in hole transport performance, charge transfer to and from the electron transport site is more likely to occur, and as a result, the general formula (1) is used. It is presumed that the amount of charge in the organic compound layer containing the polymer of the represented compound increases and the resistance decreases. Therefore, the compound represented by the general formula (1) is useful as a material used for the polymer-containing organic compound layer of the organic electroluminescent device.
Further, the hole transport compound having a styrene group as the chain polymerizable group has the solvent resistance of the chain polymerizable group and the coating of the compound as compared with the hole transport compound having only the (meth) acrylic group as the chain polymerizable group. It is considered to be excellent in aptitude. From this viewpoint as well, the compound represented by the general formula (1) is useful as a material used for the polymer-containing organic compound layer.

In the general formula (1), F represents a hole-transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S. -, One type of linking group selected from a trivalent group obtained by removing 3 hydrogen atoms from methane and a trivalent group obtained by removing 3 hydrogen atoms from ethylene, or a (n + 1) valent linking group consisting of a combination of two or more types. , R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 1 or more and 6 or less, and n represents an integer of 1 or more and 3 or less.
When a plurality of "L" s are present in the molecule, the “L” may be the same or different from each other.

The hole transporting subunit represented by F may be a subunit derived from a compound having hole transporting performance, and specifically, a phthalocyanine compound, a porphyrin compound, an azobenzene compound, or a triaryl. Derived from compounds having hole transport performance such as amine compounds, benzidine compounds, arylalcan compounds, aryl-substituted ethylene compounds, stillben compounds, anthracene compounds, hydrazone compounds, quinone compounds, and fluorenone compounds. Subunits can be mentioned. Of these, subunits derived from triarylamine compounds, which are excellent in charge mobility, oxidative stability, etc., are preferable.

The linking group represented by L is divalent, trivalent or tetravalent, with divalent or trivalent being more preferred.

The divalent linking group represented by L is selected from an alkylene group and at least -C = C-, -C (= O)-, -N (R)-, -O- and -S-. A divalent linking group formed by combining one of the above is preferable, and as the alkylene group, a linear alkylene group having 1 or more and 6 or less carbon atoms is preferable, and a linear alkylene group having 1 or more and 4 or less carbon atoms is more preferable.

Examples of the divalent linking group represented by L include the following groups. Among the following linking groups, "*" is a site to be linked to F, and a, b and c represent the number of repetitions of the methylene group.

*-(CH ₂ ) a-O- (CH ₂ ) b-
*-(CH ₂ ) a-O- (CH ₂ ) c-O- (CH ₂ ) b-
*-(CH ₂ ) a-C (= O) -O- (CH ₂ ) b-
*-(CH ₂ ) a-C (= O) -N (R)-(CH ₂ ) b-
*-(CH ₂ ) a-C (= O) -S- (CH ₂ ) b-
*-(CH ₂ ) a-N (R)-(CH ₂ ) b-
*-(CH ₂ ) a-S- (CH ₂ ) b-
* -O- (CH ₂ ) a-O- (CH ₂ ) b-
* -CH = CH- (CH ₂ ) a-O- (CH ₂ ) b-
* -CH = CH-C (= O) -O- (CH ₂ ) b-

Examples of the trivalent linking group represented by L include the following groups. Among the following linking groups, "*" is a site to be linked to F, and a, b, c, d, e and f represent the number of repetitions of the methylene group.

*-(CH ₂ ) a-CH [-C (= O) -O- (CH ₂ ) b-] ₂
*-(CH ₂ ) a-CH [-CH _2- O- (CH ₂ ) b-] ₂
* -CH = C [-C (= O) -O- (CH ₂ ) b-] ₂
* -CH = C [-(CH ₂ ) c-O- (CH ₂ ) b-] ₂
*-(CH ₂ ) a-CH [-C (= O) -N (R)-(CH ₂ ) b-] ₂
*-(CH ₂ ) a-CH [-C (= O) -S- (CH ₂ ) b-] ₂
*-(CH ₂ ) a-CH [-(CH ₂ ) c-N (R)-(CH ₂ ) b-] ₂
*-(CH ₂ ) a-CH [-(CH ₂ ) c-S- (CH ₂ ) b-] ₂
* -O- (CH ₂ ) d-CH [-(CH ₂ ) c-O- (CH ₂ ) b-] ₂
*-(CH ₂ ) f-O- (CH ₂ ) d-CH [-(CH ₂ ) c-O- (CH ₂ ) b-] ₂

Examples of the tetravalent linking group represented by L include the following groups. Among the following linking groups, "*" is a site to be linked to F, and b, c and g represent the number of repetitions of the methylene group.

As the compound represented by the general formula (1), a compound having a subunit derived from a triarylamine-based compound as the hole transporting subunit is preferable, and specifically, it is represented by the general formula (2). Compounds are preferred.

In the general formula (2), Ar ^{1 to} Ar ⁴ independently represent a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group, respectively. k represents 0 or 1, c1 to c5 independently represent integers of 0 or more and 2 or less, but the total of c1 to c5 is 1 or more. D represents a group represented by the general formula (3), and in the general formula (3), L is an alkylene group, −C = C−, −C (= O) −, −N (R) −, −O. -, -S-, one linking group selected from a trivalent group obtained by removing 3 hydrogen atoms from methane, and a trivalent group obtained by removing 3 hydrogen atoms from ethylene, or a combination of two or more (n + 1). It represents a valent linking group, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 1 or more and 3 or less.

In the general formula (2), when the total of c1 to c5 is 2 or more, a plurality of "D" (that is, groups represented by the general formula (3)) existing in the molecule may be the same or different from each other. You may be.

In the general formula (2), the ^{substituted or unsubstituted aryl groups represented by Ar 1 to} Ar ⁴ may be the same or different from each other.

Substituents other than "D" (that is, the group represented by the general formula (3)) in Ar ^{1 to} Ar ^{4 include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.} Examples thereof include an unsubstituted phenyl group, an alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with an alkoxy group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom.

Ar ^{1 to} Ar ⁴ are preferably any of the structural formulas (11) to (17). Structural formulas (11) to (17) are shown together with "-(D) _C " which collectively indicates "-(D) _C1 " to "-(D) _C4 ^{" connected to Ar 1 to} Ar ^4. ..

In the structural formula (11), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with an alkoxy group, and a phenyl group. Represents one selected from alkoxy groups having 7 or more and 10 or less carbon atoms.

In the structural formula (12), R ¹² and R ¹³ are independently hydrogen atoms, alkyl groups having 1 or more and 4 or less carbon atoms, alkoxy groups having 1 or more and 4 or less carbon atoms, unsubstituted phenyl groups, and 1 or more carbon atoms. It represents one selected from a phenyl group substituted with an alkyl group or an alkoxy group of 4 or less, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom.

In the structural formula (13), R ¹⁴ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. It represents one selected from a substituted phenyl group, an alkoxy group having 7 or more and 10 or less carbon atoms, and a halogen atom. t represents an integer of 0 or more and 4 or less.

In structural formula (17), Ar represents a substituted or unsubstituted arylene group. Ar is preferably structural formula (18) or (19).

In the structural formulas (18) and structural formula (19), R ¹⁵ is 1 or more and 4 or less carbon atoms an alkyl group, having 1 to 4 carbon atoms in the alkoxy group, a substituted or unsubstituted phenyl group, having 1 to 4 carbon It represents one selected from a phenyl group substituted with an alkyl group or an alkoxy group, an aralkyl group having 7 or more and 10 or less carbon atoms, and a halogen atom, and t represents an integer of 0 or more and 4 or less.

In structural formula (17), Z represents a divalent linking group and s represents 0 or 1. Z is preferably any of the structural formulas (21) to (28).

In the structural formula (21), s represents an integer of 1 or more and 10 or less.

In the structural formula (22), s represents an integer of 1 or more and 10 or less.

In the structural formulas (27) and (28), R ²¹ is 1 or more and 4 or less carbon atoms alkyl group, having 1 to 4 carbon atoms in the alkoxy group, an unsubstituted phenyl group, 1 to 4 alkyl group having a carbon number Alternatively, it represents one selected from a phenyl group substituted with an alkoxy group, an aralkyl group having 7 or more and 10 or less carbon atoms, and a halogen atom, t represents an integer of 0 or more and 4 or less, and W represents a divalent linking group. Represents. W is preferably any of the structural formulas (31) to (39). In the structural formula (38), s represents an integer of 0 or more and 3 or less.

^{Ar 5} in the general formula (2) is a substituted or unsubstituted aryl group when k is 0, and is a substituted or unsubstituted arylene group when k is 1.

Examples of the substituted or unsubstituted aryl group represented by Ar ^{5 include the aryl groups exemplified for Ar 1 to} Ar ^4. The substituent in the aryl group was substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Examples thereof include a phenyl group, an aralkyl group having 7 or more and 10 or less carbon atoms, and a halogen atom.

When Ar ⁵ is a substituted or unsubstituted arylene group, C 5 is preferably 0, that is, "D" (that is, a group represented by the general formula (3)) is not bonded to ^{Ar 5.} Is preferable. Examples ^{of the substituted or unsubstituted arylene group represented by Ar 5} include structural formulas (41) to (46).

In the structural formulas (41) to (43), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, and an alkyl group having 1 to 4 carbon atoms. Alternatively, it represents one selected from a phenyl group substituted with an alkoxy group, an aralkyl group having 7 or more and 10 or less carbon atoms, and a halogen atom, and x represents an integer of 0 or more and 4 or less. In the structural formula (43), Y represents a divalent linking group, and Y is preferably any of the structural formulas (51) to (60). In the structural formula (51), y represents an integer of 1 or more and 4 or less.

C1 to c5 in the general formula (2) are independently integers of 0 or more and 2 or less, but the total of c1 to c5 is 1 or more. That is, the compound represented by the general formula (2) has one or more groups represented by the general formula (3). The total number of groups represented by the general formula (3) in the molecule is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and further preferably 2. L and n in the general formula (3) are synonymous with L and n in the general formula (1).

The groups represented by the general formula (3) include a group represented by the general formula (4), a group represented by the general formula (5-1), and a group represented by the general formula (5-2). The group represented by the general formula (6-1) and the group represented by the general formula (6-2) are preferable from the viewpoint of hole transportability and film forming property.

In the general formula (4), X is one or more selected from an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group consisting of a combination of, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and p represents 0 or 1. X is a combination of an alkylene group and at least one selected from −C = C−, −C (= O) −, −N (R) −, −O− and −S− 2 A valent linking group is preferable, and as the alkylene group, a linear alkylene group having 1 or more and 6 or less carbon atoms is preferable, and a linear alkylene group having 1 or more and 4 or less carbon atoms is more preferable. When a plurality of groups represented by the general formula (4) are present in the molecule, the groups represented by the general formula (4) may be the same or different from each other.

As the group represented by the general formula (4), the group represented by the general formula (4-1) or the group represented by the general formula (4-2) is more preferable.

In the general formula (4-1) and the general formula (4-2), q represents an integer of 0 or more and 6 or less, and an integer of 1 or more and 4 or less is preferable.

In the general formula (5-1), general formula (5-2), general formula (6-1) and general formula (6-2), X is an alkylene group, -C = C-, -C (= O). Represents a divalent linking group consisting of one or a combination of one or more selected from −, −N (R) −, −O− and −S−, where R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl. It represents a group and p represents 0 or 1. When there are a plurality of groups represented by the general formula (5-1), the general formula (5-2), the general formula (6-1) or the general formula (6-2) in the molecule, these groups are the same as each other. But it can be very different.

As X, an alkylene group is preferable, as the alkylene group, a linear alkylene group having 1 or more and 6 or less carbon atoms is preferable, a linear alkylene group having 1 or more and 3 or less carbon atoms is more preferable, and a direct alkylene group having 1 or 2 carbon atoms is preferable. Chain alkylene groups are more preferred.

Specific examples of the hole transport compound having a polymerizable group (compound represented by the general formula (1)) are shown below.
Specifically, the specific examples of the hole-transporting subunit represented by F in the general formula (1) and the group linked to F (that is, the group represented by the general formula (3)) are described below. Specific examples and examples thereof are illustrated, and combinations thereof are shown in Table 1 to show specific examples of hole transport compounds having a polymerizable group (compounds represented by the general formula (1)).
The compound represented by the general formula (1) is not limited thereto. In the structural formula shown below, "*" means a connecting site.

For example, in CTM-1, the hole-transporting subunit represented by F (described as “matrix” in Table 1) is (1) -1, and the group represented by the general formula (3) (Table). (Described as "functional group" in 1) is (III) -1, and both are linked by "*" and have the following structure.

Examples of the method for synthesizing the compound represented by the general formula (1) include [0126] of JP2013-43841A, [0070] of JP2013-60422A, and [0099] of JP2013-60572A. ] To [0101] and the like.

The polymer in the polymer-containing organic compound layer in the present embodiment may be obtained by using one type of hole transport compound having a polymerizable group alone, or two or more types may be used. It may be obtained by

(Electron transport compound having a polymerizable group)
The electron-transporting compound having a polymerizable group in the present embodiment may be a compound in which a polymerizable group is directly bonded to a skeleton having electron-transporting performance or via a linking group.
Examples of the electron-transporting compound having a polymerizable group include various compounds having different skeletons having electron-transporting performance, types of polymerizable groups, number of polymerizable groups, presence or absence of linking groups, etc., but polymer-containing organic compounds. It may be selected according to the performance required for the compound layer.
The skeleton having electron transport performance may be any skeleton derived from a compound having electron transport performance, and specifically, quinone compounds such as p-benzoquinone, chloranil, bromanyl, and anthraquinone; tetracyanoquinodimethane. Compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone-based compounds; benzophenone-based compounds; cyanovinyl-based compounds; skeletons derived from ethylene-based compounds and the like can be mentioned.
The polymerizable group is preferably a functional group capable of radical polymerization, and examples thereof include a functional group having a group containing at least a carbon double bond. Specifically, examples of the polymerizable group include a vinyl group, a vinyl ether group, a vinyl thioether group, a styrene group, an acryloyl group, a methacryloyl group, and a group containing at least one selected from derivatives thereof. ..
The linking group may be any group as long as it can link the skeleton having the above-mentioned electron transport performance and the polymerizable group, and may have a linear, branched, cyclic, or a structure in which these are combined. ..

Examples of the electron-transporting compound having a polymerizable group include a compound represented by the following general formula (7) and a following general formula (8) from the viewpoints of electron transport performance, polymerization performance, solvent resistance, coating suitability and the like. It is preferable to select from the group consisting of the following compounds and the compounds represented by the following general formula (9).

In the general formula (7), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, and aryl groups, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (8), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 21} , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (9), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 31} , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ , the group represented by −Y− (Z) _m is 1 or more and 4 or less.
Among the groups represented by -Y- (Z) _m , Y was obtained by removing 3 hydrogen atoms from the alkylene group, the adamantane group, -C = C-, -C (= O)-, -O- and methane. Represents a (m + 1) valent linking group consisting of one or a combination of two or more selected from trivalent groups, where Z is an acryloyl group, a methacryloyl group or a styrene group, and m is 1 or 2.

In the general formulas (7) to (9), preferred embodiments of an alkyl group, an alkoxy group, an aryl group and an aralkyl group are shown below.
The alkyl group is preferably an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and may be linear or branched. However, from the viewpoint of ease of synthesis and coating suitability, a linear alkyl group is used. Is preferable.
As the alkoxy group, an alkoxy group having 1 or more and 4 or less carbon atoms is preferable.
As the aryl group, an unsubstituted phenyl group or a phenyl group substituted with an alkyl group having 1 or more and 4 or less carbon atoms is preferable.
As the aralkyl group, an aralkyl group having 7 or more and 10 or less carbon atoms is preferable.

In the general formulas (7) to (9), preferred embodiments of the group represented by _{−Y− (Z) m are shown below.}
The (m + 1) valent linking group represented by Y preferably contains −C (= O) − and −O− from the viewpoints of ease of synthesis, solvent resistance, film forming property and the like.
Further, from the viewpoint of ease of synthesis, film forming property, etc., it is preferable that the (m + 1) valent linking group represented by Y contains a linear alkylene group.
The (m + 1) valent linking group represented by Y preferably contains an adamantane group from the viewpoints of ease of synthesis, solvent resistance, film forming property and the like.
The (m + 1) valent linking group represented by Y may have a substituent, and the substituents that can be introduced include a substituted or unsubstituted alkyl group, a phenyl group, and further substituted or unsubstituted. Examples of a group composed of a combination of an alkyl group or a phenyl group of the above and one or more selected from -C (= O)-, -N (R)-, -O-, and -S-. ..

As the polymerizable group represented by Z, a styrene group, an acryloyl group, or a methacryloyl group is preferable from the viewpoint of polymerization performance, solvent resistance, film forming property, and the like.
Further, from the viewpoint of film forming property, solvent resistance and the like, the polymerizable group represented by Z is preferably a styrene group.
m is 1 or 2, but 1 is preferable from the viewpoint of solvent resistance.

^{The compounds represented by the general formula (7) include R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ from the viewpoints of polymerization performance, solvent resistance, coating suitability, and the like. Of these, one is _{preferably a group represented by −Y− (Z) m} , and the rest is preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms. Among them, carbon is preferable from the viewpoint of solvent resistance. It is more preferable that the number of alkyl groups of 1 or more and 3 or less is 1 or more and 4 or less.

^{The compounds represented by the general formula (8) include R 21} , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ from the viewpoints of polymerization performance, solvent resistance, coating suitability and the like. Of these, one is _{preferably a group represented by −Y− (Z) m} , and the rest is preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms. Among them, carbon is preferable from the viewpoint of solvent resistance. It is more preferable that the number of alkyl groups of 1 or more and 3 or less is 1 or more and 4 or less.

^{The compounds represented by the general formula (9) include R 31} , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ from the viewpoints of polymerization performance, solvent resistance, coating suitability and the like. Of these, one is _{preferably a group represented by −Y− (Z) m} , and the rest is preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms. Among them, carbon is preferable from the viewpoint of solvent resistance. It is more preferable that the number of alkyl groups of 1 or more and 3 or less is 1 or more and 4 or less.

The following are specific examples of electron-transporting compounds having a polymerizable group (compounds represented by the general formula (7), compounds represented by the general formula (8), and compounds represented by the general formula (9)). show.
Specifically, the specific examples of the mother nuclei of the compound represented by the general formula (7), the specific examples of the mother nuclei of the compound represented by the general formula (8), and the general formula (9) are shown below. Specific examples of the mother nucleus of the compound to be used and specific examples of the _{functional group represented by −Y− (Z) m} are illustrated, and the combinations thereof are shown in Table 2 for electron transport having a polymerizable group. Specific examples of the compound (the compound represented by the general formula (7), the compound represented by the general formula (8), and the compound represented by the general formula (9)) are shown.
The compound represented by the general formula (7), the compound represented by the general formula (8), and the compound represented by the general formula (9) are not limited thereto.
In the structural formula shown below, "*" means a connecting site and "C ₃ H ₇ " means an n-propyl group.

Examples of the method for synthesizing the compound represented by the general formula (7), the compound represented by the general formula (8), and the compound represented by the general formula (9) include the following methods.

The following scheme can be mentioned as an example of the method for synthesizing the compound represented by the general formula (7).

In a three-necked flask, 12.3 g (0.055 mol) of 9-Fluorenone-4-carboxylic acid (the above structure, manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.07 g (0.107 mol) of nitrile malonic acid were dissolved in 300 ml of toluene. , 0.5 ml of piperidine is added, and the mixture is stirred at 110 ° C. for 5 hours under a nitrogen stream. After allowing to cool to room temperature, 500 ml of hexane is added, and the precipitated precipitate is collected by filtration and purified by column chromatography (adsorbent: silica gel, solvent: ethyl acetate / hexane = 3/7).
Recrystallize from ethyl acetate / hexane to give 8.0 g of intermediate.
Subsequently, the intermediate is chlorinated with a carboxy group using thionyl chloride or the like, and then the target “functional group represented by _{−Y− (Z) m” is introduced.} The compound having a polymerizable group and a hydroxy group is reacted.

The following scheme can be mentioned as an example of the method for synthesizing the compound represented by the general formula (8).
That is, 9-Fluorenone-4-carboxylic Acid (the following structure, manufactured by Tokyo Chemical Industry Co., Ltd.) is used, and thionyl chloride or the like is used to chlorinate the carboxy group, and then the target "-Y" is used. A compound having a polymerizable group and a hydroxy group for introducing a “functional group represented by − (Z) _{m” is reacted.}

The following scheme can be mentioned as an example of the method for synthesizing the compound represented by the general formula (9).
That is, using Anthraquinone-2-carbonyl Chloride (structure below, manufactured by Tokyo Chemical Industry Co., Ltd.), polymerization for introducing the _{desired "functional group represented by -Y- (Z) m".} The compounds having a sex group and a hydroxy group are reacted.

The polymer in the polymer-containing organic compound layer in the present embodiment may be obtained by using one type of electron transport compound having a polymerizable group alone, or by using two or more types. It may be obtained.

(Heat radical generator, photo radical generator)
The polymer-containing organic compound layer in the present embodiment may further contain at least one selected from a thermal radical generator and its derivative, and a photoradical generator and its derivative.
Here, the "derivative of the thermal radical generator" means a product after the thermal radical generator generates a radical, or a product in which the thermal radical generator is bound to the end of the polymer.
Further, the “derivative of the photoradical generator” means a product after the photoradical generator generates a radical, or a product in which the photoradical generator is bound to the end of the polymer.
By obtaining a polymer of a hole transporting compound having a polymerizable group and an electron transporting compound having a polymerizable group using at least one selected from the group consisting of a thermal radical generator and a photoradical generator. At least one selected from a thermal radical generator and a derivative thereof and a photoradical generator and a derivative thereof is introduced into the polymer-containing organic compound layer.
Such a polymer-containing organic compound layer is suitable for laminating because it has excellent mechanical strength.

Examples of the thermal radical generator include azo compounds and organic peroxides.

Commercially available thermal radical generators include V-30 (10-hour half-life temperature: 104 ° C.), V-40 (same as above: 88 ° C.), V-59 (same as above: 67 ° C.), V-601 (same as above:: 66 ° C.), V-65 (same as above: 51 ° C.), V-70 (same as above: 30 ° C.), VF-096 (same as above: 96 ° C.), Vam-110 (same as above: 111 ° C.), Vam-111 (same as above:: 111 ° C.) (above, manufactured by Wako Pure Chemical Industries, Ltd.), OT _AZO- 15 (same as above: 61 ° C.), OT _AZO- 30, AIBN (same as above: 65 ° C.), AMBN (same as above: 67 ° C.), ADVN (same as above: 52 ° C.) ° C.), ACVA (same as above: 68 ° C.) (all manufactured by Otsuka Chemical Co., Ltd.) and other azo-based initiators; P, Permenta H, Perocta H, Perbutyl C, Perbutyl D, Perhexyl D, Parloyl IB, Parloyl 355, Parloyl L, Parloyl SA, Niper BW, Niper BMT-K40 / M, Parloyl IPP, Parloyl NPP, Parloyl TCP, Parloyl OPP , Perloyl SBP, Park Mill ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 25Z, Perbutyl A, Perhexyl Z, Perbutyl ZT, Perbutyl Z (all manufactured by Nichiyu Kagaku Co., Ltd.), Kayaquetal AM-C55, Trigonox 36-C75, Laurox, Percadox L-W75, Percadox CH- 50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Percadox BC-FF, Kayahexa AD, Parkadox 14, Kayabutyl C, Kayabutyl D, Kayahexa YD-E85, Parkadox 12-XL25, Parkadox 12-EB20, Trigonox 22 -N70, Trigonox 22-70E, Trigonox D-T50, Trigonox 423-C70, Kayaester CND-C70, Kayaester CND-W50, Trigonox 23-C70, Trigonox 23-W50N, Trigonox 257-C70, Kayaester P-70 , Kayaester TMPO-70, Trigonox 121, Kayaester O, Kayaester HTP-65W, Kayaeste LUAN, Trigonox 42, Trigonox F-C50, Kayabutyl B, Kayacarboxylic EH-C70, Kayacarboxylic EH-W60, Kayacarboxylic I-20, Kayacarboxylic BIC-75, Trigonox 117, Kayalen 6-70 (all manufactured by Kayaku Akzo) , Luperox LP (same: 64 ° C), Luperox 610 (same: 37 ° C), Luperox 188 (same: 38 ° C), Luperox 844 (same: 44 ° C), Luperox 259 (same: 46 ° C), Luperox 10 (same: same: 46 ° C). : 48 ° C), Luperox 701 (same: 53 ° C), Luperox 11 (same: 58 ° C), Luperox 26 (same: 77 ° C), Luperox 80 (same: 82 ° C), Luperox 7 (same: 102 ° C), Luperox 270 (same: 102 ° C), Luperox P (same: 104 ° C), Luperox 546 (same: 46 ° C), Luperox 554 (same: 55 ° C), Luperox 575 (same: 75 ° C), Luperox TANPO (same:: 96 ° C), Luperox 555 (same: 100 ° C), Luperox 570 (same: 96 ° C), Luperox TAP (same: 100 ° C), Luperox TBIC (same: 99 ° C), Luperox TBEC (same: 100 ° C), Luperox JW (same: 100 ° C), Luperox TAIC (same: 96 ° C), Luperox TAEC (same: 99 ° C), Luperox DC (same: 117 ° C), Luperox 101 (same: 120 ° C), Luperox F (same: 116 ° C) ° C), Luperox DI (same: 129 ° C), Luperox 130 (same: 131 ° C), Luperox 220 (same: 107 ° C), Luperox 230 (same: 109 ° C), Luperox 233 (same: 114 ° C), Luperox 531 (Same as above: 93 ° C.) (above, manufactured by Alchema Yoshitomi Co., Ltd.) and the like.

Examples of the photoradical generator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salts, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and keto. Examples thereof include oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds and the like.

Specific examples of the photoradical generator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, and triphenyl. Amin, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl Examples thereof include −phosphine oxide, 2,4-diethylthioxanthone, and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

The polymer-containing organic compound layer in the present embodiment may further contain at least one selected from a light emitting material, a dye compound, a hole transporting material, a hole injecting material, an electron transporting material, and an electron injecting material. good.
Specific examples of these materials will be described later.

(Formation of polymer-containing organic compound layer)
The polymer-containing organic compound layer in the present embodiment may include a polymer of a hole-transporting compound having a polymerizable group and an electron-transporting compound having a polymerizable group, but an organic electroluminescent element having a lower resistance can be obtained. For this purpose, a cured film obtained by curing a composition containing a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group is preferable.
The polymer-containing organic compound layer (cured film) may contain a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group in an unreacted state.

Further, in the composition containing the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group, the content ratio of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group is , The resistance value, the hole transport performance, the electron transport performance, their balance, and the polymerization performance required for the polymer-containing organic compound layer (cured film) may be determined.
For example, when the polymer-containing organic compound layer is a layer having hole transport performance, a composition containing more hole transport compounds having a polymerizable group than an electron transport compound having a polymerizable group is used. And a layer may be formed.
When the polymer-containing organic compound layer is used as a layer having electron transporting performance, a composition containing more electron transporting compounds having a polymerizable group than a hole transporting compound having a polymerizable group is used. , Layers may be formed.

Polymer-containing organic compound layer (cured film) from the viewpoints of easy availability of hole-transporting compounds having a polymerizable group and electron-transporting compounds having a polymerizable group, as well as solvent resistance, film-forming property, and charge injection property. Is preferably a layer having hole transport performance.
As described above, when the layer has a hole transporting performance, a composition containing more hole transporting compounds having a polymerizable group than an electron transporting compound having a polymerizable group may be used.
Specifically, for example, the electron-transporting compound having a polymerizable group is 0.1% by mass or more and 20% by mass or less (preferably 1% by mass or more and 15% by mass or less) with respect to the hole-transporting compound having a polymerizable group. Hereinafter, by using the composition used in a proportion of 2% by mass or more and 10% by mass or less), a layer having a hole transporting performance constituting the organic electroluminescent element can be obtained.

In the present embodiment, when the polymer-containing organic compound layer is a layer having hole transporting performance, the polymer contained in such a layer is a structural unit (C) derived from a hole transporting compound having a polymerizable group. The mass ratio (C): (E) with the structural unit (E) derived from the electron-transporting compound having a polymerizable group is preferably in the range of 10: 1 to 1:20, and is preferably 1: 1 to 1:15. Is more preferable, and the range of 1: 2 to 1:10 is even more preferable.
The structural unit (C) and the structural unit (E) are adjusted by changing the amount ratio of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group.

The cured film is obtained by curing a composition containing a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group with energy such as heat, light, and an electron beam.
At the time of curing, a thermal radical generator or a photoradical generator may be used in a composition containing a hole transporting compound having a polymerizable group and an electron transporting compound having a polymerizable group, depending on the energy used. It is preferable because a cured film having improved curability and excellent mechanical strength can be obtained.
In order to balance the characteristics such as electrical characteristics and mechanical strength of the cured film, thermosetting is desirable to obtain the cured film.

The amount of the thermal radical generator to be used may be appropriately determined according to the amount of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group.
For example, in a composition containing a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group, the total amount of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group: 100 parts by mass. On the other hand, 0.1 part by mass or more and 25 parts by mass or less is preferable, 1 part by mass or more and 20 parts by mass or less is more preferable, and 5 parts by mass or more and 18 parts by mass or less is further desirable.

The amount of the photoradical generator to be used may be appropriately determined according to the amount of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group.
For example, in a composition containing a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group, the total amount of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group: 100 parts by mass. On the other hand, 0.001 parts by mass or more and 10 parts by mass or less is desirable, 0.01 parts by mass or more and 5 parts by mass or less is more desirable, and 0.1 parts by mass or more and 3 parts by mass or less is further desirable.

The content of the polymer of the hole transporting compound having a polymerizable group and the electron transporting compound having a polymerizable group in the polymer-containing organic compound layer according to the present embodiment may be set according to the intended use. Generally, the total solid content is in the range of 50% by mass or more and 99% by mass or less.

The polymer-containing organic compound layer according to the present embodiment preferably has a volume resistivity of 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less, and 1 × 10 ⁵ Ω · cm or more and 1 × 10 ^{It is more preferably 13} Ω · cm or less, and further preferably 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁰ Ω · cm or less.

[Organic electroluminescent device]
An organic electroluminescent device is a device composed of a pair of electrodes whose at least one is transparent and one or a plurality of organic compound layers including a light emitting layer sandwiched between the pair of electrodes.
In the organic electroluminescent device according to the present embodiment, at least one of the organic compound layers is the polymer-containing organic compound layer described above.

In the organic electroluminescent element according to the present embodiment, when the organic compound layer is a single layer, the organic compound layer is a light emitting layer having a hole transporting performance, and the light emitting layer having this hole transporting performance is the present embodiment. It becomes the above-mentioned polymer-containing organic compound layer in.

In the organic electroluminescent device, when the organic compound layers are a plurality of layers (that is, when each layer is a function-separated type having different functions), at least one of the layers is a light emitting layer, and for example, the following layer structure (1). ) To (3). In the layer structure (1) to (3), in the organic electroluminescent device according to the present embodiment, at least one layer is the polymer-containing organic compound layer described above.

Layer structure (1): A function-separated layer structure having a hole transport layer and a light emitting layer. In this configuration, at least one of the hole transport layer and the light emitting layer may be a polymer-containing organic compound layer, and the hole transport layer is preferably a polymer-containing organic compound layer.

Layer structure (2): A function-separated layer structure having a hole transport layer, a light emitting layer, and an electron transport layer. In this configuration, at least one of the hole transport layer, the light emitting layer and the electron transport layer may be a polymer-containing organic compound layer, and the hole transport layer is preferably a polymer-containing organic compound layer.

Layer structure (3): A function-separated layer structure having a light emitting layer and an electron transport layer. In this configuration, at least one of the light emitting layer and the electron transporting layer may be a polymer-containing organic compound layer, and the light emitting layer is preferably a polymer-containing organic compound layer.

Hereinafter, the organic electroluminescent device according to the present embodiment will be described with reference to the drawings, but the present embodiment is not limited to this.

1 to 4 are schematic cross-sectional views for explaining the layer structure of the organic electroluminescent element according to the present embodiment, and FIGS. 1, 2, and 3 are composed of a plurality of organic compound layers. FIG. 4 shows an example of the case where the organic compound layer is composed of a single layer. In FIGS. 1 to 4, layers having the same function will be described with the same reference numerals.

FIG. 1 shows the layer structure (1).
The organic electroluminescent device shown in FIG. 1 is an element in which a transparent electrode 2, a hole transport layer 3, a light emitting layer 4, and a back electrode 7 are laminated in this order on a transparent insulator substrate 1. A hole injection layer may be arranged between the transparent electrode 2 and the hole transport layer 3. In the embodiment shown in FIG. 1, it is preferable that the hole transport layer 3 is the polymer-containing organic compound layer of the present embodiment, and if the hole injection layer is further arranged, the hole injection layer is formed. May be used as the polymer-containing organic compound layer in the present embodiment.

FIG. 2 shows the layer structure (2).
The organic electroluminescent device shown in FIG. 2 is an element in which a transparent electrode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a back electrode 7 are laminated in this order on a transparent insulator substrate 1. A hole injection layer may be arranged between the transparent electrode 2 and the hole transport layer 3. An electron injection layer may be arranged between the electron transport layer 5 and the back electrode 7. In the embodiment shown in FIG. 2, it is preferable that the hole transport layer 3 is the polymer-containing organic compound layer of the present embodiment, and if the hole injection layer is further arranged, the hole injection layer is formed. May be used as the polymer-containing organic compound layer in the present embodiment.

FIG. 3 shows the layer structure (3).
The organic electroluminescent device shown in FIG. 3 is an element in which a transparent electrode 2, a light emitting layer 6, an electron transport layer 5, and a back electrode 7 are laminated in this order on a transparent insulator substrate 1. An electron injection layer may be arranged between the electron transport layer 5 and the back electrode 7. In the embodiment shown in FIG. 3, it is preferable that the light emitting layer 6 is the polymer-containing organic compound layer in the present embodiment. In this case, at least one kind of light emitting material is contained in the polymer-containing organic compound layer in the present embodiment.

FIG. 4 shows a single-layer type layer structure. The organic electroluminescent device shown in FIG. 4 is an element in which a transparent electrode 2, a light emitting layer 6 having hole transporting performance, and a back electrode 7 are laminated in this order on a transparent insulator substrate 1. In the embodiment shown in FIG. 4, the light emitting layer 6 is the polymer-containing organic compound layer in the present embodiment. In this case, at least one kind of light emitting material is contained in the polymer-containing organic compound layer in the present embodiment.

In each of the organic electroluminescent devices shown in FIGS. 1 to 4, a protective layer may be provided on the back electrode 7 for the purpose of preventing deterioration of the organic electroluminescent device due to moisture or oxygen.

When the top emission structure is used, or when the two electrodes are both transparent electrodes, the layer structure shown in FIGS. 1 to 4 can be stacked in a plurality of stages.

Hereinafter, each layer in FIGS. 1 to 4 will be described in more detail.

Regarding the transparent insulator substrate 1, "transparency" means that the light transmittance in the visible region is 10% or more, and the transmittance is preferably 75% or more.
As the transparent insulator substrate 1, for example, a glass plate, a quartz plate, a metal foil, or a resin film is used. Examples of the material of the resin film include methacrylic resin such as polymethylmethacrylate (PMMA), polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polycarbonate resin.
The transparent insulator substrate 1 may be surface-treated or may have a laminated structure for the purpose of suppressing water permeability and gas permeability.

Similar to the transparent insulator substrate 1, the transparent electrode 2 is transparent because it extracts light emission, and is preferably an electrode having a large work function because holes are injected, and an electrode having a work function of 4 eV or more is preferable.

Regarding the transparent electrode 2, transparency means that the transmittance of light in the visible region is 10% or more, and the transmittance is preferably 75% or more.
As the material of the transparent electrode 2, metal oxides such as indium tin oxide (ITO), tin oxide, indium oxide, zinc oxide and zinc oxide; metals such as aluminum, nickel, gold, silver, platinum and palladium; iodide Examples thereof include metal halides such as copper; conductive polymers such as carbon black, poly (3-methylthiophene), polypyrrole, and polyaniline;
The lower the sheet resistance of the transparent electrode 2, the more desirable it is, preferably several hundred Ω / □ or less, and more preferably 100 Ω / □ or less.

The organic compound layer (layer represented by reference numerals 3 to 6 in FIGS. 1 to 4) is composed of a hole transport material, a hole injection material, an electron transport material, an electron injection material, and a light emitting material, depending on its function. Includes selected materials.
When the organic compound layer is the polymer-containing organic compound layer in the present embodiment, a composition obtained by mixing a hole transport compound having a polymerizable group and an electron transport compound having a polymerizable group together with these materials is used. Layers may be formed.

Examples of the hole transporting material include tetraphenylenediamine derivatives, triphenylamine derivatives, carbazole derivatives, stylben derivatives, arylhydrazone derivatives, and porphyrin-based compounds, and tetraphenylenediamine derivatives, spirofluorene derivatives, and triphenylamine derivatives. ..

Examples of the hole injection material include a phenylenediamine derivative, a phthalocyanine derivative, an indanslen derivative, a polyalkylenedioxythiophene derivative and the like, and these include organic acids such as Lewis acid and sulfonic acid, and inorganic acids such as iron chloride. May be mixed.

Examples of the electron transporting material include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, silol derivatives, chelated organic metal complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, triazole derivatives, and fluorenylidene. Examples include methane derivatives.

As the electron injecting material, Li, Ca, a metal or LiF in or Sr, metal fluorides MgF like, _{MgO, Al} 2 O 3, metal oxides, such as LiO and the like.

As the light emitting material, a compound showing high light emission quantum efficiency in the solid state is desirable. The light emitting material may be either a low molecular weight compound or a high molecular weight compound.
Examples of the organic low molecular weight compound include a chelated organic metal complex, a polynuclear or condensed aromatic ring compound, a perylene derivative, a coumarin derivative, a styrylarylene derivative, a silol derivative, an oxazole derivative, an oxathiazole derivative, and an oxadiazole derivative.
Examples of the organic polymer compound include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyacetylene derivatives.

Specific examples of the luminescent material include the following exemplified compounds (VI-1) to (VI-17).
The following exemplified compounds (VI-1) to (VI-17) can also be used as electron transport materials.

In the exemplified compounds (VI-13) to (VI-17), n and g are independently integers of 1 or more, and V is a divalent linking group. Examples of V include the following divalent groups.
In the following divalent group, g represents an integer of 1 or more, and h represents an integer of 0 or more and 5 or less.

For the purpose of improving the durability or the luminous efficiency of the organic electroluminescent element, a dye compound different from the light emitting material may be doped as a guest material in the light emitting material.
The doping amount of the dye compound is preferably 0.001 part by mass or more and 40 parts by mass or less, and more preferably 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the host.

Dye compounds for doping include coumarin derivatives, DCM derivatives, quinacridone derivatives, perimidone derivatives, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, rubrene derivatives, porphyrin derivatives; ruthenium, rhodium, palladium, silver, renium, osnium, iridium. , Platinum, and metal complex compounds such as gold; and the like.
Specific examples of the dye compound for doping include exemplary compounds (VII-1) to (VII-6).

Each organic compound layer may contain a binder resin.
As the binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, police styrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinyl chloride den-acrylonitrile Examples thereof include copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, silicon resins, poly-N-vinylcarbazole resins, polysilane resins, polythiophene, and conductive resins such as polypyrrole.
Each organic compound layer may contain a known antioxidant, ultraviolet absorber, plasticizer and the like, if necessary.

As the material of the back electrode 7, a material that can be vacuum-deposited and has a small work function for performing electron injection is preferable, and a metal, a metal oxide, and a metal fluoride are preferable.
Examples of the metal include magnesium, aluminum, gold, silver, indium, lithium, calcium and alloys thereof.
Examples of the metal oxide include lithium oxide, magnesium oxide, aluminum oxide, indium oxide, tin oxide, indium oxide, zinc oxide, and zinc indium oxide.
Examples of the metal fluoride include lithium fluoride, magnesium fluoride, strontium fluoride, calcium fluoride, and aluminum fluoride.

A protective layer may be provided on the back electrode 7.
As the material of the protective layer, metals such as indium, tin, lead, gold, silver, copper and aluminum; metal oxides such as magnesium oxide, silicon dioxide and titanium oxide; resins such as polyethylene resin, polyurea resin and polyimide resin; Can be mentioned.

The thickness of the transparent electrode 2, each organic compound layer, the back electrode 7, and the protective layer is generally 0.001 μm or more and 10 μm or less, preferably 0.001 μm or more and 5 μm or less.

The organic electroluminescent device shown in FIGS. 1 to 4 is manufactured by sequentially forming a transparent electrode 2, each organic compound layer, and a back electrode 7 on a transparent insulator substrate 1.
The transparent electrode 2, each organic compound layer, and the back electrode 7 can be formed by, for example, a vacuum vapor deposition method, a sputtering method, a coating method, or the like.
The coating method is a film forming method in which a coating liquid in which a material is dissolved or dispersed in an appropriate solvent is applied onto the transparent electrode 2 and the coating film is dried.
Examples of the coating method of the coating liquid include a spin coating method, a die coating method, an inkjet method, a casting method, a dip method and the like.

The content state of each material in the organic compound layer may be a state in which molecules are dispersed (molecular dispersion state) or a state in which particles are formed and dispersed (particle dispersion state).
In order to obtain a molecularly dispersed state in a film forming method using a coating liquid, the solvent of the coating liquid is selected in consideration of the dispersibility and solubility of each material.
In order to obtain a particle-dispersed state in a film forming method using a coating liquid, a coating liquid is prepared using any one of a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, and ultrasonic waves.

The organic electroluminescent elements according to the present embodiment are arranged in a matrix or segment to form an image display medium.
When the organic electroluminescent elements are arranged in a matrix, only the electrodes may be arranged in a matrix, or the electrodes and the organic compound layer may be arranged in a matrix.
When the organic electroluminescent device is arranged in a segment shape, only the electrode may be arranged in a segment shape, or the electrode and the organic compound layer may be arranged in a segment shape.
The matrix-like or segment-like organic compound layer can be formed by an inkjet method.

Examples of the driving device and driving method for the matrix-shaped organic electroluminescent element and the segmented organic electroluminescent element are JP-A-2-148678, JP-A-6-301355, JP-A5-29800, and JP-A-7. The driving device and driving method described in JP-A-134558, JP-A-8-234685, JP-A-8-241047, Patent No. 2784615, US Pat. No. 5,284,229, US Pat. No. 6,023,308, etc. Applicable.

Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited thereto. Unless otherwise specified, "%" represents "mass%".

<Synthesis of compound represented by general formula (1)>
[Synthesis Example 1: Synthesis of CTM-11]
CTM-11 shown in Table 1 was synthesized by the following scheme.

In a three-necked flask, 25 g of compound (1), 250 ml of toluene, and 12.8 g of diethyl malonate were collected and dissolved. Then, 3.4 g of piperidine and 3.6 g of acetic acid were added, and the mixture was stirred at 130 ° C. for 2 hours. Then, 0.68 g of piperidine and 0.72 g of acetic acid were added, and the mixture was stirred at 130 ° C. for 1 hour. Then, the mixture was cooled to room temperature, 250 ml of toluene was added, the organic layer was washed 3 times with 250 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 10/1) to obtain 33.3 g of the oily compound (2).
Next, 33.3 g of the oily compound (2) was collected in a eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran, 50 ml of ethanol and 2 g of 10% Pd / C were added, connected to a hydrogen gas supply source, stirred for 24 hours, and depressurized. The lower solvent was distilled off. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 32.3 g of the oily compound (3).
Next, 25 g of the oily compound (3) was collected in a eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran and 50 ml of ethanol, and a solution of 8.7 g of sodium hydroxide dissolved in 25 ml of distilled water was gradually added at 0 ° C. Was added dropwise to the mixture, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was washed twice with 100 ml of toluene. Then, the solid, 200 ml of dimethylformamide and 40 g of chloromethylstyrene were stirred at room temperature for 15 minutes and at 70 ° C. for 7 hours. Then, the mixture was cooled to room temperature, 500 ml of toluene was added, the organic layer was washed 3 times with 500 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 27.1 g of the oily compound CTM-11.

[Synthesis Example 2: Synthesis of CTM-12]
CTM-12 shown in Table 1 was synthesized by the following scheme.

25 g of compound (3) synthesized by the same method as in Synthesis Example 1 was dissolved in 250 ml of tetrahydrofuran, 8.9 g of lithium aluminum hydride was added, and the mixture was stirred at room temperature for 2 hours. Next, 500 ml of water and 1 L of toluene were added, and the solid content was filtered off with a filter paper lined with Celite. Next, the organic layer was washed 3 times with 500 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was recrystallized from 20 ml of hexane and 30 ml of ethyl acetate to obtain 18.5 g of a pale pink solid compound (4).
Then, 16.5 g of the solid compound (4) was dissolved in 200 ml of tetrahydrofuran, 18 g of 4-chloromethylstyrene and 11.9 g of potassium tert-butoxide were gradually added, and the mixture was stirred at 70 ° C. for 16 hours. Then, the mixture was cooled to room temperature, 250 ml of toluene was added, the organic layer was washed 3 times with 250 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 20.3 g of oily CTM-12.

[Synthesis Example 3: Synthesis of CTM-15]
CTM-15 shown in Table 1 was synthesized by the following scheme.

In a three-necked flask, 25 g of compound (5), 250 ml of toluene, and 12.8 g of diethyl malonate were collected and dissolved. Then, 3.4 g of piperidine and 3.6 g of acetic acid were added, and the mixture was stirred at 130 ° C. for 2 hours. Then, 0.68 g of piperidine and 0.72 g of acetic acid were added, and the mixture was stirred at 130 ° C. for 1 hour. Then, the mixture was cooled to room temperature, 250 ml of toluene was added, the organic layer was washed 3 times with 250 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 31.2 g of an oily compound (6).
Next, 31.2 g of the oily compound (6) was collected in a eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran, 50 ml of ethanol and 2 g of 10% Pd / C were added, and the mixture was connected to a hydrogen gas supply source and stirred for 24 hours under reduced pressure. The solvent was distilled off. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 29.8 g of an oily compound (7).
Next, 25 g of the oily compound (7) was collected in a eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran and 50 ml of ethanol, and a solution of 8.7 g of sodium hydroxide dissolved in 25 ml of distilled water was gradually added at 0 ° C. The mixture was added dropwise, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was washed twice with 100 ml of toluene. Then, the solid, 200 ml of dimethylformamide and 40 g of chloromethylstyrene were stirred at room temperature for 15 minutes and at 70 ° C. for 7 hours. Then, the mixture was cooled to room temperature, 500 ml of toluene was added, the organic layer was washed 3 times with 500 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 25.3 g of the oily compound CTM-15.

[Synthesis Example 4: Synthesis of CTM-16]
CTM-16 shown in Table 1 was synthesized by the following scheme.

25 g of compound (7) synthesized in the same manner as in Synthesis Example 3 was dissolved in 250 ml of tetrahydrofuran, 9.2 g of lithium aluminum hydride was added, and the mixture was stirred at room temperature for 2 hours. Next, 500 ml of water and 1 L of toluene were added, and the solid content was filtered off with a filter paper lined with Celite. Next, the organic layer was washed 3 times with 500 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 2/1) to obtain 17.8 g of an oily compound (8).
Then, 16.0 g of the oily compound (8) was dissolved in 200 ml of tetrahydrofuran, 17.5 g of 4-chloromethylstyrene and 11.2 g of potassium tert-butoxide were gradually added, and the mixture was stirred at 70 ° C. for 16 hours. Then, the mixture was cooled to room temperature, 250 ml of toluene was added, the organic layer was washed 3 times with 250 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 18.7 g of oily CTM-16.

[Synthesis Example 5: Synthesis of CTM-17]
CTM-17 shown in Table 1 was synthesized by the following scheme.

Compound (6) was synthesized from compound (5) in the same manner as in Synthesis Example 3. Next, 27.5 g of the oily compound (6) was collected in a eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran and 50 ml of ethanol, and a solution prepared by dissolving 8.7 g of sodium hydroxide in 25 ml of distilled water at 0 ° C. The mixture was gradually added dropwise, and the mixture was stirred at room temperature for 2 hours. The lower layer separated into two layers was washed twice with 100 ml of toluene. Then, the lower layer, 200 ml of dimethylformamide and 40 g of chloromethylstyrene were stirred at room temperature for 15 minutes and at 70 ° C. for 7 hours. Then, the mixture was cooled to room temperature, 500 ml of ethyl acetate was added, the organic layer was washed 3 times with 500 ml of distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Then, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 18.4 g of the oily compound CTM-17.

[Synthesis Example 6: Synthesis of ETM-3]
The ETM-3 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 12.3 g (0.055 mol) of compound (9) and 7.07 g (0.107 mol) of nitrile malonic acid were dissolved in 300 ml of toluene, 0.5 ml of piperidine was added, and the mixture was subjected to a nitrogen stream. The mixture was stirred at 110 ° C. for 5 hours. After allowing to cool to room temperature, 500 ml of hexane was added, and the precipitated precipitate was collected by filtration and purified by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7). It was recrystallized from methylene chloride / hexane to obtain 8.0 g of compound (10).
Next, in a three-necked flask, 8.0 g (0.025 mol) of compound (10) was dissolved in 20 ml of toluene, 0.1 ml of pyridine was added, and 2 ml of thionyl chloride (0.028) was cooled with water and stirred under a nitrogen stream. ) Was gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 5 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then 20 ml of hexane was added and recrystallized to obtain 6.2 g of compound (11).
Then, in a three-necked flask, a mixture of 3 ml (0.037 mol) of pyridine, 0.020 g of hydroquinone, and 20 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 1- (acryloyloxy) -3- (methacryloyl). Dissolve 3.86 g (0.018 mol) of oxy) -2-propanol and dissolve 6.2 g (0.018 mol) of compound (11) in 50 ml of methylene chloride while stirring this solution at 5 ° C. over 2 hours. And dropped. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 200 ml of water, then with 200 ml of dilute hydrochloric acid, and finally with 200 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 5.1 g of ETM-3.

[Synthesis Example 7: Synthesis of ETM-5]
The ETM-5 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 13.8 g (0.055 mol) of compound (12) and 7.07 g (0.107 mol) of nitrile malonic acid were dissolved in 250 ml of toluene, 0.5 ml of piperidine was added, and 110 under a nitrogen stream. The mixture was stirred at ° C. for 5 hours. After allowing to cool to room temperature, 400 ml of hexane was added, and the precipitated precipitate was collected by filtration and purified by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7). Recrystallization from methylene chloride / hexane gave 7.5 g of compound (13).
Next, in a three-necked flask, 7.5 g (0.025 mol) of compound (13) was dissolved in 20 ml of toluene, 0.1 ml of pyridine was added, and 2 ml (0.028 mol) of thionyl chloride was cooled with water under a nitrogen stream and stirred. ) Was gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 5 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then 25 ml of hexane was added and recrystallized to obtain 6.2 g of compound (14).
Then, in a three-necked flask, a mixture of 3 ml (0.037 mol) of pyridine, 0.020 g of hydroquinone, and 20 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then allyl 2-methyl-3-hydroxypropionic acid 3 .86 g (0.018 mol) was dissolved, and 5.7 g (0.018 mol) of compound (14) was dissolved in 50 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 200 ml of water, then with 200 ml of dilute hydrochloric acid, and finally with 200 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 4.4 g of ETM-5.

[Synthesis Example 8: Synthesis of ETM-10]
The ETM-10 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 13.8 g (0.055 mol) of compound (15) and 7.07 g (0.107 mol) of nitrile malonic acid were dissolved in 250 ml of toluene, 0.5 ml of piperidine was added, and 110 under a nitrogen stream. The mixture was stirred at ° C. for 5 hours. After allowing to cool to room temperature, 400 ml of hexane was added, and the precipitated precipitate was collected by filtration and purified by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7). Recrystallization from methylene chloride / hexane gave 7.5 g of compound (16).
Next, in a three-necked flask, 7.5 g (0.025 mol) of compound (16) was dissolved in 20 ml of toluene, 0.1 ml of pyridine was added, and 2 ml (0.028 mol) of thionyl chloride was cooled with water under a nitrogen stream and stirred. ) Was gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 5 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then 25 ml of hexane was added and recrystallized to obtain 6.2 g of compound (17).
Then, in a three-necked flask, a mixture of 3 ml (0.037 mol) of pyridine, 0.020 g of hydroquinone, and 20 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 2.34 g (0.34 g (0.34 mol) of 2-hydroxypropyl ester). 018 mol) was dissolved, and 5.7 g (0.018 mol) of the compound (17) was dissolved in 50 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 200 ml of water, then with 200 ml of dilute hydrochloric acid, and finally with 200 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 4.1 g of ETM-10.

[Synthesis Example 9: Synthesis of ETM-15]
The ETM-15 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 13.8 g (0.055 mol) of compound (18) and 7.07 g (0.107 mol) of nitrile malonic acid were dissolved in 300 ml of toluene, 0.5 ml of piperidine was added, and 110 under a nitrogen stream. The mixture was stirred at ° C. for 5 hours. After allowing to cool to room temperature, 500 ml of hexane was added, and the precipitated precipitate was collected by filtration and purified by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7). Recrystallization from methylene chloride / hexane gave 7.5 g of compound (19).
Next, in a three-necked flask, 7.5 g (0.025 mol) of compound (19) was dissolved in 20 ml of toluene, 0.1 ml of pyridine was added, and 2 ml (0.028 mol) of thionyl chloride was cooled with water under a nitrogen stream and stirred. ) Was gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 5 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then 25 ml of hexane was added and recrystallized to obtain 6.2 g of compound (20).
Then, in a three-necked flask, a mixture of 3 ml (0.037 mol) of pyridine, 0.020 g of hydroquinone, and 20 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 1- (acryloyloxy) -3- (methacryloyl). Dissolve 3.85 g (0.018 mol) of oxy) -2-propanol and dissolve 5.7 g (0.018 mol) of compound (20) in 50 ml of methylene chloride while stirring this solution at 5 ° C. over 2 hours. And dropped. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 200 ml of water, then with 200 ml of dilute hydrochloric acid, and finally with 200 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 4.8 g of ETM-15.

[Synthesis Example 10: Synthesis of ETM-18]
The ETM-18 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 18.1 g (0.059 mol) of compound (21) was dissolved in 50 ml of toluene, 0.2 ml of pyridine was added, and 4 ml (0.056 mol) of thionyl chloride was added while water-cooling and stirring under a nitrogen stream. Gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 10 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then hexane was added and recrystallized to obtain 14 g of compound (22).
Then, in a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 40 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 6.34 g (0) of 4-hydroxybutyl acrylate. .044 mol) was dissolved, and 12 g (0.044 mol) of compound (22) was dissolved in 80 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 300 ml of water, then with 300 ml of dilute hydrochloric acid, and finally with 300 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 9.6 g of ETM-18.

[Synthesis Example 11: Synthesis of ETM-22]
The ETM-22 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 15 g (0.059 mol) of compound (23) was dissolved in 50 ml of toluene, 0.2 ml of pyridine was added, and 4 ml (0.056 mol) of thionyl chloride was gradually added while being water-cooled and stirred under a nitrogen stream. Added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 10 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then hexane was added and recrystallized to obtain 12 g of compound (24).
Then, in a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 40 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 5.72 g (0.72 g) of 2-hydroxypropyl ester (0.72 g). 044 mol) was dissolved, and 12 g (0.044 mol) of the compound (24) was dissolved in 80 ml of methylene chloride while stirring the solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 300 ml of water, then with 300 ml of dilute hydrochloric acid, and finally with 300 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 8.2 g of ETM-22.

[Synthesis Example 12: Synthesis of ETM-28]
ETM-28 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 15.7 g (0.059 mol) of compound (25) was dissolved in 50 ml of toluene, 0.2 ml of pyridine was added, and 4 ml (0.056 mol) of thionyl chloride was added while water-cooling and stirring under a nitrogen stream. Gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 10 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then hexane was added and recrystallized to obtain 12.5 g of compound (26).
Then, in a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 40 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 3-chloro-2-hydroxypropyl methacrylate 7 .14 g (0.044 mol) was dissolved, and 12.5 g (0.044 mol) of compound (26) was dissolved in 80 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 300 ml of water, then with 300 ml of dilute hydrochloric acid, and finally with 300 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 9.1 g of ETM-28.

[Synthesis Example 13: Synthesis of ETM-30]
The ETM-30 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 14.8 g (0.059 mol) of compound (27) was dissolved in 50 ml of toluene, 0.2 ml of pyridine was added, and 4 ml (0.056 mol) of thionyl chloride was added while water-cooling and stirring under a nitrogen stream. Gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 10 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then hexane was added and recrystallized to obtain 11.9 g of compound (28).
Then, in a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 40 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 6.34 g (0) of 4-hydroxybutyl acrylate. .044 mol) was dissolved, and 11.9 g (0.044 mol) of compound (28) was dissolved in 80 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 300 ml of water, then with 300 ml of dilute hydrochloric acid, and finally with 300 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 8.3 g of ETM-30.

[Synthesis Example 14: Synthesis of ETM-32]
ETM-32 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, 14.0 g (0.059 mol) of compound (29) was dissolved in 50 ml of toluene, 0.2 ml of pyridine was added, and 4 ml (0.056 mol) of thionyl chloride was added while being water-cooled and stirred under a nitrogen stream. Gradually added. After completion of the addition, the mixture was gradually heated and stirred at 120 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool, hexane was added, and crystals were precipitated. The obtained crystals were dissolved by heating in 10 ml of methylene chloride, unnecessary substances were filtered and concentrated, and then hexane was added and recrystallized to obtain 11.2 g of compound (30).
Then, in a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 40 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 5.72 g (0) of 2-hydroxyethyl methacrylate. .044 mol) was dissolved, and 11.2 g (0.044 mol) of compound (30) was dissolved in 80 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 300 ml of water, then with 300 ml of dilute hydrochloric acid, and finally with 300 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. bottom. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 7.4 g of ETM-32.

[Synthesis Example 15: Synthesis of ETM-38]
ETM-38 shown in Table 2 was synthesized by the following scheme.

In a three-necked flask, a mixture of 6 ml (0.074 mol) of pyridine, 0.040 g of hydroquinone, and 50 ml of methylene chloride was cooled to 5 ° C. under a nitrogen stream, and then 11 g of 3-hydroxy-1-methacryloyloxyadaman (0. 047 mol) was dissolved, and 15 g (0.047 mol) of compound (31) was dissolved in 120 ml of methylene chloride while stirring this solution at 5 ° C., and the solution was added dropwise over 2 hours. After stirring at 5 ° C. for 30 minutes, the mixture was washed with 400 ml of water, then with 400 ml of dilute hydrochloric acid, and finally with 400 ml of aqueous potassium carbonate solution (0.1%), dried with anhydrous sodium sulfate, and the solvent was retained under reduced pressure. I left. Purification by column chromatography (adsorbent: silica gel, solvent: methylene chloride / hexane = 3/7) gave 12.3 g of ETM-38.

<Manufacturing of organic electroluminescent device>
[Example 1]
An ITO (manufactured by Geomatec Co., Ltd.) formed on a glass substrate was patterned by photolithography using a strip-shaped photomask, and further etched to form a strip-shaped ITO electrode (width 2 mm). Next, the ITO glass substrate is immersed in each liquid in the order of neutral detergent, water, acetone (for the electronics industry, manufactured by Kanto Chemical Co., Inc.) and isopropanol (for the electronics industry, manufactured by Kanto Chemical Co., Inc.), and ultrasonic waves are applied for 5 minutes each. After applying and washing, it was dried with a spin coater.

A solution prepared by dissolving 11: 3 parts by mass of CTM and 0.05 parts by mass of ETM-3 in 77 parts by mass of toluene and further dissolving 0.5 parts by mass of the thermal radical generator V-601: 0.5 parts by mass is prepared. A coating solution was obtained by filtering with a 0.1 μm PTFE filter. The coating liquid was applied to an ITO glass substrate by a dip method, and a film was formed in a glove box having an oxygen concentration of 200 ppm or less at a temperature of 145 ° C. for 35 minutes to obtain a hole transport layer having a thickness of about 0.03 μm.

An exemplary compound (VI-1) was deposited on the hole transport layer as a light emitting material to form a light emitting layer having a thickness of 0.055 μm.

A metal mask with strip-shaped holes is installed on the light emitting layer, and Mg-Ag alloy is co-deposited so that the back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed in. The effective area of the formed organic electroluminescent device was 0.04 cm ² .

[Examples 2 to 5]
In Example 1, the organic electroluminescent devices of Examples 2 to 5 were produced in the same manner as in Example 1 except that CTM-11 was changed to the hole transport compounds shown in Table 3 below.

[Examples 6 to 15]
In Example 1, the organic electroluminescence of Examples 6 to 15 was carried out in the same manner as in Example 1 except that ETM-3: 0.05 parts by mass was changed to the electron transporting compounds and amounts shown in Table 3 below. The device was manufactured.

[Comparative Example 1]
An organic electroluminescent device of Comparative Example 1 was produced in the same manner as in Example 1 except that a hole transport layer was obtained without using an electron transport compound in Example 1.

[Comparative Examples 2 to 4]
In Example 1, the organic electroluminescence of Comparative Examples 2 to 4 was carried out in the same manner as in Example 1 except that ETM-3: 0.05 parts by mass was changed to the electron transporting compounds and amounts shown in Table 3 below. The device was manufactured.
The structures of the electron-transporting compounds (Compound 7, Compound 8, and Compound 9) used in Comparative Examples 2 to 4 are shown below.

<Performance evaluation>
[Resistance of polymerizable organic compound layer (hole transport layer)]
A film was formed on the gold electrode in the same manner as in the above embodiment and cured.
A gold electrode having a diameter of 100 nm ^{was attached to this monolayer film at 1 cm 2} as a counter electrode by a vacuum sputtering method to prepare a sample for resistivity measurement. The measurement method uses SI 1287 Electrochemical Interface (manufactured by Toyo Technica) as the power supply, SI 1260 Inpedance / Gain Phase Analyzer (manufactured by Toyo Technica) as the current meter, and 1296 Dielectric Interface (manufactured by Toyo Technica) as the current amplifier, and 1V AC voltage. Is applied from the high frequency side in the frequency range of 1 MHz to 1 MHz, the AC impedance of each sample is measured, and the graph of the Core Core plot obtained from this measurement is fitted to the RC parallel equivalent circuit to obtain the volume resistance ( Ω · cm) was obtained.
The results are shown in Table 3 for the obtained values. The values obtained here were the resistance before heating and before rinsing.
Further, a film was formed on the gold electrode by the same method as in the above example and cured to obtain a monolayer film, and then the monolayer film was stored in an environment of 40 ° C. and 40% RH for 3 hours. A gold electrode of 100 nm as a counter electrode was ^{attached to the monolayer film after storage at 1 cm 2} by the vacuum sputtering method to prepare a sample for resistivity measurement, and the volume resistivity of this sample was determined by the same method as described above. It was measured. The obtained value is used as the resistance after heating, and the results are shown in Table 3.
Separately, a film is formed on the gold electrode in the same manner as in the above embodiment and cured to obtain a monolayer film, and then the gold electrode having the monolayer film is immersed in a toluene solvent for 30 seconds and then taken out. , Blow-dried with toluene. A 100 nm gold electrode as a counter electrode was ^{attached to the dried monolayer film at 1 cm 2} by the vacuum sputtering method to prepare a sample for resistivity measurement, and the volume resistivity of this sample was determined by the same method as described above. It was measured. The obtained value is used as the resistance after rinsing, and the results are shown in Table 3.

[Luminescent life]
The emission lifetime was measured with the ITO electrode of the organic electroluminescent device as positive and the Mg-Ag back electrode as negative. The measurement conditions were dry nitrogen, room temperature, DC drive method (DC drive), and initial brightness of 1000 cd / m ² .
The “relative time” in Table 3 is the drive time at the time when the brightness (L) of the element of Comparative Example 1 becomes _{half of the initial brightness (L 0} ) (that is, L / L _{0 = 0.5).} Let it be 00 and indicate the relative time.
The “voltage rise” in Table 3 is the voltage rise (= voltage-initial) when the brightness (L) of each element becomes _{half of the initial brightness (L 0} ) (that is, L / L _{0 = 0.5).} Drive voltage) (unit: V) is shown.

1 Transparent insulator substrate, 2 Transparent electrode, 3 Hole transport layer, 4 Light emitting layer, 5 Electron transport layer, 6 Light emitting layer, 7 Back electrode

Claims (8)

It has a pair of electrodes, at least one of which is transparent, and one or more organic compound layers, including a light emitting layer sandwiched between the pair of electrodes.
Wherein at least one organic compound layer, seen containing a polymer of an electron transport compound having a hole-transporting compound and a polymerizable group having a polymerizable group,
The hole transporting compound having a polymerizable group is a compound represented by the following general formula (2).
The group in which the electron-transporting compound having a polymerizable group consists of a compound represented by the following general formula (7), a compound represented by the following general formula (8), and a compound represented by the following general formula (9). An organic electroluminescent element , which is a more selected compound.

In the general formula (2), Ar ^{1 to} Ar ⁴ independently represent a substituted or unsubstituted phenyl group, and Ar ⁵ represents an unsubstituted biphenyl group or a substituted or unsubstituted dibenzyl group. k represents 1, c1 to c4 independently represent an integer of 0 or more and 1 or less, c5 represents an integer of 0, and the total of c1 to c5 is 1 or more. D represents a group represented by the general formula (3), and in the general formula (3), L is an alkylene group, a trivalent group obtained by removing 3 hydrogen atoms from methane, and a trivalent group obtained by removing 3 hydrogen atoms from ethylene. Represents a (n + 1) -valent linking group consisting of one type of linking group selected from the groups or a combination of two or more types .

In the general formula (7), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, and aryl groups, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 11} , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (8), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 21} , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ , the number of _{groups represented by −Y− (Z) m} is 1 or more and 4 or less.
In the general formula (9), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are independently hydrogen atom, halogen atom, alkyl group, alkoxy group and aryl group, respectively. , Aralkyl group or group represented by −YZ. However, ^{among R 31} , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ , the group represented by −Y− (Z) _m is 1 or more and 4 or less.
Among the groups represented by -Y- (Z) _m , Y was obtained by removing 3 hydrogen atoms from the alkylene group, the adamantane group, -C = C-, -C (= O)-, -O- and methane. Represents a (m + 1) valent linking group consisting of one or a combination of two or more selected from trivalent groups, where Z is an acryloyl group, a methacryloyl group or a styrene group, and m is 1 or 2. The organic electroluminescent device according to claim 1 , wherein the group represented by the general formula (3) in the compound represented by the general formula (2) is a group represented by the following general formula (4).

In the general formula (4), X and table an alkylene group, p is 0 or 1. The group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the group represented by the following general formula (5-1) or the following general formula (5-2). that is a group, the organic electroluminescent device according to claim 1.

In the general formula (5-1) and the general formula (5-2), X represents an alkylene group and p represents 0 or 1. The group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the group represented by the following general formula (6-1) or the group represented by the following general formula (6-2). that is a group, the organic electroluminescent device according to claim 1.

In the general formula (6-1) and the general formula (6-2), X represents an alkylene group and p represents 0 or 1. The organic electroluminescent device according to any one of claims 1 to 4 , further containing at least one selected from a thermal radical generator and a derivative thereof and a photoradical generator and a derivative thereof. The mass ratio (C) of the structural unit (C) derived from the hole transporting compound having a polymerizable group and the structural unit (E) derived from the electron transporting compound having a polymerizable group in the polymer: The organic electroluminescent element according to any one of claims 1 to 5, wherein (E) is in the range of 10: 1 to 1:20. The mass ratio (C) of the structural unit (C) derived from the hole transporting compound having a polymerizable group and the structural unit (E) derived from the electron transporting compound having a polymerizable group in the polymer: The organic electroluminescent element according to claim 6 , wherein (E) is in the range of 1: 1 to 1:15. When the volume resistivity of the organic compound layer containing the polymer of the hole transport compound having a polymerizable group and the electron transport compound having a polymerizable group is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less. The organic electric field light emitting element according to any one of claims 1 to 7.

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