JP6370225B2 - Compound having indenoacridan ring structure and organic electroluminescence device - Google Patents

Description

  The present invention relates to a compound suitable for an organic electroluminescence element, which is a self-luminous element suitable for various display devices, and to the element. Specifically, the present invention relates to a compound having an indenoacridan ring structure and the compound. The present invention relates to an organic electroluminescence device.

  Since organic electroluminescent elements are self-luminous elements, they have been actively researched because they are brighter and have better visibility than liquid crystal elements and can be clearly displayed.

In 1987, Eastman Kodak's C.I. W. Tang et al. Have made organic electroluminescence elements using organic materials practical by developing a laminated structure element that shares various roles with each material. They are composed of a phosphor that can transport electrons, tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) and an aromatic amine compound that can transport holes, Was injected into the phosphor layer to emit light, whereby high luminance of 1000 cd / m ² or more was obtained at a voltage of 10 V or less (see, for example, Patent Document 1 and Patent Document 2).

  To date, many improvements have been made for the practical application of organic electroluminescence devices, and various roles have been further subdivided, and sequentially on the substrate, anode, hole injection layer, hole transport layer, light emitting layer, electron High efficiency and durability are achieved by an electroluminescent device provided with a transport layer, an electron injection layer, and a cathode (see, for example, Non-Patent Document 1).

  Further, the use of triplet excitons has been attempted for the purpose of further improving the luminous efficiency, and the use of phosphorescent emitters has been studied (for example, see Non-Patent Document 2).

  The light-emitting layer can also be produced by doping a charge transporting compound generally called a host material with a phosphor or a phosphorescent material. As described in Non-Patent Document 2 described above, selection of an organic material in an organic electroluminescence element greatly affects various characteristics such as efficiency and durability of the element.

  In an organic electroluminescence device, the light injected from both electrodes recombines in the light emitting layer to obtain light emission. However, it is important how efficiently both holes and electrons are transferred to the light emitting layer. Improve the probability of recombination of holes and electrons by increasing the hole injection property and blocking the electron injected from the cathode, and further confine excitons generated in the light emitting layer Thus, high luminous efficiency can be obtained. Therefore, the role of the hole transport material is important, and there is a demand for a hole transport material that has high hole injectability, high hole mobility, high electron blocking properties, and high durability against electrons. ing.

  In addition, the heat resistance and amorphousness of the material are important for the lifetime of the element. In a material having low heat resistance, thermal decomposition occurs even at a low temperature due to heat generated when the element is driven, and the material is deteriorated. In the case of a material having low amorphous property, the thin film is crystallized even in a short time, and the element is deteriorated. For this reason, the material used is required to have high heat resistance and good amorphous properties.

Examples of hole transport materials that have been used in organic electroluminescence devices so far include N, N′-diphenyl-N, N′-di (α-naphthyl) benzidine (hereinafter abbreviated as NPD) and various aromatics. Amine derivatives have been known (see, for example, Patent Document 1 and Patent Document 2). NPD has a good hole transport capability, but its glass transition point (Tg), which is an index of heat resistance, is as low as 96 ° C., and device characteristics are degraded due to crystallization under high temperature conditions (for example, Non-Patent Document 3). Further, among the aromatic amine derivatives described in Patent Document 1 and Patent Document 2, compounds having excellent mobility such as hole mobility of 10 ⁻³ cm ² / Vs or more are known. Because of insufficient electron blocking properties, some of the electrons pass through the light emitting layer and cannot be expected to improve luminous efficiency. For higher efficiency, the electron blocking properties are higher and the thin film is more stable. Therefore, a material having high heat resistance has been demanded.

  As compounds having improved properties such as heat resistance, hole injection properties, and electron blocking properties, arylamine compounds having a substituted acridan structure represented by the following formula (for example, compounds A to C) have been proposed. (For example, see Patent Documents 3 to 5).

(Compound A)

(Compound B)

(Compound C)

  However, devices using these compounds in the hole injection layer or hole transport layer have been improved in heat resistance and light emission efficiency, but are still not sufficient. The efficiency was not sufficient, and there was a problem with amorphousness. For this reason, there has been a demand for further lower drive voltage and higher light emission efficiency while enhancing amorphousness.

JP-A-8-048656 Japanese Patent No. 3194657 WO2006 / 033563 publication WO2007 / 110228 publication WO 2010/147319

Proceedings of the 9th meeting of the Japan Society of Applied Physics 55-61 pages (2001) Proceedings of the 9th Workshop of the Japan Society of Applied Physics 23-31 pages (2001) Proceedings of the 3rd Regular Meeting of the Organic EL Discussion Group, 13-14 pages (2006) J. et al. Org. Chem., 60, 7508 (1995) Synth. Commun. , 11, 513 (1981)

  The object of the present invention is as a highly efficient and durable organic electroluminescent device material, excellent in hole injection / transport performance, electron blocking ability, high stability in a thin film state, and heat resistance It is another object of the present invention to provide an organic compound having excellent characteristics and to provide an organic electroluminescence device having high luminous efficiency and durability using this compound.

  The physical characteristics that the organic compound to be provided by the present invention should have include (1) good hole injection characteristics, (2) high hole mobility, and (3) electron blocking ability. (4) The thin film state is stable, and (5) The heat resistance is excellent. The physical characteristics of the organic electroluminescent device to be provided by the present invention include (1) high luminous efficiency and power efficiency, (2) low emission start voltage, and (3) practical use. The drive voltage is low.

  Therefore, in order to achieve the above object, the inventors of the present invention have an aromatic tertiary amine structure having a high hole injection / transport capability, and an indenoacridan ring structure has an electron blocking property. In addition, in anticipation of the effects of this partial structure on heat resistance and thin film stability, a compound having an indenoacridan ring structure is designed and chemically synthesized. As a result of prototyping an electroluminescence element and intensively evaluating the characteristics of the element, the present invention has been completed.

  1) That is, the present invention is a compound having an indenoacridan ring structure represented by the following general formula (1).

(1)

(In the formula, A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, or a single bond; A substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or an optionally substituted vinyl group, aromatic carbonized A di-substituted amino group substituted by a group selected from a hydrogen group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, wherein R _{1 to} R ₁₀ may be the same or different from each other; An atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, and an optionally substituted carbon Cycloa having 5 to 10 atoms A kill group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a straight chain or branched chain having 1 to 6 carbon atoms which may have a substituent Alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted Or an unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which is bonded to each other via a single bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring R _{11 to} R ₁₄ may be the same as or different from each other, and may have a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a substituent, or a substituent. Even if A cycloalkyl group having 5 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a carbon atom which may have a substituent 1 to 6 linear or branched alkyloxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted A substituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, wherein R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ are a single bond, substituted or A ring may be bonded to each other via an unsubstituted methylene group, an oxygen atom or a sulfur atom, where A is a substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted aromatic complex. Or a substituted or unsubstituted condensed polycyclic aromatic divalent group, wherein B is a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed group A polycyclic aromatic group, or a di-substituted amino group substituted by a group selected from an optionally substituted vinyl group, aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group In some cases, A and B may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. )

  2) Moreover, this invention is a compound which has the indenoacridan ring structure of the said 1) description represented by the following general formula (1-1).

(1-1)

(In the formula, A represents a substituted or unsubstituted aromatic hydrocarbon, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic aromatic divalent group, and Ar ₁ and Ar ₂ represent They may be the same as or different from each other, and may have a substituent, a vinyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensation. Represents a polycyclic aromatic group, and Ar ₁ and Ar ₂ may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, R _{1 to} R _10. May be the same or different from each other, and may be a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group or a linear or branched chain having 1 to 6 carbon atoms which may have a substituent. With alkyl groups and substituents A cycloalkyl group having 5 to 10 carbon atoms which may be present, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and a substituent. A linear or branched alkyloxy group having 1 to 6 carbon atoms, an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, A substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, which is a single bond, a substituted or unsubstituted methylene group, an oxygen atom or R _{11 to} R ₁₄ may be the same or different from each other and may have a substituent, and may be a straight chain having 1 to 6 carbon atoms. Shape Or a branched alkyl group, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, an optionally substituted straight chain or branched chain having 2 to 6 carbon atoms An alkenyl group, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, and an optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms A group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom, where A and Ar ₁ are Single bond, substitution Properly unsubstituted methylene group may be bonded to each other through an oxygen atom or a sulfur atom to form a ring. )

  3) The present invention also provides an index according to the above 1), wherein in the general formula (1), A is a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted condensed polycyclic aromatic divalent group. It is a compound having a noacridan ring structure.

4) The present invention also provides an indenoacridan ring structure according to the above 3), wherein in the general formula (1), A is a divalent group formed by removing two hydrogen atoms from substituted or unsubstituted benzene. It is a compound that has.

  5) The present invention also provides an indenoacridan ring structure according to 3) above, wherein in the general formula (1), A is a divalent group formed by removing two hydrogen atoms from substituted or unsubstituted biphenyl. It is a compound that has.

  6) The present invention also provides an indenoacridan ring structure according to the above 1), wherein, in the general formula (1), A is a divalent group formed by removing two hydrogen atoms from a substituted or unsubstituted indole. It is a compound that has.

  7) Moreover, this invention is a compound which has the indenoacridan ring structure of the said 1) description whose B is a substituted or unsubstituted carbazolyl group in the said General formula (1).

  8) Moreover, this invention is a compound which has the indenoacridan ring structure of said 1) description whose said B is a substituted or unsubstituted dibenzofuranyl group in the said General formula (1).

  9) Moreover, this invention is a compound which has the indenoacridane ring structure of said 1) whose B is a substituted or unsubstituted phenyl group in the said General formula (1).

  10) Moreover, this invention is a compound which has the indenoacridan ring structure of said 1) description whose said B is a substituted or unsubstituted biphenyl group in the said General formula (1).

  11) Moreover, this invention is an organic electroluminescent element which has at least one organic layer pinched | interposed between a pair of electrodes, The indenoacridan ring structure as described in any one of said 1) -10) is included. The organic electroluminescent element is characterized in that the compound having the above-mentioned compound is used as a constituent material of at least one organic layer.

  12) Moreover, this invention is an organic electroluminescent element of the said 11) description whose said organic layer is a positive hole transport layer.

  13) Moreover, this invention is an organic electroluminescent element of the said 11) description whose said organic layer is an electron blocking layer.

  14) Moreover, this invention is an organic electroluminescent element of the said 11) description whose said organic layer is a positive hole injection layer.

  15) Moreover, this invention is an organic electroluminescent element of the said 11) description whose said organic layer is a light emitting layer.

In the “substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted aromatic heterocyclic ring or substituted or unsubstituted condensed polycyclic aromatic divalent group” represented by A in the general formula (1) “Aromatic hydrocarbon”, “Aromatic heterocycle” of “Substituted or unsubstituted aromatic hydrocarbon”, “Substituted or unsubstituted aromatic heterocycle” or “Substituted or unsubstituted condensed polycyclic aromatic” Or, as the “fused polycyclic aromatic”, specifically, benzene, biphenyl, terphenyl, tetrakisphenyl, styrene, naphthalene, anthracene, acenaphthalene, fluorene, phenanthrene, indane, pyrene, pyridine, pyrimidine, triazine, furan, Pyran, thiophene, indole, quinoline, isoquinoline, benzofuran, benzothiophene, indoline, carbazol Can carboline, benzoxazole, benzothiazole, quinoxaline, benzimidazole, pyrazole, dibenzofuran, dibenzothiophene, naphthyridine, phenanthroline, and the like Akurijinin.
And represented by A in the general formula (1), “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted aromatic heterocyclic ring” or “substituted or The “unsubstituted fused polycyclic aromatic divalent group” is a divalent group formed by removing two hydrogen atoms from the above “aromatic hydrocarbon”, “aromatic heterocycle” or “fused polycyclic aromatic”. Represent.
Here, the “aromatic heterocycle” in the “divalent group of a substituted or unsubstituted aromatic heterocycle” is a sulfur-containing aromatic heterocycle such as thiophene, benzothiophene, benzothiazole, dibenzothiophene, or furan. Oxygen-containing aromatic heterocycles such as pyran, benzofuran, benzoxazole and dibenzofuran, indole and carbazole are preferred.
As A in the general formula (1), “a divalent group of a substituted or unsubstituted aromatic hydrocarbon”, “a divalent group of a substituted or unsubstituted condensed polycyclic aromatic”, an indole or carbazole to a hydrogen atom Is preferably a divalent group formed by removing two hydrogen atoms from benzene, biphenyl or indole.

In the “substituted or unsubstituted aromatic hydrocarbon, substituted or unsubstituted aromatic heterocyclic ring or substituted or unsubstituted condensed polycyclic aromatic divalent group” represented by A in the general formula (1) Specific examples of the “substituent” of “substituted aromatic hydrocarbon”, “substituted aromatic heterocycle” or “substituted condensed polycyclic aromatic” include deuterium atom, cyano group, nitro group; fluorine atom, chlorine Halogen atoms such as atoms, bromine atoms and iodine atoms; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, straight or branched alkyl groups having 1 to 6 carbon atoms such as n-hexyl group; straight chain having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group and propyloxy group; Are branched alkyloxy groups; alkenyl groups such as allyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; arylalkyloxy groups such as benzyloxy groups and phenethyloxy groups; phenyl groups, biphenylyl groups, terphenylyl groups, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, thienyl group, furyl Group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group Groups, aromatic heterocyclic groups such as dibenzothienyl groups and carbolinyl groups; aryl vinyl groups such as styryl groups and naphthyl vinyl groups; and groups such as acyl groups such as acetyl groups and benzoyl groups. The group may be further substituted by the above-exemplified substituents.
These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

  “Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group” represented by B in the general formula (1) As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group”, specifically, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group , Fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl Group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group Dibenzofuranyl group, dibenzothienyl group, and the like carbolinyl group may be mentioned.

  As the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by B in the general formula (1), specifically, , Deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert A linear or branched alkyl group having 1 to 6 carbon atoms such as a butyl group, an n-pentyl group, an isopentyl group, a neopentyl group or an n-hexyl group; a methyloxy group, an ethyloxy group, a propyloxy group or the like; A linear or branched alkyloxy group having 1 to 6 carbon atoms; an alkenyl group such as an allyl group; an aryloxy group such as a phenyloxy group or a tolyloxy group; Arylalkyloxy groups such as ruoxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group Aromatic hydrocarbon group or condensed polycyclic aromatic group such as: pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl Group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group and other aromatic heterocyclic groups; styryl group, naphthylvinyl group and other aryl vinyl groups; Group, can be mentioned groups such as acyl groups such as benzoyl group, these substituents may further the exemplified substituents may be substituted. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

  “Aromatic hydrocarbon” in “a disubstituted amino group substituted by a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group” represented by B in the general formula (1) As the “group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group”, specifically, “substituted or unsubstituted aromatic hydrocarbons” represented by B in the above general formula (1) "Aromatic hydrocarbon group", "aromatic heterocyclic group" or "fused polycycle" in "group", "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensed polycyclic aromatic group" The same groups as those shown for the “aromatic group” can be mentioned. Further, these groups may have a substituent, and as the substituent, the above-mentioned “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” The thing similar to what was shown regarding "substituent" can be mention | raise | lifted, and a preferable aspect can also mention the same thing.

The “aromatic heterocyclic group” in the “substituted or unsubstituted aromatic heterocyclic group” of B in the general formula (1) is sulfur-containing such as thienyl group, benzothienyl group, benzothiazolyl group, dibenzothienyl group, etc. An aromatic heterocyclic group, a furyl group, a pyranyl group, a benzofuranyl group, a benzoxazolyl group, a dibenzofuranyl group, or other oxygen-containing aromatic heterocyclic ring, or a carbazolyl group is preferable.
As B in the general formula (1), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted condensed polycyclic aromatic group”, “aromatic hydrocarbon group, aromatic heterocyclic group” Or a “disubstituted amino group substituted by a group selected from condensed polycyclic aromatic groups”, a carbazolyl group, a dibenzofuranyl group, or a dibenzothienyl group, and particularly “a substituted or unsubstituted aromatic hydrocarbon”. Group "," substituted or unsubstituted condensed polycyclic aromatic group "," disubstituted amino group substituted by a group selected from aromatic hydrocarbon group or condensed polycyclic aromatic group ", carbazolyl group, or dibenzofura It is preferably a nyl group.
A and B in the general formula (1) may be bonded directly or via respective substituents to form a ring. In this case, a single bond, a substituted or unsubstituted methylene group, an oxygen atom Alternatively, it is preferable to bond via a sulfur atom, and it is more preferable to form a ring via a substituted or unsubstituted methylene group.

“A linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent” represented by R _{1 to} R ₁₀ in the general formula (1), “having a substituent In the “cycloalkyl group having 5 to 10 carbon atoms” or “straight or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent”. Examples of “straight or branched alkyl group of 6”, “cycloalkyl group of 5 to 10 carbon atoms” or “straight chain or branched alkenyl group of 2 to 6 carbon atoms” specifically include , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclopentyl group, cyclyl Hexyl group, 1-adamantyl, 2-adamantyl, vinyl group, allyl group, isopropenyl group, and the like 2-butenyl group. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyl group having 1 to 6 carbon atoms having a substituent” represented by R _{1 to} R ₁₀ in the general formula (1), “5 to 10 carbon atoms having a substituent” Specific examples of the “substituent” in the “cycloalkyl group of” or “straight-chain or branched alkenyl group having 2 to 6 carbon atoms having a substituent” include a deuterium atom, a cyano group, and a nitro group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; linear or branched alkyloxy group having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group and propyloxy group; Alkenyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; arylalkyloxy groups such as benzyloxy groups and phenethyloxy groups; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as enylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl Group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofura Examples thereof include a group such as an aromatic heterocyclic group such as a nyl group, a dibenzothienyl group, and a carbolinyl group, and these substituents may be further substituted by the above-exemplified substituents. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent” represented by R _{1 to} R ₁₀ in the general formula (1) or “having a substituent. Or a "C1-C6 linear or branched alkyloxy group" or "C5-C10 cycloalkyloxy group" in the "optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms". Specifically, methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group Cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2-adamantyloxy And the like. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyloxy group having 1 to 6 carbon atoms having a substituent” represented by R _{1 to} R ₁₀ in the general formula (1) or “having 5 to 5 carbon atoms having a substituent” Specific examples of the “substituent” in “10 cycloalkyloxy groups” include deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyloxy group, ethyloxy A linear or branched alkyloxy group having 1 to 6 carbon atoms such as a propyloxy group; an alkenyl group such as an allyl group; an aryloxy group such as a phenyloxy group or a tolyloxy group; a benzyloxy group or a phenethyloxy group Arylalkyloxy groups such as groups; phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthracenyl groups, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as nantril group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl Group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group, etc. And a group such as a group heterocyclic group, and these substituents may be further substituted by the above-exemplified substituents. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by R _{1 to} R ₁₀ in the general formula (1), or “substituted or unsubstituted condensed poly group” Specific examples of the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “condensed polycyclic aromatic group” in the “ring aromatic group” include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group. Group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, Indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, Razoriru group include dibenzofuranyl group, dibenzothienyl group, and carbolinyl group and the like. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R _{1 to} R ₁₀ in the general formula (1), Specifically, deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, A linear or branched alkyl group having 1 to 6 carbon atoms such as isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group; methyloxy group, ethyloxy group, propyl Straight or branched alkyloxy groups having 1 to 6 carbon atoms such as oxy groups; alkenyl groups such as allyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; Si group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl Group, aromatic hydrocarbon group such as triphenylenyl group or condensed polycyclic aromatic group; pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, Aromatic heterocyclic groups such as benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl and carbolinyl; arylbiyl such as styryl and naphthylvinyl Le group; an acetyl group, can be mentioned groups such as acyl groups such as benzoyl group, these substituents may further the exemplified substituents may be substituted. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R _{1 to} R ₁₀ in the general formula (1) include a phenyloxy group, a biphenylyloxy group, and a terfeny group. Examples thereof include a tolyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, an indenyloxy group, a pyrenyloxy group, and a perylenyloxy group. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “substituent” in the “substituted aryloxy group” represented by R _{1 to} R ₁₀ in the general formula (1) include a deuterium atom, a cyano group, a nitro group; a fluorine atom, a chlorine atom, Halogen atoms such as bromine atom and iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- A linear or branched alkyl group having 1 to 6 carbon atoms such as a hexyl group; a linear or branched alkyloxy group having 1 to 6 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group Alkenyl group such as allyl group; aryloxy group such as phenyloxy group and tolyloxy group; ant such as benzyloxy group and phenethyloxy group A rualkyloxy group; an aromatic hydrocarbon group such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, or a triphenylenyl group; Condensed polycyclic aromatic group; pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, Aromatic heterocyclic groups such as benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group and carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; acyl groups such as acetyl group and benzoyl group It can be mentioned, these substituents Furthermore, the exemplified substituents may be substituted. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent” represented by R _{11 to} R ₁₄ in the general formula (1), “having a substituent In the “cycloalkyl group having 5 to 10 carbon atoms” or “straight or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent”. Examples of “straight or branched alkyl group of 6”, “cycloalkyl group of 5 to 10 carbon atoms” or “straight chain or branched alkenyl group of 2 to 6 carbon atoms” specifically include Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclopentyl group, Rohekishiru group, 1-adamantyl, 2-adamantyl, vinyl group, allyl group, isopropenyl group include a 2-butenyl group, and the like. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyl group having 1 to 6 carbon atoms having a substituent” represented by R _{11 to} R ₁₄ in the general formula (1), “5 to 10 carbon atoms having a substituent” Specific examples of the “substituent” in the “cycloalkyl group of” or “straight-chain or branched alkenyl group having 2 to 6 carbon atoms having a substituent” include a deuterium atom, a cyano group, and a nitro group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; linear or branched alkyloxy group having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group and propyloxy group; Alkenyl group; aryloxy group such as phenyloxy group and tolyloxy group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; phenyl group; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl Group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, pyrazolyl group, dibenzofura Examples thereof include a group such as an aromatic heterocyclic group such as a nyl group, a dibenzothienyl group, and a carbolinyl group, and these substituents may be further substituted by the above-exemplified substituents. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent” represented by R _{11 to} R ₁₄ in the general formula (1) or “having a substituent. Or a "C1-C6 linear or branched alkyloxy group" or "C5-C10 cycloalkyloxy group" in the "optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms". Specifically, methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group Cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2-adamantyloxy group Such as it is possible to increase the group. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“A linear or branched alkyloxy group having 1 to 6 carbon atoms having a substituent” represented by R _{11 to} R ₁₄ in the general formula (1) or “C5 to C having a substituent” Specific examples of the “substituent” in “10 cycloalkyloxy groups” include deuterium atom, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyloxy group, ethyloxy A linear or branched alkyloxy group having 1 to 6 carbon atoms such as a propyloxy group; an alkenyl group such as an allyl group; an aryloxy group such as a phenyloxy group or a tolyloxy group; a benzyloxy group or a phenethyloxy group Arylalkyloxy groups such as a group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as entanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group Group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group, etc. And a group such as a group heterocyclic group, and these substituents may be further substituted by the above-exemplified substituents. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by R _{11 to} R ₁₄ in the general formula (1), or “substituted or unsubstituted condensed poly group” Specific examples of the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “condensed polycyclic aromatic group” in the “ring aromatic group” include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group. Group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, Indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group Pyrazolyl group include dibenzofuranyl group, dibenzothienyl group, and carbolinyl group and the like. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

As the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by R _{11 to} R ₁₄ in the general formula (1), Specifically, deuterium atom, trifluoromethyl group, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group; methyloxy group A linear or branched alkyloxy group having 1 to 6 carbon atoms such as ethyloxy group and propyloxy group; alkenyl group such as allyl group; benzyl group and naphthylmethyl Group, aralkyl group such as phenethyl group; aryloxy group such as phenyloxy group and tolyloxy group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyranyl group, thienyl group, furyl group, pyrrolyl Group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzofuranyl group Aromatic heterocyclic groups such as nzothienyl group and carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; acyl groups such as acetyl group and benzoyl group; dialkylamino groups such as dimethylamino group and diethylamino group; diphenylamino group Disubstituted amino groups substituted with aromatic hydrocarbon groups such as dinaphthylamino groups or condensed polycyclic aromatic groups; diaralkylamino groups such as dibenzylamino groups and diphenethylamino groups; dipyridylamino groups and dithienyls Disubstituted amino groups substituted with aromatic heterocyclic groups such as amino groups; dialkenylamino groups such as diallylamino groups; alkyl groups, aromatic hydrocarbon groups, condensed polycyclic aromatic groups, aralkyl groups, aromatic hetero groups A group such as a disubstituted amino group substituted with a substituent selected from a cyclic group or an alkenyl group; These substituents may be further substituted with the substituents exemplified above. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R _{11 to} R ₁₄ in the general formula (1) include a phenyloxy group, a biphenylyloxy group, a terfeny group. Examples thereof include a tolyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, an indenyloxy group, a pyrenyloxy group, and a perylenyloxy group. These groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “substituent” in the “substituted aryloxy group” represented by R _{11 to} R ₁₄ in the general formula (1) include deuterium atom, trifluoromethyl group, cyano group, nitro group; fluorine Halogen atoms such as atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, Linear or branched alkyl group having 1 to 6 carbon atoms such as neopentyl group or n-hexyl group; linear or branched alkyl group having 1 to 6 carbon atoms such as methyloxy group, ethyloxy group or propyloxy group Alkyloxy groups; alkenyl groups such as allyl groups; aralkyl groups such as benzyl groups, naphthylmethyl groups, and phenethyl groups; phenyloxy groups Aryloxy groups such as tolyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl Group, fluoranthenyl group, triphenylenyl group and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group An aromatic heterocyclic group such as a group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbolinyl group; Aryl vinyl groups such as tyryl and naphthyl vinyl groups; acyl groups such as acetyl and benzoyl groups; dialkylamino groups such as dimethylamino and diethylamino groups; aromatic hydrocarbon groups such as diphenylamino and dinaphthylamino groups; Disubstituted amino groups substituted with condensed polycyclic aromatic groups; Diaralkylamino groups such as dibenzylamino groups and diphenethylamino groups; Substituted with aromatic heterocyclic groups such as dipyridylamino groups and dithienylamino groups Disubstituted amino groups; dialkenylamino groups such as diallylamino groups; substituted with substituents selected from alkyl groups, aromatic hydrocarbon groups, condensed polycyclic aromatic groups, aralkyl groups, aromatic heterocyclic groups or alkenyl groups And a group such as the above-mentioned di-substituted amino group. The substituent may be substituted. These substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted group” represented by Ar ₁ or Ar ₂ in formula (1-1) As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “fused polycyclic aromatic group”, specifically, in B in the above general formula (1), The “aromatic hydrocarbon group” in the “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group” represented by , The same groups as those mentioned for the “aromatic heterocyclic group” or “fused polycyclic aromatic group” can be mentioned. Moreover, the substituent which these groups may have is also represented by the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensation” represented by B in the general formula (1). The thing similar to what was shown regarding "substituent" of "polycyclic aromatic group" can be mention | raise | lifted.
The “aromatic heterocyclic group” in the “substituted or unsubstituted aromatic heterocyclic group” represented by Ar ₁ and Ar ₂ in the general formula (1-1) is a thienyl group, a benzothienyl group, or a benzothiazolyl group. Sulfur-containing aromatic heterocyclic groups such as dibenzothienyl group, oxygen-containing aromatic heterocyclic groups such as furyl group, pyranyl group, benzofuranyl group, benzoxazolyl group, dibenzofuranyl group, and carbazolyl group are preferable.

Ar ₁ and Ar ₂ in the general formula (1-1) are “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted condensed polycyclic aromatic group”, or carbazolyl group. Is preferred.
Ar ₁ and Ar _{2 in} formula (1-1) may be bonded directly or via respective substituents to form a ring, in which case a single bond, a substituted or unsubstituted methylene group, Bonding is preferably via an oxygen atom or a sulfur atom, more preferably forming a ring via a substituted or unsubstituted methylene group.
Ar ₁ and A in formula (1-1) may be bonded directly or via respective substituents to form a ring. In this case, a single bond, a substituted or unsubstituted methylene group, oxygen The bonding is preferably via an atom or a sulfur atom, more preferably a ring is formed through a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom, and the ring is formed through a substituted or unsubstituted methylene group. It is particularly preferred to form.

  The compound represented by the general formula (1) of the present invention, which has an indenoacridan ring structure, is a novel compound, and has an excellent electron blocking ability than a conventional hole transport material, and an excellent amorphous And a thin film state is stable.

  The compound having an indenoacridan ring structure represented by the general formula (1) of the present invention is a hole injection layer and / or a hole transport layer of an organic electroluminescence device (hereinafter abbreviated as an organic EL device). It can be used as a constituent material. By using a material with higher hole injection properties, higher mobility, higher electron blocking properties, and higher electron stability than conventional materials, it is possible to confine excitons generated in the light emitting layer. In addition, the probability of recombination of holes and electrons can be improved, high luminous efficiency can be obtained, the driving voltage is lowered, and the durability of the organic EL element is improved.

  The compound having an indenoacridan ring structure represented by the general formula (1) of the present invention can also be used as a constituent material of an electron blocking layer of an organic EL device. By using a material with excellent electron blocking ability and hole transportability compared to conventional materials and high stability in the thin film state, the driving voltage is lowered and current resistance is maintained while having high luminous efficiency. Is improved and the maximum light emission luminance of the organic EL element is improved.

  The compound having an indenoacridan ring structure represented by the general formula (1) of the present invention can also be used as a constituent material of a light emitting layer of an organic EL device. The material of the present invention, which has excellent hole transportability compared to conventional materials and has a wide band gap, is used as a host material for the light-emitting layer, and supports a fluorescent or phosphorescent emitter called a dopant to emit light. By using it as a layer, it has the effect | action that a drive voltage falls and can implement | achieve the organic EL element by which luminous efficiency was improved.

  The organic EL device of the present invention has a higher hole mobility than that of a conventional hole transport material, an excellent electron blocking ability, an excellent amorphous property, and a stable thin film state. Since a compound having a clidan ring structure is used, high efficiency and high durability can be realized.

  The compound having an indenoacridan ring structure of the present invention is useful as a constituent material of a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer of an organic EL device, and has an excellent electron blocking ability. In addition, the amorphous property is good, the thin film state is stable, and the heat resistance is excellent. The organic EL device of the present invention has high luminous efficiency and high power efficiency, which can reduce the practical driving voltage of the device. The emission start voltage can be lowered and the durability can be improved.

1 is a ¹ H-NMR chart of the compound of Example 1 of the present invention (Compound 2). ^{1 is} a ¹ H-NMR chart of a compound of Example 2 of the present invention (Compound 19). FIG. 3 is a ¹ H-NMR chart of the compound of Example 3 of the present invention (Compound 30). FIG. 3 is a ¹ H-NMR chart of the compound of Example 4 of the present invention (Compound 31). FIG. 6 is a ¹ H-NMR chart of the compound of Example 5 of the present invention (Compound 32). FIG. 6 is a ¹ H-NMR chart of the compound of Example 6 of the present invention (Compound 33). FIG. 6 is a ¹ H-NMR chart of the compound of Example 7 of the present invention (Compound 34). It is the figure which showed the EL element structure of Examples 10-16 and the comparative example 1. FIG.

  The compound having an indenoacridan ring structure of the present invention is a novel compound, and these compounds can be synthesized as follows, for example. For example, methyl 2- (9,9-dimethylfluoren-2-yl) aminobenzoate is synthesized by reaction of methyl 2-aminobenzoate with 9,9-dimethyl-2-iodofluorene, and methyl magnesium chloride By reacting, 2- {2- (9,9-dimethylfluoren-2-yl) amino) phenyl} propan-2-ol is synthesized and subjected to a cyclization reaction, whereby 7,7,13,13 -Tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine can be synthesized. Subsequently, by carrying out a condensation reaction such as the Buchwald-Hartwig reaction between 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine and aryl halide. A compound having an indenoacridan ring structure of the present invention in which the 5-position is substituted with an aryl group can be synthesized.

In addition, the introduction of a substituent to the indenoacridan ring can be achieved, for example, by bromination of the indenoacridan substituted with an aryl group at the 5-position with N-bromosuccinimide or the like at the 2-position. Indenoacridan derivatives can be synthesized, and bromo-substituted products with different substitution positions can be obtained by changing the bromination reagent and conditions.
By performing a cross-coupling reaction such as Suzuki coupling (for example, see Non-Patent Document 5) between this bromo-substituted product and various boronic acids or boronic acid esters (for example, see Non-Patent Document 4), A compound having an indenoacridan ring structure of the present invention in which a substituent is introduced into the cridane ring can be synthesized.

  Specific examples of preferable compounds among the compounds having an indenoacridan ring structure represented by the general formula (1) are shown below, but the present invention is not limited to these compounds.

(Compound 2)

(Compound 3)

(Compound 4)

(Compound 5)

(Compound 6)

(Compound 7)

(Compound 8)

(Compound 9)

(Compound 10)

(Compound 11)

(Compound 12)

(Compound 13)

(Compound 14)

(Compound 15)

(Compound 16)

(Compound 17)

(Compound 18)

(Compound 19)

(Compound 20)

(Compound 21)

(Compound 22)

(Compound 23)

(Compound 24)

(Compound 25)

(Compound 26)

(Compound 27)

(Compound 28)

(Compound 29)

(Compound 30)

(Compound 31)

(Compound 32)

(Compound 33)

(Compound 34)

(Compound 35)

(Compound 36)

(Compound 37)

(Compound 38)

(Compound 39)

(Compound 40)

(Compound 41)

(Compound 42)

(Compound 43)

(Compound 44)

(Compound 45)

(Compound 46)

(Compound 47)

(Compound 48)

(Compound 49)

(Compound 50)

(Compound 51)

(Compound 52)

(Compound 53)

(Compound 54)

(Compound 55)

(Compound 56)

(Compound 57)

  These compounds were purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, and the like. The compound was identified by NMR analysis. As a physical property value, a glass transition point (Tg) and a work function were measured. The glass transition point (Tg) is an index of stability in a thin film state, and the work function is an index of hole transportability.

  The glass transition point (Tg) was determined with a high sensitivity differential scanning calorimeter (Bruker AXS, DSC3100SA) using powder.

  The work function was measured using an ionization potential measuring device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.) after forming a 100 nm thin film on the ITO substrate.

  The structure of the organic EL device of the present invention includes an anode, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, and a cathode sequentially on the substrate. And those having an electron injection layer between the electron transport layer and the cathode. In these multilayer structures, several organic layers can be omitted. For example, a structure having an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode sequentially on a substrate can be used. .

  As the anode of the organic EL element of the present invention, an electrode material having a large work function such as ITO or gold is used. As a hole injection layer of the organic EL device of the present invention, in addition to a compound having an indenoacridan ring structure represented by the general formula (1) of the present invention, a porphyrin compound typified by copper phthalocyanine, a starburst type Materials such as triphenylamine derivatives and various triphenylamine tetramers, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating polymer materials can be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

  As a hole transport layer of the organic EL device of the present invention, in addition to the compound having an indenoacridan ring structure represented by the general formula (1) of the present invention, N, N′-diphenyl-N, N′-di (M-tolyl) benzidine (hereinafter abbreviated as TPD), N, N′-diphenyl-N, N′-di (α-naphthyl) benzidine (hereinafter abbreviated as NPD), N, N, N ′, Benzidine derivatives such as N′-tetrabiphenylylbenzidine, 1,1-bis [4- (di-4-tolylamino) phenyl] cyclohexane (hereinafter abbreviated as TAPC), various triphenylamine trimers and tetramers The body can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. Further, as a hole injection / transport layer, a coating type such as poly (3,4-ethylenedioxythiophene) (hereinafter abbreviated as PEDOT) / poly (styrene sulfonate) (hereinafter abbreviated as PSS) is used. These polymer materials can be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

  In addition, in the hole injection layer or the hole transport layer, a material that is usually used for the layer is further P-doped with trisbromophenylamine hexachloroantimony or the like, or a TPD structure having a partial structure. Molecular compounds and the like can be used.

  As an electron blocking layer of the organic EL device of the present invention, in addition to the compound having an indenoacridan ring structure represented by the general formula (1) of the present invention, 4,4 ′, 4 ″ -tri (N-carbazolyl) ) Triphenylamine (hereinafter abbreviated as TCTA), 9,9-bis [4- (carbazol-9-yl) phenyl] fluorene, 1,3-bis (carbazol-9-yl) benzene (hereinafter referred to as mCP) Carbazole derivatives such as 2,2-bis (4-carbazol-9-ylphenyl) adamantane (hereinafter abbreviated as Ad-Cz), 9- [4- (carbazol-9-yl) phenyl]- A compound having an electron blocking action such as a compound having a triphenylamine group and a triarylamine structure represented by 9- [4- (triphenylsilyl) phenyl] -9H-fluorene It is possible to use the thing. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As the light emitting layer of the organic EL device of the present invention, various metal complexes, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, etc., in addition to metal complexes of quinolinol derivatives including Alq ₃ Can be used. It is also possible to constitute a light-emitting layer is a host material and a dopant material, a host material, in addition to the compound having an indeno acridan ring structure represented by the general formula (1) of the present invention, in addition to the light emitting material, Thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, and the like can be used. As the dopant material, quinacridone, coumarin, rubrene, perylene, and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.

In addition, a phosphorescent material can be used as the light emitting material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir (ppy) ₃ , blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp ₂ Ir (acac), and the like are used as host materials. In addition to carbazole derivatives such as 4,4′-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP), TCTA, mCP, etc. as a hole injection / transport host material, it is possible to use a compound having an indeno acridan ring structure represented. As an electron transporting host material, p-bis (triphenylsilyl) benzene (hereinafter abbreviated as UGH2) and 2,2 ′, 2 ″-(1,3,5-phenylene) -tris (1-phenyl) -1H-benzimidazole) (hereinafter abbreviated as TPBI) and the like, and a high-performance organic EL device can be produced.

  In order to avoid concentration quenching, the host material of the phosphorescent light emitting material is preferably doped by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer.

  These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

  As a hole blocking layer of the organic EL device of the present invention, a phenanthroline derivative such as bathocuproine (hereinafter abbreviated as BCP) or aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate In addition to metal complexes of quinolinol derivatives such as BAlq), various rare earth complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, and the like can be used. These materials may also serve as the material for the electron transport layer. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

As an electron transport layer of the organic EL device of the present invention, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline, in addition to metal complexes of quinolinol derivatives including Alq ₃ and BAlq. Derivatives, phenanthroline derivatives, silole derivatives and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.

  As the electron injection layer of the organic EL device of the present invention, an alkali metal salt such as lithium fluoride and cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, and a metal oxide such as aluminum oxide can be used. In the preferred selection of the electron transport layer and the cathode, this can be omitted.

  As the cathode of the organic EL device of the present invention, an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as the electrode material.

  Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

<7,7,13,13-tetramethyl-5- {4- (9-phenyl-9H-carbazol-3-yl) phenyl} -7,13-dihydro-5H-indeno [1,2-b] acridine Synthesis of (Compound 2)>
To a reaction vessel purged with nitrogen, 35.4 g of methyl 2-aminobenzoate, 50.0 g of 2-iodo-9,9-dimethyl-9H-fluorene, 22.51 g of tert-butoxy sodium and 500 ml of xylene were added and nitrogen was added for 1 hour. Gas was aerated. 2.9 g of tris (dibenzylideneacetone) dipalladium (0) and 3.8 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 5 hours. After cooling to room temperature and adding water and toluene, the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) and yellow powder of methyl 2-{(9,9-dimethyl-9H-fluoren-2-yl) amino} benzoate 25.8 g (yield 48%) of the product was obtained.

  The obtained 2-{(9,9-dimethyl-9H-fluoren-2-yl) amino} methylbenzoate (31.0 g) and THF (310 ml) were added to a nitrogen-substituted reaction vessel, and methylmagnesium chloride in THF (3 mol / mol) was added. L) 108 ml was added dropwise. After stirring at room temperature for 1 hour, 300 ml of a 20% aqueous ammonium chloride solution was added, and the organic layer was collected by extraction with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure to give 2- [2-{(9,9-dimethyl-9H-fluoren-2-yl) amino} phenyl] propan-2-ol. 31.0 g (yield 100%) of pale yellow oil was obtained.

The obtained 2- [2-{(9,9-dimethyl-9H-fluoren-2-yl) amino} phenyl] propan-2-ol 31.0 g and phosphoric acid 62 ml were added to a reaction vessel purged with nitrogen, Stir at room temperature for 2 hours. After 300 ml of toluene and 300 ml of water were added and stirred, the precipitate was collected by filtration, and a thin 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine solution was collected. 26.2 g (yield 89%) of yellow powder was obtained.

  The resulting 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine 10.0 g, 3- (4-bromophenyl) -9-phenyl-9H -8.2 g of carbazole, 3.6 g of tert-butoxy sodium, and 100 ml of xylene were added to a nitrogen-substituted reaction vessel, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 2 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) and 7,7,13,13-tetramethyl-5- {4- (9-phenyl-9H-carbazole-3). -Il) phenyl} -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 2) (12.1 g, yield 75%) was obtained.

The structure of the obtained white powder was identified using NMR. ^{The 1} H-NMR measurement results are shown in FIG.

^The following 38 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.65 (1H), 8.28 (1H), 8.11 (2H), 7.88 (1H), 7.86 (1H), 7.60-7.70 (5H) 7.35-7.60 (7H), 7.20-7.35 (3H), 7.12 (1H), 6.80-7.00 (2H), 6.53 (1H), 6. 38 (1H), 1.76 (6H), 1.27 (6H).

Synthesis of <7,7,13,13-tetramethyl-5- {4- (dibenzofuran-4-yl) phenyl} -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 19) >
9. 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine 10.0 g synthesized in Example 1, 4- (4-bromophenyl) dibenzofuran10. 9 g, 3.6 g of tert-butoxy sodium, and 100 ml of xylene were added to a nitrogen-substituted reaction vessel, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 3 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) and 7,7,13,13-tetramethyl-5- {4- (dibenzofuran-4-yl) phenyl}- 13.9 g (yield 80%) of white powder of 7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 19) was obtained.

The structure of the obtained white powder was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.

^The following 33 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.37 (2H), 8.05-8.15 (2H), 7.85-7.95 (2H), 7.62-7.72 (2H), 7.45-7 .62 (5H), 7.40 (1H), 7.31 (1H), 7.23 (1H), 7.12 (1H), 6.88-7.02 (2H), 6.53 (1H) ), 6.41 (1H), 1.76 (6H), 1.27 (6H).

<Synthesis of 7,7,13,13-tetramethyl-5- (p-terphenyl-3-yl) -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 30)>
7.0 g of 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine synthesized in Example 1, 10.0 g of 3-bromo-p-terphenyl Then, 3.2 g of tert-butoxy sodium and 90 ml of xylene were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.4 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 3 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) and 7,7,13,13-tetramethyl-5- (p-terphenyl-3-yl) -7, 12.3 g (yield 80%) of white powder of 13-dihydro-5H-indeno [1,2-b] acridine (Compound 30) was obtained.

The structure of the obtained white powder was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.

^The following 35 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 7.95 (1H), 7.90 (1H), 7.60-7.88 (9H), 7.50 (1H), 7.36-7.48 (3H), 7. 28-7.37 (2H), 7.22 (1H), 7.13 (1H), 6.85-7.00 (2H), 6.48 (1H), 6.36 (1H), 1. 76 (6H), 1.27 (6H).

Synthesis of <7,7,13,13-tetramethyl-5- {3- (dibenzofuran-4-yl) phenyl} -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 31) >
7. 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine 10.0 g synthesized in Example 1, 4- (3-bromophenyl) dibenzofuran10. 9 g, 3.6 g of tert-butoxy sodium, and 100 ml of xylene were added to a nitrogen-substituted reaction vessel, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 2 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) and 7,7,13,13-tetramethyl-5- {3- (dibenzofuran-4-yl) phenyl}- 12.2 g (yield 70%) of a white powder of 7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 31) was obtained.

The structure of the obtained white powder was identified using NMR. ^The result of ¹ H-NMR measurement is shown in FIG.

^The following 33 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.25 (1H), 8.00-8.10 (3H), 7.81-7.92 (2H), 7.77 (1H), 7.69 (1H), 7. 57 (1H), 7.40-7.52 (4H), 7.28-7.39 (2H), 7.24 (1H), 7.13 (1H), 6.85-7.00 (2H) ), 6.57 (1H), 6.44 (1H), 1.76 (6H), 1.27 (6H).

<Synthesis of 7,7,13,13-tetramethyl-5- (p-terphenyl-4-yl) -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 32)>
7.0 g of 7,7,13,13-tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine synthesized in Example 1, 10.0 g of 4-bromo-p-terphenyl Then, 3.2 g of tert-butoxy sodium and 90 ml of xylene were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.4 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 2 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane), and 7,7,13,13-tetramethyl-5- (p-terphenyl-4-yl) -7, 12.6 g (yield 82%) of white powder of 13-dihydro-5H-indeno [1,2-b] acridine (Compound 32) was obtained.

The structure of the obtained white powder was identified using NMR. ^The results of ¹ H-NMR measurement are shown in FIG.

^The following 35 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.08 (2H), 7.88-7.94 (3H), 7.76-7.84 (2H), 7.67-7.76 (3H), 7.40-7 .52 (5H), 7.28-7.38 (2H), 7.22 (1H), 7.13 (1H), 6.83-6.98 (2H), 6.48 (1H), 6 .36 (1H), 1.76 (6H), 1.27 (6H).

<Synthesis of 7,7,13,13-tetramethyl-5- (1-phenylindol-4-yl) -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 33)>
7,7,13,13-Tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine 10.0 g, 4-bromo-1-phenylindole 9.3 g synthesized in Example 1 Then, 3.6 g of tert-butoxy sodium and 100 ml of xylene were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 5 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane) to give 7,7,13,13-tetramethyl-5- (1-phenylindol-4-yl) -7, 10.7 g (yield 67%) of white powder of 13-dihydro-5H-indeno [1,2-b] acridine (Compound 33) was obtained.

The structure of the obtained white powder was identified using NMR. ¹ H-NMR measurement results are shown in FIG.

^The following 32 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 7.90 (1H), 7.79 (1H), 7.32-7.70 (9H), 7.28 (1H), 7.20 (2H), 7.11 (1H) 6.80-6.90 (2H), 6.44 (1H), 6.35 (1H), 6.22 (1H), 1.76 (6H), 1.15 (6H).

<Synthesis of 7,7,13,13-tetramethyl-5- (1-phenylindol-6-yl) -7,13-dihydro-5H-indeno [1,2-b] acridine (Compound 34)>
7,7,13,13-Tetramethyl-7,13-dihydro-5H-indeno [1,2-b] acridine 10.0 g, 6-bromo-1-phenylindole 9.3 g synthesized in Example 1 Then, 3.6 g of tert-butoxy sodium and 100 ml of xylene were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through for 1 hour. 0.5 g of tris (dibenzylideneacetone) dipalladium (0) and 1.5 g of a toluene solution of tri-tert-butylphosphine (50%, w / v) were added and heated, followed by stirring at 115 ° C. for 6 hours. After cooling to room temperature and adding 100 ml of water, the organic layer was collected by extracting with toluene. The organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane), and 7,7,13,13-tetramethyl-5- (1-phenylindol-6-yl) -7, 10.4 g (yield 65%) of white powder of 13-dihydro-5H-indeno [1,2-b] acridine (Compound 34) was obtained.

The structure of the obtained white powder was identified using NMR. ^{The 1} H-NMR measurement results are shown in FIG.

^The following 32 hydrogen signals were detected by ¹ H-NMR (THF-d ₈ ). δ (ppm) = 8.25 (1H), 8.19 (1H), 7.90 (1H), 7.60-7.80 (5H), 7.35-7.60 (4H), 7. 15-7.30 (3H), 7.12 (1H), 6.86 (2H), 6.51 (1H), 6.25 (1H), 1.76 (6H), 1.18 (6H) .

About the compound of this invention, the glass transition point was calculated | required with the highly sensitive differential scanning calorimeter (The Bruker AXS make, DSC3100SA).
Glass transition point Compound 138 ° C of Example 1 of the present invention
Inventive Example 2 Compound 114 ° C.
Inventive Example 3 Compound 103 ° C.
Inventive Example 4 Compound 104 ° C.
Inventive Example 5 Compound 114 ° C.
Inventive Example 6 Compound 105 ° C.
Inventive Example 7 Compound 138 ° C.

  The compound of the present invention has a glass transition point of 100 ° C. or higher, which indicates that the thin film state is stable in the compound of the present invention.

Using the compound of the present invention, a deposited film having a film thickness of 100 nm was produced on an ITO substrate, and the work function was measured with an ionization potential measuring device (PYS-202 type, manufactured by Sumitomo Heavy Industries, Ltd.).
Work Function Compound of Invention Example 1 5.74 eV
Inventive Example 2 compound 5.67 eV
Compound of Example 3 of the present invention 5.70 eV
Inventive Example 4 compound 5.73 eV
Compound of Example 5 of the present invention 5.70 eV
The compound of Inventive Example 6 5.64 eV
Inventive Example 7 Compound 5.65 eV

  As described above, the compound of the present invention exhibits a suitable energy level as compared with the work function 5.54 eV of general hole transport materials such as NPD and TPD, and has a good hole transport capability. You can see that

  The organic EL element has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2 as shown in FIG. 6, an electron injection layer 7 and a cathode (aluminum electrode) 8 were deposited in this order.

Specifically, the glass substrate 1 on which ITO having a thickness of 150 nm was formed was washed with an organic solvent, and then the surface was washed by oxygen plasma treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less. Subsequently, HIM-1 having the following structural formula was formed to a thickness of 20 nm as a hole injection layer 3 so as to cover the transparent anode 2. On this hole injection layer 3, the compound (compound 2) of Example 1 of the present invention was formed as a hole transport layer 4 so as to have a film thickness of 40 nm. On this hole transport layer 4, EMD-1 having the following structural formula and EMH-1 having the following structural formula are used as the light emitting layer 5, and the deposition rate is such that the deposition rate ratio is EMD-1: EMH-1 = 5: 95. Binary vapor deposition was performed to form a film thickness of 30 nm. On this emitting layer 5 was formed to have the Alq ₃ film thickness 30nm as an electron transport layer 6. On the electron transport layer 6, lithium fluoride was formed as the electron injection layer 7 so as to have a film thickness of 0.5 nm. Finally, aluminum was deposited to a thickness of 150 nm to form the cathode 8. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.

  Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the organic EL device produced using the compound of Example 1 (Compound 2) of the present invention.

(HIM-1)

(EMD-1)

(EMH-1)

  In Example 10, except that the compound (Compound 19) of Example 2 of the present invention was formed so as to have a film thickness of 40 nm instead of the compound (Compound 2) of Example 1 of the present invention as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

  In Example 10, except that the compound (Compound 30) of Example 3 of the present invention was formed so as to have a film thickness of 40 nm instead of the compound (Compound 2) of Example 1 of the present invention as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

  In Example 10, except that the compound (Compound 31) of Example 4 of the present invention was formed so as to have a film thickness of 40 nm instead of the compound (Compound 2) of Example 1 of the present invention as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

  In Example 10, except that the compound of Example 5 of the present invention (Compound 32) was formed to a film thickness of 40 nm instead of the compound of Compound 1 of the present invention (Compound 2) as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

  In Example 10, except that the compound (Compound 33) of Example 6 of the present invention was formed so as to have a film thickness of 40 nm instead of the compound (Compound 2) of Example 1 of the present invention as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

  In Example 10, except that the compound (Compound 34) of Example 7 of the present invention was formed so as to have a film thickness of 40 nm instead of the compound (Compound 2) of Example 1 of the present invention as the material of the hole transport layer 4. An organic EL element was produced under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

[Comparative Example 1]
For comparison, in Example 10, HTM-1 having the following structural formula was formed to a film thickness of 40 nm in place of the compound (Compound 2) of Example 1 of the present invention as the material for the hole transport layer 4. Produced an organic EL device under the same conditions. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the produced organic EL element.

(HTM-1)

As shown in Table 1, the driving voltage when a current density of 10 mA / cm ² was passed was 5.17 V of the organic EL element using HTM-1, and Examples 1 to 7 of the present invention. The organic EL element using the compound could be driven at a low voltage of 4.75 to 4.94V. In addition, in terms of power efficiency, the organic EL element using the compounds of Examples 1 to 7 of the present invention is 6.30-7.5 compared to 5.49 lm / W of the organic EL element using HTM-1. Both were greatly improved at 18 lm / W. Further, both the luminance and the luminous efficiency were improved in the organic EL device using the compound of the present invention compared to the organic EL device using HTM-1.

  As is clear from the above results, the organic EL device using the compound having the indenoacridan ring structure of the present invention is more efficient than the known organic EL device using HTM-1. It was found that an improvement and a decrease in practical driving voltage can be achieved.

  The compound having an indenoacridan ring structure of the present invention is excellent as a compound for an organic EL device because it has a high hole transport ability, an excellent electron blocking ability, an excellent amorphous property, and a stable thin film state. ing. By producing an organic EL device using the compound, high luminous efficiency and power efficiency can be obtained, practical driving voltage can be lowered, and durability can be improved. For example, it has become possible to develop home appliances and lighting.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Transparent anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode

Claims (6)

A compound having an indenoacridan ring structure represented by the following general formula (1).
(1)
(In the formula, A is a deuterium atom, cyano group, nitro group, halogen atom, straight or branched alkyl group having 1 to 6 carbon atoms, straight chain having 1 to 6 carbon atoms or A branched alkyloxy group, an alkenyl group, an aryloxy group, an arylalkyloxy group, an aromatic hydrocarbon group, a condensed polycyclic aromatic group or an arylvinyl group , or an unsubstituted phenylene group; Deuterium atom, cyano group, nitro group, halogen atom, linear or branched alkyl group having 1 to 6 carbon atoms, linear or branched alkyloxy group having 1 to 6 carbon atoms as substituents , Alkenyl group, aryloxy group, arylalkyloxy group, aromatic hydrocarbon group, condensed polycyclic aromatic group or arylvinyl group, or Conversion biphenyl group, a dibenzofuranyl group or .R ₁ to R ₁₀ representing a carbazolyl group may be the same or different, a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, A linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent. An optionally substituted linear or branched alkenyl group having 2 to 6 carbon atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, and a substituent. cycloalkyloxy group having 5 carbon atoms that may have a group 10, a substituted or unsubstituted aromatic hydrocarbon group, a deuterium atom as a substituent, a cyano group, a nitro group, a halogen atom, TansoHara A linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyloxy group having 1 to 6 carbon atoms, an alkenyl group, an aryloxy group, an arylalkyloxy group, an aromatic hydrocarbon group A fused polycyclic aromatic group or an aryl vinyl group, or an unsubstituted furyl group, a thienyl group, a benzofuranyl group, a benzothienyl group, a dibenzofuranyl group, or a dibenzothienyl group , a substituted or unsubstituted condensed polycycle an aromatic group or a substituted or unsubstituted aryloxy group, a single bond, a substituted or unsubstituted methylene group, may be bonded to each other to form a ring via an oxygen atom or a sulfur atom .R ₁₁ to R ₁₄ represents a methyl group.   In the organic electroluminescence device having at least one organic layer sandwiched between a pair of electrodes, the compound having an indenoacridan ring structure according to claim 1 is used as a constituent material of at least one organic layer. An organic electroluminescence device characterized by being made.   The organic electroluminescence device according to claim 2, wherein the organic layer in which the compound having the indenoacridan ring structure is used as a constituent material is a hole transport layer.   The organic electroluminescent device according to claim 2, wherein the organic layer in which the compound having the indenoacridan ring structure is used as a constituent material is an electron blocking layer.   The organic electroluminescence device according to claim 2, wherein the organic layer in which the compound having the indenoacridan ring structure is used as a constituent material is a hole injection layer.   The organic electroluminescence device according to claim 2, wherein the organic layer in which the compound having the indenoacridan ring structure is used as a constituent material is a light emitting layer.