JP2018133454A - Composition for organic electroluminescent element, charge-transporting film, and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for an organic electroluminescent element, by which a charge-transporting film with a low resistance can be obtained.SOLUTION: A composition for an organic electroluminescent element comprises: a compound represented by the general formula (1); and at least one dopant selected from an onium salt, a proton acid, a metal halide and a halogen atom. In the general formula (1), F represents a charge-transporting sub-unit; L represents one coupling group selected from an alkylene group, -C=C-, -C(=O)-, -N(R)-, -O-, -S-, a trivalent group taking a form of methane with 3 hydrogen atoms removed therefrom, and a trivalent group taking a form of ethylene with 3 hydrogen atoms removed therefrom, or a (n+1)-valent coupling group formed by a combination of two or more kinds thereof; R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, m represents an integer of 1 to 6, inclusive; and n represents an integer of 1 to 3, inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a composition for an organic electroluminescent device, a charge transporting film, and an organic electroluminescent device.

  Films having charge transport performance (hereinafter referred to as “charge transport films”) provided in electronic devices such as electrophotographic photoreceptors, organic electroluminescent elements, organic transistors, and organic solar cells have been actively developed.

For example, Patent Document 1 discloses a charge transport film made of a polymerized or cured film of a composition containing a compound represented by the general formula (I).
For example, Patent Document 2 discloses a charge transporting film containing a polymer of a compound represented by the general formula (I).
For example, Patent Document 3 discloses a charge transporting film 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).

JP 2013-43841 A JP 2013-44819 A JP2013-60422A JP 2013-60572 A

  The present invention contains a compound represented by the general formula (1), and has a charge transport property having a low resistance as compared with a composition not containing an onium salt, a proton acid, a metal halide and a dopant selected from a halogen atom. It is an object of the present invention to provide a composition for an organic electroluminescent element from which a film can be obtained.

  Specific means for solving the above-described problems include the following modes.

The invention according to claim 1
A compound represented by the following general formula (1):
At least one dopant selected from onium salts, protonic acids, metal halides and halogen atoms;
The composition for organic electroluminescent elements containing this.

In general formula (1), F represents a charge transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S-. 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 formed by combining two or more kinds. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, m represents an integer of 1 to 6, and n represents an integer of 1 to 3.

The invention according to claim 2
The composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In General Formula (2), Ar ^{1 to} Ar ⁴ each 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. k represents 0 or 1, and c1 to c5 each independently represents an integer of 0 or more and 2 or less, provided that the sum of c1 to c5 is 1 or more. D represents a group represented by the general formula (3). In the general formula (3), L represents an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O. -, -S-, 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 linking groups (n + 1) R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 3.

The invention according to claim 3
The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 4).

In General Formula (4), X is an alkylene group, one or more selected from —C═C—, —C (═O) —, —N (R) —, —O—, and —S—. 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 claim 4
The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 5-1) or a group represented by the following general formula (5-2).

In general formula (5-1) and general formula (5-2), X is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group formed by combining one or two or more selected from R, 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 claim 5
The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 6-1) or a group represented by the following general formula (6-2).

In general formulas (6-1) and (6-2), X represents an alkylene group, —C═C—, —C (═O) —, —N (R) —, —O—, and —S—. Represents a divalent linking group formed by combining one or two or more selected from R, 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 claim 6
The onium salt is a compound represented by the following general formula (7-1), a compound represented by the following general formula (7-2), a compound represented by the following general formula (7-3), and the following general The composition according to any one of claims 1 to 5, which is at least one selected from compounds represented by formula (7-4).

In General Formula (7-1), R ¹ , R ² and R ³ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In General Formula (7-2), R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In general formula (7-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In general formula (7-4), R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aromatic heterocyclic group, ^- represents a counter anion.

The invention according to claim 7 provides:
The composition according to any one of claims 1 to 6, wherein the metal contained in the metal halide is a metal of Group 8 to Group 15 and 3 to 6 cycles.

The invention according to claim 8 provides:
The composition according to any one of claims 1 to 7, further comprising at least one selected from a thermal radical generator and a photo radical generator.

The invention according to claim 9 is:
The composition of any one of Claims 1-8 which contains the said dopant in the range of 0.1 mass% or more and 20 mass% or less.

The invention according to claim 10 is:
The charge transport film | membrane which the composition of any one of Claims 1-9 hardened | cured.

The invention according to claim 11 is:
The charge transport film according to claim 10, wherein the resistance value is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less.

The invention according to claim 12
An organic electroluminescent element provided with the cured film which the composition of any one of Claims 1-9 hardened | cured.

The invention according to claim 13 is:
The organic electroluminescent element according to claim 12, wherein the cured film has a resistance value of 1 × 10 ⁵ Ω · cm to 1 × 10 ¹⁵ Ω · cm.

According to the invention according to claims 1, 2, 3, 4 and 5, the dopant represented by the general formula (1) is selected from an onium salt, a proton acid, a metal halide and a halogen atom. There is provided a composition capable of obtaining a charge transporting film having a lower resistance than a composition not containing the same.
According to the invention which concerns on Claim 6, compared with the composition whose onium salt to contain is not the said compound, the composition from which a charge transporting film | membrane with low resistance is obtained is provided.
According to the seventh aspect of the present invention, there is provided a composition capable of obtaining a charge transporting film having a lower resistance than a composition in which the metal contained in the contained metal halide is not the metal.
According to the invention which concerns on Claim 8, compared with the case where it does not contain at least 1 sort (s) selected from a thermal radical generator and a photoradical generator, the composition excellent in sclerosis | hardenability is provided.
According to the invention concerning Claim 9, compared with the case where content of a dopant remove | deviates from the said range, the composition from which charge resistance film | membrane which is low in resistance and excellent in charge transport performance is obtained is provided.
According to the invention which concerns on Claim 10 and 11, hardening of the composition which contains the compound represented by General formula (1), and does not contain the dopant selected from onium salt, a proton acid, a metal halide, and a halogen atom A charge transporting membrane having a lower resistance than the membrane is provided.
According to the invention which concerns on Claim 12 and 13, hardening of the composition which contains the compound represented by General formula (1) and does not contain the dopant selected from an onium salt, a proton acid, a metal halide, and a halogen atom. An organic electroluminescent element provided with a cured film having a lower resistance than the film is provided.

It is typical sectional drawing of an example of the organic electroluminescent element which concerns on this embodiment. It is typical sectional drawing of an example of the organic electroluminescent element which concerns on this embodiment. It is typical sectional drawing of an example of the organic electroluminescent element which concerns on this embodiment. It is typical sectional drawing of an example of the organic electroluminescent element which concerns on this embodiment.

  Embodiments of the invention will be described below. These descriptions and examples illustrate embodiments and do not limit the scope of the invention.

  In the present specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. Means the total amount of substances.

<Composition for organic electroluminescence device>
The composition for an organic electroluminescent device according to the present embodiment includes a compound represented by the general formula (1), at least one dopant selected from an onium salt, a proton acid, a metal halide, and a halogen atom, Containing.

  In general formula (1), F represents a charge transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S-. 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 formed by combining two or more kinds. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, m represents an integer of 1 to 6, and n represents an integer of 1 to 3.

The compound represented by the general formula (1) is a compound in which a styrene group which is a chain polymerizable group is bonded to the charge transporting subunit represented by F via a linking group L.
Generally, the charge transport performance of a charge transport compound tends to decrease as the degree of cure of the charge transport compound increases, that is, the number of cross-linking sites increases. This is presumably because when the number of crosslinking sites of the charge transporting compound is increased, the charge transporting subunit is distorted when cured (crosslinked).
On the other hand, the compound represented by the general formula (1) has a structure in which a styrene group that is a chain polymerizable group is bonded to the charge transporting subunit via the linking group L. When cured (crosslinked), the charge transporting subunit is unlikely to be distorted, and it is possible to achieve both curing performance and charge transport performance. Therefore, the compound represented by the general formula (1) is useful as a material for forming a charge transport film.
In addition, the charge transporting compound having a styrene group as a chain polymerizable group is more resistant to the solvent of the chain polymerizable group and the coating of the compound than the charge transporting compound having only a (meth) acrylic group as the chain polymerizable group. It is thought that it is excellent in aptitude. Also from this viewpoint, the compound represented by the general formula (1) is useful as a material for forming a charge transport film.

  When the present inventors coexist the polymer of the compound represented by the general formula (1) with at least one dopant selected from an onium salt, a proton acid, a metal halide, and a halogen atom, a charge transporting film is obtained. It was found that the resistance of the remarkably decreased. This is presumed that partial charge transfer occurs between the charge transport molecule and the dopant material, resulting in the formation of a charged molecule, increasing the amount of charge in the film and reducing the resistance. The

  Reducing the resistance of the charge transporting film in the organic electroluminescence device is important from the viewpoints of charge injection from the electrode, adjustment of the charge amount, and increase. Therefore, the composition according to the present embodiment is useful as a composition for forming a charge transporting film included in the organic electroluminescent element.

  Hereinafter, the components contained in the composition according to this embodiment will be described in detail.

[Compound represented by general formula (1)]

  In general formula (1), F represents a charge transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S-. 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 formed by combining two or more kinds. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, m represents an integer of 1 to 6, and n represents an integer of 1 to 3. When a plurality of “L” are present in the molecule, “L” may be the same as or different from each other.

  The charge transporting subunit represented by F may be any subunit derived from a compound having charge transporting performance, and specifically includes a phthalocyanine compound, a porphyrin compound, an azobenzene compound, a triarylamine compound. Subunits derived from compounds having charge transport performance such as compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, fluorenone compounds, etc. Can be mentioned. Among these, subunits derived from triarylamine compounds that are excellent in charge mobility, oxidation stability, and the like are preferable.

  The linking group represented by L is divalent, trivalent or tetravalent, more preferably divalent or trivalent.

  The divalent linking group represented by L is at least selected from an alkylene group and —C═C—, —C (═O) —, —N (R) —, —O— and —S—. A divalent linking group formed by combining one type is preferable, and the alkylene group is preferably a linear alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

  Examples of the divalent linking group represented by L include the following groups. In the following linking groups, “*” is a site linked to F, and a, b and c represent the number of repeating methylene groups.

_{* - (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. In the following linking groups, “*” is a site linked to F, and a, b, c, d, e and f represent the number of repeating methylene groups.

_{* - (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. In the following linking groups, “*” is a site linked to F, and b, c and g represent the number of repeating methylene groups.

  As the compound represented by the general formula (1), a compound having a subunit derived from a triarylamine compound as a charge transporting subunit is preferable, and specifically, a compound represented by the general formula (2) Is preferred.

In General Formula (2), Ar ^{1 to} Ar ⁴ each 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. k represents 0 or 1, and c1 to c5 each independently represents an integer of 0 or more and 2 or less, provided that the sum of c1 to c5 is 1 or more. D represents a group represented by the general formula (3). In the general formula (3), L represents an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O. -, -S-, 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 linking groups (n + 1) R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 3.

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

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

As substituents other than “D” (that is, a group represented by the general formula (3)) in Ar ^{1 to} Ar ⁴ , an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Examples thereof include an unsubstituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or 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 structural formulas (11) to (17). Structural formulas (11) to (17) are shown together with “— (D) _C ” which collectively indicates “— (D) _C1 ” to “— (D) _C4 ” linked to Ar ^{1 to} Ar ^4. .

In Structural Formula (11), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and 1 type selected from a C7-C10 aralkyl group is represented.

In Structural Formula (12), R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, or 1 or more carbon atoms. 1 type selected from the phenyl group substituted by the alkyl group or alkoxy group of 4 or less, the C7-C10 aralkyl group, and a halogen atom.

In 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. 1 type selected from the substituted phenyl group, the C7-C10 aralkyl group, 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 either structural formula (18) or (19).

In Structural Formula (18) and Structural Formula (19), R ¹⁵ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, and 1 to 4 carbon atoms. 1 type selected from the phenyl group substituted by the alkyl group or the alkoxy group, the C7-C10 aralkyl group, and a halogen atom, and t represents the integer of 0-4.

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

  In Structural Formula (21), s represents an integer of 1 to 10.

  In Structural Formula (22), s represents an integer of 1 to 10.

In Structural Formulas (27) and (28), R ²¹ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, or 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 to 10 carbon atoms, and a halogen atom, t represents an integer of 0 to 4 and W represents a divalent linking group. Represents. W is preferably any one of structural formulas (31) to (39). In 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 is 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 to 10 carbon atoms, and a halogen atom.

When Ar ⁵ is a substituted or unsubstituted arylene group, C5 is preferably 0, that is, “D” (that is, a group represented by the general formula (3)) is not bonded to Ar ^5. It 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, or 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 to 10 carbon atoms, and a halogen atom, and x represents an integer of 0 to 4 inclusive. In Structural Formula (43), Y represents a divalent linking group, and Y is preferably any one of Structural Formulas (51) to (60). In Structural Formula (51), y represents an integer of 1 to 4.

  C1 to c5 in the general formula (2) are each independently an integer of 0 or more and 2 or less, provided that the sum 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 even more preferably 2. L and n in General formula (3) are synonymous with L and n in General formula (1).

  Examples of the group represented by the general formula (3) include a group represented by the general formula (4), a group represented by the general formula (5-1), 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 viewpoints of charge transport properties and film forming properties.

  In General Formula (4), X is an alkylene group, one or more selected from —C═C—, —C (═O) —, —N (R) —, —O—, and —S—. 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—. A valent linking group is preferable, and the alkylene group is preferably a linear alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms. 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 as or different from each other.

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

  In general formula (4-1) and 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 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 formed by combining one or more selected from —, —N (R) —, —O— and —S—, wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl. Represents a group, and p represents 0 or 1. When a plurality of groups represented by general formula (5-1), general formula (5-2), general formula (6-1) or general formula (6-2) are present in the molecule, these groups are the same as each other. But it can be different.

  X is preferably an alkylene group, and the alkylene group is preferably a linear alkylene group having 1 to 6 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, and a straight chain having 1 or 2 carbon atoms. More preferred are chain alkylene groups.

  Hereinafter, specific examples of the charge transporting subunit represented by F in the general formula (1) and specific examples of the group linked to F (that is, the group represented by the general formula (3)) will be exemplified. These combinations are shown in Table 1, and specific examples of the compound represented by the general formula (1) are shown. The compound represented by the general formula (1) is not limited by these. In the structural formulas shown below, “*” means a linking site.

  For example, in CTM-1, the charge transporting subunit represented by F (described as “host nucleus” in Table 1) is (1) -1, and the group represented by the general formula (3) (Table 1) (Described as “functional group”) is (III) -1, and both are connected by “*”, and has the following structure.

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

  The composition which concerns on this embodiment may contain 1 type as a compound represented by General formula (1), and may contain multiple types.

  The composition according to this embodiment contains at least one dopant selected from an onium salt, a protonic acid, a metal halide, and a halogen atom, together with the compound represented by the general formula (1). Hereinafter, these dopants will be described.

[Onium salt]
Examples of onium salts include sulfonium salts, iodonium salts, ammonium salts, carbonium salts, and phosphonium salts. The onium salt is preferably at least one selected from the compounds represented by the general formulas (7-1) to (7-4) from the viewpoint of further reducing the resistance of the charge transporting film.

In General Formula (7-1), R ¹ , R ² and R ³ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.

In General Formula (7-2), R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group, and X ⁻ represents a counter anion.

In general formula (7-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.

In general formula (7-4), R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aromatic heterocyclic group, ^- represents a counter anion.

In the general formulas (7-1) to (7-4), the following groups are preferable.
As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.
The aryl group is preferably an unsubstituted phenyl group or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms.
As the aralkyl group, an aralkyl group having 7 to 10 carbon atoms is preferable.
As an alkoxy group, a C1-C4 alkoxy group is preferable.
As the aryloxy group, a phenyloxy group is preferable.
Examples of the aromatic heterocyclic group include a furan group, a pyrrole group, an imidazole group, a pyrazole group, an oxazole group, a thiazole group, a thienyl group (a group in which one hydrogen atom is removed from thiophene), and the imidazole group and the pyrazole group. preferable.

Examples of the counter anion represented by X ⁻ in the general formulas (7-1) to (7-4) include an alkyl borate anion, an aryl borate anion, a perchlorate ion, a halogen anion, and the like. Or an aryl borate anion is preferable. Examples of the alkyl borate anion include a tetraethyl borate anion, a tetramethyl borate anion, a tetraisobutyl borate anion, and a tetra-n-propyl borate anion. Examples of the aryl borate anion include a tetraphenyl borate anion and a tetra-4-methylphenyl borate anion.

In general formula (7-1), R ¹ , R ² and R ³ are preferably an aryl group or an alkyl group, and are an unsubstituted phenyl group or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms. Is more preferable. X ⁻ includes PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , RfSO _{^{3 -, Cl -, ClO 4}} - are preferred.

In General Formula (7-2), R ⁴ and R ⁵ are preferably an aryl group, and more preferably an unsubstituted phenyl group or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms. X ⁻ includes PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , RfSO _{^{3 -, Cl -, ClO 4}} - are preferred.

In general formula (7-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably an aryl group or an alkyl group, and substituted with an unsubstituted phenyl group or an alkyl group having 1 to 4 carbon atoms. More preferred is a phenyl group. X ⁻ includes PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , RfSO _{^{3 -, Cl -, ClO 4}} - are preferred.

In general formula (7-4), R ¹⁰ , R ^11, and R ¹² are preferably an aryl group or an alkyl group, an unsubstituted phenyl group, or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms. Is more preferable. X ⁻ includes PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , RfSO _{^{3 -, Cl -, ClO 4}} - are preferred.

Specific examples of the onium salt include compounds represented by the following structural formula. In the following structural formula, X ⁻ includes PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ⁻ , BF ₄ ⁻ , (C ₆ H ₅ ) ₄ B ⁻ , and (C ₆ F ₅ ) ₄ B ⁻ , RfSO ₃ ⁻ , Cl ⁻ , ClO ₄ ^— .

[Proton acid]
Examples of the protonic acid include inorganic salts such as HF, HCl, HBr, HNO ₃ , H ₂ SO ₄ , HClO; benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, Trifluoromethanesulfonic acid, trifluoroacetic acid; and the like. As the proton acid, a sulfonic acid compound is preferable from the viewpoint of further reducing the resistance of the charge transporting membrane.

[Metal halide]
Metal halides include ferric chloride, ferric bromide, ferric iodide, aluminum chloride, aluminum bromide, aluminum iodide, gallium chloride, gallium bromide, gallium iodide, indium chloride, bromide Examples thereof include indium, indium iodide, antimony trichloride, antimony pentachloride, arsenic pentafluoride, boron trifluoride, and titanium tetrachloride.

  The metal contained in the metal halide is preferably a metal of group 8 to group 15 and 3 to 6 cycles from the viewpoint of further reducing the resistance of the charge transport film. Group 10 to group 15 and 3 to 5 cycles More preferred are metals.

  The halogen contained in the metal halide is preferably chlorine or iodine from the viewpoint of stability and ease of doping.

  Specifically, antimony pentachloride and ferric chloride are preferable as the metal halide.

[Halogen atom]
Examples of the halogen atom include chlorine, bromine and iodine, and chlorine and iodine are preferable from the viewpoint of further reducing the resistance of the charge transporting film.

  The composition which concerns on this embodiment may contain 1 type of these dopants, and may contain 2 or more types. The mass ratio of these dopants in the composition according to this embodiment is preferably 0.1% by mass or more and 20% by mass or less from the viewpoint of the balance between the charge transport performance and the low resistance of the charge transport film. 1 mass% or more and 10 mass% or less are more preferable, and 0.1 mass% or more and 5 mass% or less are still more preferable.

[Thermal radical generator, photo radical generator]
The composition according to this embodiment may contain a thermal radical generator or a photo radical generator from the viewpoint of enhancing the curability of the charge transport film. That is, a thermal radical generator or a photo radical generator may be used for forming the charge transport film.

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

Commercially available products of thermal radical generators include V-30 (10-hour half-life temperature: 104 ° C.), V-40 (same: 88 ° C.), V-59 (same: 67 ° C.), V-601 (same as above: 66 ° C), V-65 (same: 51 ° C), V-70 (same: 30 ° C), VF-096 (same: 96 ° C), Vam-110 (same: 111 ° C), Vam-111 (same: 111 ° C.) (made by Wako Pure Chemical Industries, Ltd.), OT _AZO- 15 (same as 61 ° C.), OT _AZO- 30, AIBN (same as 65 ° C.), AMBN (same as 67 ° C.), ADVN (same as 52). ° C), ACVA (same as above: 68 ° C) (above, manufactured by Otsuka Chemical Co., Ltd.) and the like; Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Park Mill H, Park Mill P, permenta H, per octa H, parb Chill C, Perbutyl D, Perhexyl D, Parroyl IB, Parroyl 355, Parroyl L, Parroyl SA, Nyper BW, Nyper BMT-K40 / M, Parroyl IPP, Parroyl NPP, Parroyl TCP, Parroyl OPP, Parroyl SBP, Park Mill ND, Parocta ND 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 (above, manufactured by NOF Chemical Co., Ltd.), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Parka L-W75, Parkadox CH-50L, Trigonox TMBH, Kayacumen H, Kayabutyl H-70, Percadox BC-FF, Kaya Hexa AD, Parkadox 14, Kayabutyl C, Kayabutyl D, Kaya Hexa 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, Kaya ester P-70, Kaya ester TMPO-70, Trigonox 121, Kaya ester O, Kaya ester HTP-65W, Kaya ester A , Trigonox 42, Trigonox F-C50, Kayabutyl B, Kaya-Carbon EH-C70, Kaya-Carbon EH-W60, Kaya-Carbon I-20, Kaya-Carbon BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo), Luperox LP (same as above: 64 ° C), Lupelox 610 (same as above: 37 ° C), Lupelox 188 (same as above: 38 ° C), Lupelox 844 (same as above: 44 ° C), Lupelox 259 (same as above: 46 ° C), Lupelox 10 (same as above: 48) ), Lupelox 701 (same: 53 ° C), Lupelox 11 (same: 58 ° C), Lupelox 26 (same: 77 ° C), Lupelox 80 (same: 82 ° C), Lupelox 7 (same: 102 ° C), Lupelox 270 (Same as above: 102 ° C), Lupelox P (same as above: 104 ° C), Lupelox Lupelox 554 (same as above: 55 ° C), Lupelox 575 (same as above: 75 ° C), Lupelox TANPO (same as 96 ° C), Lupelox 555 (same as above: 100 ° C), Lupelox 570 (same as above: 96 ° C), Lupelox TAP (same: 100 ° C), Lupelox TBIC (same: 99 ° C), Lupelox TBEC (same: 100 ° C), Lupelox JW (same: 100 ° C), Lupelox TAIC (same: 96 ° C), Lupelox TAEC (same as above: 99 ° C.), Lupelox DC (same as 117 ° C.), Lupelox 101 (same as 120 ° C.), Lupelox F (same as 116 ° C.), Lupelox DI (same as 129 ° C.), Lupelox 130 (same as 131) ° C), Lupelox 220 (same as 107 ° C), Lupelox 230 (same as 109 ° C) Box 233 (the same: 114 ℃), Luperox 531 (the same: 93 ℃) (or higher, Arkema Yoshitomi Co., Ltd.) and the like.

  The amount of the thermal radical generator used is preferably 0.001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1) in the composition. The amount is more preferably equal to or less than part by weight, and further preferably equal to or greater than 0.1 part by weight and equal to or less than 3 parts by weight.

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

  Specific examples of the photoradical generator include, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenyl. Amine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Is mentioned.

  The amount of the photo radical generator used is preferably 0.001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1) in the composition. The amount is more preferably equal to or less than part by weight, and further preferably equal to or greater than 0.1 part by weight and equal to or less than 3 parts by weight.

  The composition according to this embodiment may further contain at least one selected from light emitting materials, dye compounds, hole transport materials, hole injection materials, electron transport materials, and electron injection materials. Specific examples of these materials will be described later.

<Charge transport film>
The charge transport film according to the present embodiment is a cured film obtained by curing the composition according to the present embodiment, that is, a polymer of a compound represented by the general formula (1), an onium salt, a protonic acid, a metal A charge transporting film containing a halide and at least one dopant selected from halogen atoms. In the charge transport film according to the present embodiment, the compound represented by the general formula (1) itself (unreacted state) may be contained.

In the charge transport film according to this embodiment, a polymer of the compound represented by the general formula (1) and at least one dopant selected from an onium salt, a proton acid, a metal halide, and a halogen atom coexist. Therefore, the resistance of the charge transport film is low.
In addition, since the compound represented by the general formula (1) makes it possible to achieve both a high degree of curing and excellent charge transport performance, the charge transport film according to the present embodiment has mechanical strength and charge transport performance. Excellent.

  The charge transport film according to the present embodiment can be obtained by curing the composition according to the present embodiment with energy such as heat, light, or electron beam. In order to balance the properties of the cured film such as electrical properties and mechanical strength, thermosetting is desirable.

  The content of the polymer of the compound represented by the general formula (1) in the charge transporting film according to this embodiment may be set according to the use of the charge transporting film. It is the range of 50 mass% or more and 99 mass% or less of solid content.

The charge transport film according to this embodiment preferably has a resistance value 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 ¹³ Ω · cm or less. It is more preferable that it is cm or less, and it is still more preferable that it is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁰ Ω · cm or less.

  The charge transport film according to this embodiment is suitable as a charge transport film included in the organic electroluminescent element.

<Organic electroluminescent device>
An organic electroluminescent element is a device composed of a pair of electrodes, at least one of which is transparent or translucent, and one or a plurality of organic compound layers including a light emitting layer sandwiched between the electrodes. In the organic electroluminescent element according to this embodiment, at least one of the organic compound layers includes a cured film obtained by curing the composition according to this embodiment. The cured film contains a polymer of the compound represented by the general formula (1) and at least one dopant selected from an onium salt, a proton acid, a metal halide, and a halogen atom. The cured film may contain the compound represented by the general formula (1) itself (unreacted state).

  In the organic electroluminescence device 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 charge transport function, and the composition according to the present embodiment is cured by the light emitting layer. Includes cured film.

  In the organic electroluminescent element according to the present embodiment, when the organic compound layer has a plurality of layers (that is, in the case of a function separation type in which each layer has a different function), at least one of the layers is a light emitting layer. The layer configurations (1) to (3) are listed. In layer composition (1)-(3), any one layer contains the cured film which the composition concerning this embodiment hardened.

Layer structure (1): Function separation type layer structure having a hole transport layer and a light emitting layer. In this configuration, the hole transport layer is preferably a cured film obtained by curing the composition according to this embodiment.

Layer structure (2): Function separation type layer structure having a hole transport layer, a light emitting layer, and an electron transport layer. In this configuration, the hole transport layer is preferably a cured film obtained by curing the composition according to this embodiment.

Layer structure (3): Function separation type layer structure having a light emitting layer and an electron transport layer. In this configuration, the light emitting layer is preferably a cured film obtained by curing the composition according to the present embodiment.

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

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

  FIG. 1 shows the layer structure (1). The organic electroluminescent element 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 on a transparent insulator substrate 1 in this order. A hole injection layer may be disposed between the transparent electrode 2 and the hole transport layer 3. In the embodiment shown in FIG. 1, the hole transport layer 3 is preferably a cured film obtained by curing the composition according to this embodiment.

  FIG. 2 shows the layer configuration (2). The organic electroluminescent element 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 on a transparent insulator substrate 1 in this order. A hole injection layer may be disposed between the transparent electrode 2 and the hole transport layer 3. An electron injection layer may be disposed between the electron transport layer 5 and the back electrode 7. In the embodiment shown in FIG. 2, the hole transport layer 3 is preferably a cured film obtained by curing the composition according to this embodiment.

  FIG. 3 shows the layer structure (3). The organic electroluminescent element 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 on a transparent insulator substrate 1 in this order. An electron injection layer may be disposed between the electron transport layer 5 and the back electrode 7. In the embodiment shown in FIG. 3, the light emitting layer 6 is preferably a cured film obtained by curing the composition according to this embodiment. In this case, the composition according to this embodiment contains at least one luminescent material.

  FIG. 4 shows a single layer type layer structure. The organic electroluminescent element shown in FIG. 4 is an element in which a transparent electrode 2, a light emitting layer 6 having a charge transport function, and a back electrode 7 are laminated on a transparent insulator substrate 1 in this order. In the embodiment shown in FIG. 4, the light emitting layer 6 is a cured film obtained by curing the composition according to this embodiment. In this case, the composition according to this embodiment contains at least one luminescent material.

  In each of the organic electroluminescent elements 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 element 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 may be stacked in a plurality of stages.

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

  Transparent in the transparent insulator substrate 1 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 for the resin film include methacrylic resins such as polymethyl methacrylate (PMMA), polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polycarbonate resins. The transparent insulator substrate 1 may be subjected to surface treatment or a laminated structure for the purpose of suppressing water permeability and gas permeability.

  The transparent electrode 2 is transparent in order to extract emitted light in the same manner as the transparent insulator substrate 1 and is preferably an electrode having a large work function for injecting holes, and an electrode having a work function of 4 eV or more is preferable.

  Transparent with respect to the transparent electrode 2 means that the light transmittance in the visible region is 10% or more, and the transmittance is preferably 75% or more. The material of the transparent electrode 2 includes metal oxides such as indium tin oxide (ITO), tin oxide, indium oxide, zinc oxide and indium zinc oxide; metals such as aluminum, nickel, gold, silver, platinum and palladium; iodide Metal halides such as copper; conductive polymers such as carbon black, poly (3-methylthiophene), polypyrrole, and polyaniline. The sheet resistance of the transparent electrode 2 is desirably as low as possible, preferably several hundred Ω / □ or less, and more preferably 100 Ω / □ or less.

  The organic compound layers (layers indicated by reference numerals 3 to 6 in FIGS. 1 to 4) are made of a hole transport material, a hole injection material, an electron transport material, an electron injection material, and a light emitting material depending on the function. Contains the selected material. These materials and the composition according to this embodiment may be mixed and used for film formation.

  Examples of hole transport materials include tetraphenylenediamine derivatives, triphenylamine derivatives, carbazole derivatives, stilbene derivatives, arylhydrazone derivatives, porphyrin compounds, and tetraphenylenediamine derivatives, spirofluorene derivatives, and triphenylamine derivatives. .

  Examples of the hole injection material include phenylenediamine derivatives, phthalocyanine derivatives, indanthrene derivatives, polyalkylenedioxythiophene derivatives, etc. These include organic acids such as Lewis acid and sulfonic acid, inorganic acids such as iron chloride, and the like. May be mixed.

  Electron transport materials include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyran dioxide derivatives, silole derivatives, chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, triazole derivatives, fluorenylidene Examples include methane derivatives.

Examples of the electron injection material include metals such as Li, Ca, and Sr, metal fluorides such as LiF and MgF, and metal oxides such as MgO, Al ₂ O ₃ , and LiO.

  As the light emitting material, a compound exhibiting high emission quantum efficiency in a solid state is desirable. The light emitting material may be either a low molecular compound or a high molecular compound. Examples of the organic low molecular weight compound include chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, styrylarylene derivatives, silole derivatives, oxazole derivatives, oxathiazole derivatives, and oxadiazole derivatives. Examples of the organic polymer compound include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyacetylene derivatives. Specific examples of the light emitting material include Exemplified Compounds (VI-1) to (VI-17). The exemplified compounds (VI-1) to (VI-17) can also be used as an electron transport material.

  In exemplary compounds (VI-13) to (VI-17), n and g are each independently an integer of 1 or more, and V is a divalent linking group. Examples of V include the following groups. In the following structural formula, 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 of the organic electroluminescent device or improving the light emission efficiency, the light emitting material or the charge transporting polymer may be doped with a dye compound different from the light emitting material as a guest material. The doping amount of the coloring compound is preferably 0.001 to 40 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the host.

  Examples of coloring 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, rhenium, osnium, iridium And metal complex compounds such as platinum and gold. Specific examples of the dye compound for doping include exemplified compounds (VII-1) to (VII-6).

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

  The material of the back electrode 7 is preferably a material that can be vacuum-deposited and has a low work function for performing electron injection, and is preferably a metal, a metal oxide, or a metal fluoride. 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 tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc 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. Examples of the material for the protective layer include 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; Is mentioned.

  The thicknesses of the transparent electrode 2, each organic compound layer, the back electrode 7, and the protective layer are generally 0.001 μm to 10 μm, preferably 0.001 μm to 5 μm.

  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 deposition method, a sputtering method, a coating method, or the like. The coating method is a film forming method in which a coating solution 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 for the coating solution include spin coating, die coating, ink jet, casting, and dip.

  The content of each material in the organic compound layer may be a state where molecules are dispersed (molecular dispersion state) or a state where particles are formed and dispersed (particle dispersion state). In order to obtain a molecular dispersion state in a film forming method using a coating solution, the solvent of the coating solution 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 solution, a coating solution is prepared using any of a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, and an ultrasonic wave.

  The organic electroluminescent elements according to the present embodiment are arranged in a matrix or a 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 elements are arranged in segments, the electrodes may be arranged in segments, or the electrodes and the organic compound layer may be arranged in segments. The matrix-like or segment-like organic compound layer can be formed by an inkjet method.

  As a driving apparatus and a driving method for a matrix-shaped organic electroluminescent element and a segment-shaped organic electroluminescent element, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7 -134558, JP-A-8-234665, JP-A-8-2441047, JP2784615, U.S. Pat. No. 5,828,429, U.S. Pat. No. 6,023,308, and the like. Applicable.

  Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.

<Synthesis of Compound Represented by General Formula (1)>
[Synthesis Example 1: Synthesis of CTM-11]
CTM-11 shown in Table 1 was synthesized according to 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. Next, 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. Next, 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. Next, 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. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 10/1) to obtain 33.3 g of oily compound (2).

  Next, 33.3 g of oily compound (2) was collected in an eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran, added with 50 ml of ethanol, 2 g of 10% Pd / C, connected to a hydrogen gas supply source, stirred for 24 hours, The lower solvent was distilled off. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 32.3 g of an oily compound (3).

  Next, 25 g of oily compound (3) was collected in an 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 was gradually added at 0 ° C. And stirred at room temperature for 2 hours. The precipitated solid was washed twice with 100 ml of toluene. Subsequently, 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. Subsequently, it cooled to room temperature, 500 ml of toluene was added, the organic layer was wash | cleaned 3 times with 500 ml of distilled water, and the solvent was distilled off under pressure reduction after drying with anhydrous sodium sulfate. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 27.1 g of oily compound CTM-11.

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

  25 g of compound (3) synthesized in the same manner 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 separated by a filter paper covered with celite. Next, the organic layer was washed with 500 ml of distilled water three times and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Subsequently, recrystallization from 20 ml of hexane and 30 ml of ethyl acetate gave 18.5 g of a light pink solid compound (4).

  Next, 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. Next, 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. Subsequently, 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 according to 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. Next, 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. Next, 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. Next, 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. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 31.2 g of oily compound (6).

  Next, 31.2 g of oily compound (6) was collected in an eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran, added with 50 ml of ethanol and 2 g of 10% Pd / C, connected to a hydrogen gas supply source, stirred for 24 hours, The solvent was distilled off. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 29.8 g of oily compound (7).

  Next, 25 g of oily compound (7) was collected in an 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 was gradually added at 0 ° C. The solution was added dropwise and stirred at room temperature for 2 hours. The precipitated solid was washed twice with 100 ml of toluene. Subsequently, 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. Subsequently, it cooled to room temperature, 500 ml of toluene was added, the organic layer was wash | cleaned 3 times with 500 ml of distilled water, and the solvent was distilled off under pressure reduction after drying with anhydrous sodium sulfate. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 25.3 g of oily compound CTM-15.

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

  25 g of the compound (7) synthesized by the same method 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 separated by a filter paper covered with celite. Next, the organic layer was washed with 500 ml of distilled water three times and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Subsequently, the residue was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 2/1) to obtain 17.8 g of oily compound (8).

  Next, 16.0 g of 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. Next, 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. Subsequently, the residue 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 according to the following scheme.

  Compound (6) was synthesized from compound (5) in the same manner as in Synthesis Example 3. Next, 27.5 g of oily compound (6) was collected in an eggplant-shaped flask, dissolved in 200 ml of tetrahydrofuran and 50 ml of ethanol, and a solution obtained by dissolving 8.7 g of sodium hydroxide in 25 ml of distilled water was obtained at 0 ° C. The solution was gradually added dropwise and stirred at room temperature for 2 hours. The lower layer separated into two layers was washed twice with 100 ml of toluene. Next, 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. Next, 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. Subsequently, it was purified by column chromatography (adsorbent: silica gel, solvent: toluene / ethyl acetate = 20/1) to obtain 18.4 g of oily compound CTM-17.

<Production of organic electroluminescence device>
[Example 1]
ITO formed on a glass substrate (manufactured by Geomatek) 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 solution in the order of neutral detergent, water, acetone (for electronics industry, manufactured by Kanto Chemical) and isopropanol (for electronics industry, manufactured by Kanto Chemical), and ultrasonic waves are applied for 5 minutes each. And washed with a spin coater.

  CTM-11: 3 parts by mass and antimony pentachloride: 0.03 parts by mass as a dopant dissolved in toluene: 77 parts by mass, and further a thermal radical generator V-601: 0.5 parts by mass Was filtered with a PTFE filter having a pore diameter of 0.1 μm to obtain a coating solution. A coating solution is applied to an ITO glass substrate by a dip method, and is formed in a glove box with an oxygen concentration of 200 ppm or less at a temperature of 145 ° C. for 35 minutes. )

  On the hole transport layer, the exemplified compound (VI-1) was deposited as a luminescent material to form a luminescent layer having a thickness of 0.055 μm.

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

[Examples 2 to 5]
An organic electroluminescent element was produced in the same manner as in Example 1 except that CTM-11 was changed to CTM-12, CTM-15, CTM-16, or CTM-17.

[Examples 6 to 15]
An organic electroluminescent element was produced in the same manner as in Example 1 except that in Example 1, antimony pentachloride was changed to another dopant. The dopant used in Examples 6-15 and its usage-amount are as follows.
Example 6: Triphenylsulfonium tetrafluoroborate, 0.5 parts by mass Example 7: Diphenyliodonium chloride, 1 part by mass Example 8: Triphenylmethylium tetrakis (pentafluorophenyl) borate, 1 part by mass Example 9 : Tri-p-tolylsulfonium trifluoromethanesulfonate, 2 parts by mass Example 10: diphenyliodonium perchlorate, 2 parts by mass Example 11: bis (4-tert-butylphenyl) iodonium hexafluorophorus, 3 parts by mass Example 12: Benzenesulfonic acid, 5 parts by weight Example 13: p-toluenesulfonic acid, 5 parts by weight Example 14: ferric chloride, 2 parts by weight Example 15: ferric iodide, 1.5 parts by weight Part

[Comparative Examples 1-5]
An organic electroluminescent element was produced in the same manner as in any one of Examples 1 to 5 except that antimony pentachloride was not used for forming the hole transport layer.

[Comparative Example 11]
An organic electroluminescent device was produced in the same manner as in Example 1 except that CTM-11 was changed to the following comparative compound (VIII).

[Comparative Example 12]
An organic electroluminescent element was produced in the same manner as in Example 1 except that CTM-11 was changed to polyvinyl carbazole (PVK).

[Comparative Example 13]
An organic electroluminescent element was produced in the same manner as in Example 1 except that CTM-11 was changed to the following comparative polymer (IX).

<Performance evaluation>
[Resistance of charge transport film (hole transport layer)]
A film was formed on the gold electrode in the same manner as in the above example and cured. About this single layer film, a 100 nm gold electrode was mounted at 1 cm ² as a counter electrode by vacuum sputtering, and was used for resistivity measurement. The measuring method is SI 1287 Electrochemical Interface (Toyo Technica) as power source, SI 1260 Inpedance / Gain Phase Analyzer (Toyo Technica) as ammeter, 1296 Dielectric Interface (Toyo Technica) as current amplifier, and 1V AC voltage. Applying from the high frequency side in the frequency range from 1 MHz to 1 mHz, measuring the AC impedance of each sample, fitting the graph of the Cole Cole plot obtained from this measurement to an RC parallel equivalent circuit, the volume resistivity (Ω Cm) was obtained.

[Luminescence life]
The lifetime of the light emission was measured with the ITO electrode of the organic electroluminescent element as positive and the Mg-Ag back electrode as negative. The measurement conditions were room temperature, direct current drive method (DC drive), and initial luminance of 1000 cd / m ² in dry nitrogen.
“Relative time” in Table 2 indicates the drive time when the luminance (L) of the element of Comparative Example 11 becomes half the initial luminance (L ₀ ) (ie, L / L ₀ = 0.5). 00 is the relative time.
“Voltage rise” in Table 2 is a voltage rise (= voltage−initial stage) when the luminance (L) of each element becomes half of the initial luminance (L ₀ ) (ie, L / L ₀ = 0.5). Drive voltage) (unit: V).

DESCRIPTION OF SYMBOLS 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 (13)

A compound represented by the following general formula (1):
At least one dopant selected from onium salts, protonic acids, metal halides and halogen atoms;
The composition for organic electroluminescent elements containing this.

In general formula (1), F represents a charge transporting subunit, L is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O-, -S-. 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 formed by combining two or more kinds. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, m represents an integer of 1 to 6, and n represents an integer of 1 to 3. The composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In General Formula (2), Ar ^{1 to} Ar ⁴ each 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. k represents 0 or 1, and c1 to c5 each independently represents an integer of 0 or more and 2 or less, provided that the sum of c1 to c5 is 1 or more. D represents a group represented by the general formula (3). In the general formula (3), L represents an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O. -, -S-, 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 linking groups (n + 1) R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 3. The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 4).

In General Formula (4), X is an alkylene group, one or more selected from —C═C—, —C (═O) —, —N (R) —, —O—, and —S—. R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and p represents 0 or 1. The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 5-1) or a group represented by the following general formula (5-2).

In general formula (5-1) and general formula (5-2), X is an alkylene group, -C = C-, -C (= O)-, -N (R)-, -O- and -S-. Represents a divalent linking group formed by combining one or two or more selected from R, R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and p represents 0 or 1. The group connected to F in the compound represented by the general formula (1) or the group represented by the general formula (3) in the compound represented by the general formula (2) is represented by the following general formula ( The composition according to claim 1 or 2, which is a group represented by 6-1) or a group represented by the following general formula (6-2).

In general formulas (6-1) and (6-2), X represents an alkylene group, —C═C—, —C (═O) —, —N (R) —, —O—, and —S—. Represents a divalent linking group formed by combining one or two or more selected from R, R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and p represents 0 or 1. The onium salt is a compound represented by the following general formula (7-1), a compound represented by the following general formula (7-2), a compound represented by the following general formula (7-3), and the following general The composition according to any one of claims 1 to 5, which is at least one selected from compounds represented by formula (7-4).

In General Formula (7-1), R ¹ , R ² and R ³ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In General Formula (7-2), R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, an aralkyl group, or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In general formula (7-3), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group, an aryl group, an aralkyl group or an aromatic heterocyclic group, and X ⁻ represents a counter anion.
In general formula (7-4), R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an aromatic heterocyclic group, ^- represents a counter anion.   The composition according to any one of claims 1 to 6, wherein the metal contained in the metal halide is a metal of Group 8 to Group 15 and 3 to 6 cycles.   The composition according to any one of claims 1 to 7, further comprising at least one selected from a thermal radical generator and a photo radical generator.   The composition of any one of Claims 1-8 which contains the said dopant in the range of 0.1 mass% or more and 20 mass% or less.   The charge transport film | membrane which the composition of any one of Claims 1-9 hardened | cured. The charge transport film according to claim 10, wherein the resistance value is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ¹⁵ Ω · cm or less.   An organic electroluminescent element provided with the cured film which the composition of any one of Claims 1-9 hardened | cured. The organic electroluminescent element according to claim 12, wherein the cured film has a resistance value of 1 × 10 ⁵ Ω · cm to 1 × 10 ¹⁵ Ω · cm.