JP4980938B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent device.

  Electroluminescent devices that use electroluminescence are self-luminous compared to liquid crystal displays and thus have high visibility and high-speed responsiveness, so that they can display clear images when used in displays. In addition, since it is an all solid-state device, it has characteristics such as excellent impact resistance. Therefore, in recent years, it is expected to be widely used for thin displays, liquid crystal display backlights, flat light sources, and the like.

  Electroluminescent devices can be broadly classified into inorganic electroluminescent devices and organic electroluminescent devices depending on the constituent materials. The inorganic electroluminescent device is a dispersive electroluminescent device using an inorganic material such as zinc sulfide. The driving method of this dispersive electroluminescent device is that an accelerated electron collides and excites the emission center by applying a high electric field. Therefore, it is necessary to drive with a high AC voltage. Therefore, there are problems such as a complicated driving circuit and low luminance.

  On the other hand, an organic electroluminescence device (organic electroluminescence device: organic EL device) emits light by recombining charges (holes and electrons) injected from an electrode in a light emitting layer made of an organic compound. Because it is “light emission”, it can be driven at a low voltage (Non-patent Document 1 and Patent Document 1). Further, there is an advantage that an arbitrary emission color and characteristics can be easily changed by changing the molecular design of the organic compound. For this reason, various materials and element configurations have been proposed at present, and research and development has been activated.

  On the other hand, various problems and problems still remain in the organic electroluminescent devices using the materials proposed so far. For example, there is a problem in the light emission life that the function of the element deteriorates and the light emission luminance decreases only by storing, regardless of the drive state or the non-drive state. In general, the emission luminance is still low, which is not sufficient for practical use.

  As a method for improving emission luminance, an organic electroluminescence device using tris (8-quinolinolato) aluminum or the like as a host material in a light emitting layer, a coumarin derivative or a pyran derivative as a guest compound (Non-patent Document 2), and a guest compound An organic electroluminescent device using N, N-dimethylquinacridone (for example, Non-Patent Document 3) and an organic electroluminescent device using rubrene as a guest compound (for example, Non-Patent Document 4) have been proposed.

  These organic electroluminescence emits light when an organic molecule forms an excited state by recombination of carrier electrons and holes injected from an electric field and falls to a ground state. In this case, the excited organic molecule takes a high energy excited singlet state (electrons are reverse spin) and a low energy excited triplet state (electrons are the same spin).

  In recent years, organic phosphorescent materials have attracted attention as a material for improving luminous efficiency in research on organic electroluminescent devices. It has also been proposed to use a phosphorescent material as a guest material for the light emitting layer of the organic EL element (Non-patent Documents 5 and 6). In general, in the phosphorescence process, an organic molecule is excited from a ground state to a singlet excited state, and then a non-radiative transition called intersystem crossing from a singlet excited state to a triplet excited state occurs. Phosphorescence emission shows light emission of triplet excited state → ground state.

  It is expected that high luminous efficiency can be achieved by using the singlet excited state and the triplet excited state of the organic phosphorescent material in the light emitting layer of the organic electroluminescent element. The reason for using the triplet excited state is that when electrons and holes are recombined in the organic electroluminescent device, the ratio of singlet excitons and triplet excitons is 3: 1 due to the difference in spin multiplicity. This is because it is considered to achieve a luminous efficiency three times that of an element using fluorescence.

  In recent years, in order to improve the light emission efficiency and durability of organic electroluminescence devices using phosphorescence, improvements have been actively made on the host material of the organic light emitting layer and the material of the layer adjacent to the light emitting layer. For example, a light-emitting layer including a phosphorescent material may be formed using 4,4′-bis (N-carbazolyl) -1,1′-biphenyl (also referred to as “CBP”) or 1,3-bis (N-carbazolyl) benzene ( It is well known to use a carbazole derivative typified by “m-CP”) as a host material. However, it is still difficult to say that it has sufficient performance, and further improvements in efficiency and durability are desired (see, for example, Patent Documents 2 and 3).

Furthermore, a technique in which a compound having a fluorenyl skeleton is contained in a light emitting layer of an organic electroluminescent element is also known (see, for example, Patent Document 4).
Appl.Phys.Lett., 51,913 (1987) J.Appl.Phys., 65,3610 (1989) Appl.Phys.Lett., 70,1665 (1997) Jpn.J.Appl.Phys., 34, L824 (1995) Appl.Phys.Lett., 74,442 (1999) Appl.Phys.Lett., 75,4 (1999) Japanese Unexamined Patent Publication No. 63-264692 International Publication No. 03/80760 Pamphlet WO04 / 74399 pamphlet JP 2004-277368 A

  An object of the present invention is to improve the luminous efficiency and durability of an “organic electroluminescent device using a phosphorescent material” containing a phosphorescent material in a light emitting layer.

  In the “organic electroluminescent device using a phosphorescent light emitting material” containing a phosphorescent light emitting material in the light emitting layer, the inventor includes a specific compound as a host compound contained in the light emitting layer, or an anode of the light emitting layer. It has been found that when it is contained in the hole injection transport layer adjacent to the side, the luminous efficiency and durability of the organic electroluminescence device are improved.

That is, this invention relates to the organic electroluminescent element shown below.
[1] An organic electroluminescent device comprising a functional layer including a light emitting layer sandwiched between a pair of electrodes,
The light emitting layer contains a phosphorescent material;
Any one of the functional layers is an organic electroluminescence device containing at least one fluorene compound represented by the general formula (1).

In equation (1),
R _{1 to} R ₆ each independently represent a substituent, and R _{1 to} R ₆ may form a ring together with adjacent groups,
n _{1 to} n ₆ represent 0 or an integer of 1 to 3,
A and B represent a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, but A and B are not the same group, and n is 1 or 2 Represents.
However, the case where both A and B are aryl groups is excluded.

  [2] The organic electroluminescence device according to [1], wherein the layer containing the compound represented by the general formula (1) is a light emitting layer, a hole injection transport layer, or an electron injection transport layer.

  According to the present invention, it is possible to provide an organic electroluminescent element using a phosphorescent material having excellent luminous efficiency and durability.

  The organic electroluminescent element of the present invention has a pair of electrodes, and a functional layer having at least a light emitting layer is sandwiched between the pair of electrodes. The light emitting layer contains a phosphorescent material. The functional layer sandwiched between the pair of electrodes includes a charge injection transport layer according to a hole injection function and a hole transport function, and an electron injection function and an electron transport function of the compound included in the light emitting layer. Can be. The charge injection transport layer is a hole injection transport layer containing a hole injection component (arranged on the anode side of the light emitting layer) or an electron injection transport layer containing an electron injection transport component (on the cathode side of the light emitting layer). Arranged).

When the hole injection function, hole transport function, electron injection function, and electron transport function of the compound contained in the light emitting layer are high, a single-layer device (no electron injection transport layer) having only the light emitting layer may be used. it can. In the single-layer device, the light emitting layer has a function of a hole injection transport layer and / or an electron injection transport layer.
Moreover, when the hole injection function and hole transport function of the compound contained in the light emitting layer are not sufficient, it is preferable to use a two-layer element in which a hole injection transport layer is provided on the anode side of the light emitting layer. On the other hand, when the electron injection function and the electron transport function of the compound contained in the light emitting layer are not sufficient, a two-layer device in which an electron injection transport layer is provided on the cathode side of the light emitting layer can be obtained. Of course, a three-layered device in which the light emitting layer is sandwiched between a hole injection transport layer and an electron injection transport layer can also be used.

  In addition, each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single layer structure or a multilayer structure. Each of the hole injection / transport layer and the electron injection / transport layer may have a layer having an injection function and a layer having a transport function.

More specifically, examples of the structure of the organic light emitting device of the present invention are shown in FIGS. 1 to 8, but are not particularly limited thereto.
FIG. 1 shows an element (EL-1) including a substrate 1 / anode 2 / hole injection / transport layer 3 / light emitting layer 4 / electron injection / transport layer 5 / cathode 6 and a power source 7; FIG. 1 / anode 2 / hole injection transport layer 3 / light emitting layer 4 / cathode 6 and an element (EL-2) including a power source 7; FIG. 3 shows a substrate 1 / anode 2 / light emitting layer 4 / electron injection transport. Layer 5 / cathode 6 and element (EL-3) including power source 7; FIG. 4 shows substrate 1 / anode 2 / light emitting layer 4 / cathode type 6 and element (EL-4) including power source 7. Indicated.

  FIG. 5A shows an element (EL-5A) including a substrate 1 / anode 2 / hole injection layer 3 ′ / hole transport layer 3 ″ / light emitting layer 4 / electron injection transport layer 5 / cathode 6 and a power source 7. Indicated.

  On the other hand, FIG. 5B includes substrate 1 / anode 2 / hole injection transport layer 3 / light emitting layer 4 / hole blocking layer (electron transport layer) 5 ′ / electron injection transport layer 5 / cathode 6 and power source 7. An element (EL-5B) is shown.

  5C shows substrate 1 / anode 2 / hole injection layer 3 ′ / hole transport layer 3 ″ / light emitting layer 4 / hole blocking layer (electron transport layer) 5 ′ / electron injection transport layer 5 / cathode. 6 and an element (EL-5C) including a power source 7 is shown.

  6 to 8 show an element similar to EL-4. That is, FIG. 6 shows an element (EL-6) of a type in which a light emitting layer in which a hole injecting and transporting component 3a, a light emitting component 4a, and an electron injecting component 5a are mixed is sandwiched between a pair of electrodes; FIG. 7 shows a device (EL-7) of a type in which a light emitting layer obtained by mixing a hole injecting and transporting component 3a and a light emitting component 4a is sandwiched between a pair of electrodes; As shown, a light emitting layer (EL-8) in which a light emitting layer in which a light emitting component 4a and an electron injecting and transporting component 5a are mixed is sandwiched between a pair of electrodes is shown.

  Preferred element configurations of the organic electroluminescent element of the present invention are (EL-1) type element, (EL-2) type element, (EL-3) type element, (EL-5A) type element, (EL-5B). Type element, (EL-5C) type element, (EL-6) type element or (EL-7) type element, more preferably (EL-1) type element, (EL-2) type element, ( EL-5A) type element, (EL-5B) type element, (EL-5C) type element or (EL-7) type element.

  Of course, the element structure of the organic electroluminescent element of the present invention is not limited thereto. In each type of element, a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers may be provided. In each type of device, a mixed layer of a light emitting component and a hole injecting and transporting component may be provided between the hole injecting and transporting layer and the light emitting layer, and between the electron injecting and transporting layer and the light emitting layer. A mixed layer of a light emitting component and an electron injecting and transporting component may be provided.

Phosphorescent material The light emitting layer of the organic light emitting device of the present invention contains a phosphorescent material. The phosphorescent light emitting material preferably acts as a dopant material (or guest material) in the light emitting layer. The phosphorescent materials contained in the light emitting layer may be used singly or in combination of two or more. The phosphorescent material is not particularly limited but is preferably a transition metal complex. Examples of the transition metal complex include compounds represented by the following general formula (a-1) or general formula (a-2).

M ₁ in the general formula (a-1) represents an m-valent metal atom, and preferably represents ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, or gold.

A ₁ in the general formula (a-1) represents an atomic group for forming a 5-membered or 6-membered nitrogen-containing heterocycle. The formed nitrogen-containing heterocycle may have a substituent. Preferable examples of the nitrogen-containing heterocyclic ring include pyridyl, pyrimidyl, pyrazine, triazine, benzothiazole, benzoxazole, benzimidazole, quinolyl, isoquinolyl, quinoxaline, phenanthrylene and the like.

A ₂ in the general formula (a-1) represents an atomic group for forming a 5-membered or 6-membered cyclic structure. The formed cyclic structure is an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent. Preferable examples of the aromatic hydrocarbon ring or aromatic heterocyclic ring include phenyl, biphenyl, naphthyl, anthryl, thienyl, pyridyl, quinolyl, isoquinolyl and the like.

Examples of the substituent of A ₁ or A ₂ in the general formula (a-1) include a halogen atom such as a fluorine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; a vinyl group and an allyl group. C2-C6 alkenyl group such as methoxycarbonyl group and ethoxycarbonyl group; C2-C6 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; C1-C6 alkoxy group such as methoxy group and ethoxy group; Phenoxy group and benzyl Aryloxy groups such as oxy groups; dialkylamine groups such as dimethylamino groups and diethylamino groups; acyl groups such as acetyl groups; haloalkyl groups such as trifluoromethyl groups; cyano groups and the like.

L and L ′ represent an atom capable of coordinating to M ₁ , and a dotted line connecting L and L ′ represents that a bond may be formed or separated. N _d represents an integer of 1 to m.

On the other hand, in General Formula (a-2), V _{1 to} V ₈ represent a hydrogen atom, an alkyl group, or a substituent selected from an aryl group; Y _{1 to} Y ₄ represent CV ₉ (V ₉ Represents a hydrogen atom, an alkyl group, or an aryl group), or represents a nitrogen atom; M ₂ represents a metal atom.

  Specific examples of the phosphorescent material represented by the general formula (a-1) or the general formula (a-2) are shown below, but are not limited to the following compounds.

  When the light emitting layer containing a phosphorescent material contains a compound represented by the general formula (1) and / or a compound having a light emitting function other than the compound represented by the general formula (1) as a host compound, phosphorescent light emission The content of the material is preferably 0.001 to 40% by weight, more preferably 0.01 to 30% by weight, and more preferably 0.1 to 20% by weight with respect to the host compound. Further preferred.

  The content of the compound having a light emitting function other than the general formula (1) in the light emitting layer is preferably 0.001 to 40% by weight with respect to the compound represented by the general formula (1). It is more preferably ˜30% by weight, and further preferably 0.1˜20% by weight.

Compound represented by general formula (1) (host material)
The organic electroluminescent element of this invention contains the compound represented by General formula (1) in at least any one layer of the functional layer sandwiched between a pair of electrodes. The compound represented by the general formula (1) is preferably contained in the hole injecting and transporting layer and / or the light emitting layer, and more preferably contained in the light emitting layer. The compound represented by the general formula (1) contained in the light emitting layer preferably acts as a host material.

_R 1 to R ₆ in the formula (1) each independently represent a substituent, _n 1 ~n ₆ in the formula (1) represents an integer of 0 or 1-3. R _{1 to} R ₆ may form a ring together with adjacent groups.
A and B in Formula (1) represent a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. However, A and B are not the same group. Furthermore, when both A and B are aryl groups, it is excluded.
N in Formula (1) represents 1 or 2.

  That is, the fluorene compound represented by the general formula (1) has the following two types of structures (1-A) or (1-B) depending on the value of n. ) Structure (n = 1).

R _{1 to} R ₆ , n _{1 to} n ₆ , A and B in formula (1-A) or formula (1-B) are defined in the same manner as in general formula (1).

R _{1 to} R ₆ in the compound represented by the general formula (1) each independently represent a substituent.
The substituents represented by R _{1 to} R ₆ are a hydrogen atom; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted amino group; an ester group; a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; A linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms; a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms; a substituted or unsubstituted aralkyloxy group having 7 to 20 carbon atoms; 4 to 20 carbon atoms Or a substituted or unsubstituted aryloxy group having 4 to 20 carbon atoms.
The substituent represented by R _{1 to} R ₆ is a hydrogen atom; a halogen atom; a cyano group; a nitro group; a substituted or unsubstituted amino group; a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms; -8 linear, branched or cyclic alkoxy group; a substituted or unsubstituted aralkyl group having 7 to 16 carbon atoms; a substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms; a substituted or unsubstituted aralkyloxy group having 4 to 16 carbon atoms; More preferably, it is an unsubstituted aryl group; or a substituted or unsubstituted aryloxy group having 4 to 16 carbon atoms.

R _{1 to} R ₆ may each form a ring together with adjacent groups.

Examples of the halogen atom represented by R _{1 to} R ₆ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the amino group of R _{1 to} R ₆ include (unsubstituted) amino group, N-methylamino group, N-ethylamino group, Nn-propylamino group, N-iso-propylamino group, N -n-butylamino group, N-iso-butylamino group, N-sec-butylamino group, N-tert-butylamino group, Nn-pentylamino group, N-cyclopentylamino group, Nn-hexyl Amino group, N-cyclohexylamino group, N-benzylamino group, N-phenethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, N- ( 4-phenylphenyl) amino group, N- (3-phenylphenyl) amino group, N- (2-phenylphenyl) amino group, N- (4-methylphenyl) amino group, N- (2-methylphenyl) amino Group, N- (2-anthranyl) amino group, N- (9-anthranyl) Amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-di-iso-propylamino group, N, N-di-n- Butylamino group, N, N-di-iso-butylamino group, N, N-di-sec-butylamino group, N, N-di-n-pentylamino group, N, N-dicyclopentylamino group, N , N-dicyclohexylamino group, N, N-dibenzylamino group, N, N-diphenethylamino group, N-methyl-N-ethylamino group, N-methyl-Nn-propylamino group, N-methyl -N-iso-propylamino group, N-methyl-Nn-butylamino group, N-methyl-N-tert-butylamino group, N-methyl-N-cyclopentylamino group, N-methyl-N-cyclohexyl Amino group, N-methyl-N-benzylamino group, N-methyl-N-phenethylamino group, N-ethyl-N-tert-butylamino group, N-ethyl Ru-N-cyclohexylamino group, N-ethyl-N-benzylamino group, N-iso-propyl-N-cyclopentylamino group, N-iso-propyl-N-cyclohexylamino group, N-iso-propyl-N- Benzylamino group, N-tert-butyl-N-cyclohexylamino group, N-tert-butyl-N-benzylamino group, N-cyclopentyl-N-benzylamino group, N-cyclohexyl-N-benzylamino group, N, N-diphenylamino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N, N-di (4-phenylphenyl) amino group, N, N- (4-methylphenyl) amino group, N, N-di (3-methylphenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group N-phenyl-N- (4-phenylphenyl) amino group, N-phenyl-N— 4-methylphenyl) amino group, and the like N-(1-naphthyl)-N-(4'-phenylphenyl) amino group.

The ester group of R _{1 to} R ₆ may be either an oxycarbonyl group or a carbonyloxy group. Examples of oxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, tert-butyloxycarbonyl group N-pentyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, benzyloxycarbonyl group, phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group and the like. Examples of carbonyloxy groups include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyloxy group, cyclohexylcarbonyloxy group, benzylcarbonyloxy group, phenylcarbonyl An oxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, and the like are included.

Among the alkyl groups of R _{1 to} R ₆ , specific examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group Group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n -Tetradecyl group, n-pen Decyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octylnonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n-eicosyl group, n-docosyl group, n-tetracosyl group, cyclohexylmethyl group, (1-isopropylcyclohexyl) methyl group, 2-cyclohexylethyl group, bornel group, isobornel group, 1-norbornyl group, 2-norbornanemethyl group, 1-bicyclo [2.2.2 ] Octyl group, 1-adamantyl group, 3-noradamantyl group, 1-adamantylmethyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 3-methylcyclohexyl group, 2- Methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethyl group Rucyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 2, 6-diisopropylcyclohexyl group, 4-tert-butylcyclohexyl group, 3-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 2-phenylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclo Tetradecyl group and the like are included.

Specific examples of the alkyl group having an oxy group among the alkyl groups of R _{1 to} R ₆ include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, (2-ethylbutyloxy ) Methyl group, n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxy Ethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group Group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxy Til group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (n -Pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2'-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) Propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4 -Ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4 -n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, tetrahydrofurfuryl group, 2- (2′-methoxyethoxy) ethyl group, 2- (2 ′ -Ethoxyethoxy) ethyl group, 2- (2'-n-butoxyethoxy) ethyl group, 3- (2'-ethoxyethoxy) propyl group, 2-allyloxyethyl 2- (4′-pentenyloxy) ethyl group, 3-allyloxypropyl group, 3- (2′-hexenyloxy) propyl group, 3- (2′-heptenyloxy) propyl group, 3- (1′-cyclo Hexenyloxy) propyl group, 4-allyloxybutyl group, benzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4'-methylbenzyloxy) ethyl group, 2- (2 ' -Methylbenzyloxy) ethyl group, 2- (4'-fluorobenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4'-methoxybenzyloxy) ) Propyl group, 4-benzyloxybutyl group, 2- (benzyloxymethoxy) ethyl group, 2- (4′-methylbenzyloxymethoxy) ethyl group, phenyloxymethyl group, 4-methyl Tylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group Group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 2- (2'-naphthyloxy) ethyl group, 3-phenyl Oxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxybutyl group, 4- (2′-ethylphenyloxy) butyl group, 5- (4′-tert) -Butylphenyloxy) pentyl group, 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-chlorophenyloxy) decyl group, 2- (2 '-Phenyloxyethoxy) ethyl group, 3- (2'-phenyloxyethoxy) propyl group, 4- (2'-phenyloxyethoxy) butyl group and the like are included.

Examples of the alkyl group having a thio group among the alkyl groups of R _{1 to} R ₆ include an n-butylthiomethyl group, an n-hexylthiomethyl group, a 2-methylthioethyl group, a 2-ethylthioethyl group, 2 -n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octylthioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3- n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group, 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group Group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, 2- (2′-methoxyethylthio) ethyl group, 4- (3′-ethoxypropylthio) butyl group, 2- (2′-ethyl group) Thioethylthio) ethyl group, 2-ali Ruthioethyl group, 2-benzylthioethyl group, 3- (4′-methylbenzylthio) propyl group, 4-benzylthiobutyl group, 2- (2′-benzyloxyethylthio) ethyl group, 3- (3′- Benzylthiopropylthio) propyl group, 2-phenylthioethyl group, 2- (4′-methoxyphenylthio) ethyl group, 2- (2′-phenyloxyethylthio) ethyl group, 3- (2′-phenylthio) An ethylthio) propyl group and the like.

Examples of the alkyl group having a hydroxyl group among the alkyl groups of R _{1 to} R ₆ include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. Group, 6-hydroxyhexyl group, 5-hydroxyheptyl group, 8-hydroxyoctyl group, 10-hydroxydecyl group, 12-hydroxydodecyl group, 2-hydroxycyclohexyl group and the like.

Specific examples of the alkoxy group of R _{1 to} R ₆ include a linear, branched or cyclic alkoxy group derived from the above alkyl group.

Specific examples of the aralkyl group represented by R _{1 to} R ₆ include (unsubstituted) benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, β-methylphenethyl group, α , α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-ethylbenzyl group, 2-ethylbenzyl group 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 2-tert-butylbenzyl group, 4-tert-pentylbenzyl group, 4-cyclohexylbenzyl group, 4-n-octylbenzyl group, 4-tert-octyl group Benzyl group, 4-allylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4- (4′-methylphenyl) benzyl group, 4-methoxybenzyl group 2-methoxybenzyl group, 2-ethoxybenzyl group, 4-n-butoxybenzyl group, 4-n-heptyloxybenzyl group, 4-n-decyloxybenzyl group, 4-n-tetradecyloxybenzyl group, 4- n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-isobutoxymethylbenzyl group, 4-allyloxybenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxy Benzyl group, 4-phenethyloxybenzyl group, 4-phenyloxybenzyl group, 3-phenyloxybenzyl group, 4-hydroxybenzyl group, 3-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-methoxybenzyl Group, 4-fluorobenzyl group, 2-fluorobenzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2 -Chlorobenzyl group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like are included.

Specific examples of the aralkyloxy group of R _{1 to} R ₆ are, for example, a substituted or unsubstituted aralkyloxy group derived from the aralkyl group.

The first example of the aryl group R ₁ to R ₆ is a phenyl group having an unsubstituted phenyl group and a substituted group.

Examples of the phenyl group having an alkyl group among the aryl groups of R _{1 to} R ₆ include a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, and a 3-ethylphenyl group. Group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert -Pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4- n-nonyl Phenyl group, 4-n-decylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecylphenyl group, 4-cyclopentylphenyl group 4-cyclohexylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, 4- (4′-methylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 2,3-dimethyl Phenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethyl Phenyl group, 3,4,5-trimethylphenyl group, 2,4-diethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-diethylphenyl group Group, 2,6-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 3,5-di-tert -Butylphenyl group, 2,4-dineopentylphenyl group, 2,5-di-tert-pentylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2 -Methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 2,3,5,6-tetramethylphenyl group and the like are included.

Examples of the phenyl group having an alkoxy group among the aryl groups of R _{1 to} R ₆ include 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 2-ethoxyphenyl group. Group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-isobutoxyphenyl group, 2-sec- Butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2 '-Ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2,3-dimethoxyphenyl group 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group Group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5- Etc. Li-methoxyphenyl group.

Among the aryl groups of R _{1 to} R ₆ , examples of the phenyl group having a halogen atom include a 4-fluorophenyl group, a 3-fluorophenyl group, a 2-fluorophenyl group, a 4-chlorophenyl group, a 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3 , 4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,3,6-tribromophenyl group, 3,4,5-trifluorophenyl Enyl group, 2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 4-fluoro-2-methyl Phenyl group, 5-fluoro-2-methylphenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 3-chloro-2-methyl Phenyl group, 4-chloro-2-methylphenyl group, 4-chloro-3-methylphenyl group, 2-chloro-4,6-dimethylphenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-6 -Methoxyphenyl group, 3-fluoro-4-ethoxyphenyl group, 5-chloro-2-methoxyphenyl group, 6-chloro-3-methoxyphenyl group, 5-chloro-2,4-dimethoxyphenyl group, 2-chloro -4-nitrophenyl group, 4-chloro-2-nitrate Phenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 4-trifluoromethyloxyphenyl group, etc. included.

Examples of the phenyl group having an alkenyl group, an aralkyl group, or an aryl group among the aryl groups of R _{1 to} R ₆ include a 4-allylphenyl group, a 2-allylphenyl group, a 2-isopropenylphenyl group, 4- Benzylphenyl group, 2-benzylphenyl group, 4- (4′-methylbenzyl) phenyl group, 4-cumylphenyl group, 4- (4′-methoxycumyl) phenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-ethylphenyl) phenyl group, 4- (4′-isopropylphenyl) phenyl group, 4- (4′-tert- Butylphenyl) phenyl group, 4- (4′-n-hexylphenyl) phenyl group, 4- (4′-n-octylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4- (4 '-Etoki Cyphenyl) phenyl group, 4- (4′-n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4- (4′-fluorophenyl) phenyl group, 4- (4′-chlorophenyl) ) Phenyl group, 3-methyl-4-phenyl group, 2-methoxy-5-phenylphenyl group, 3-methoxy-4-phenylphenyl group and the like.

  Examples of the phenyl group having an alkoxyalkyl group (including an alkoxyalkyloxy group) include a 4-methoxymethylphenyl group, a 4-ethoxymethylphenyl group, a 4-n-butoxymethylphenyl group, a 3-methoxymethylphenyl group, 4- (2′-methoxyethyl) phenyl group, 4- (2′-ethoxyethyloxy) phenyl group, 4- (2′-n-butoxyethyloxy) phenyl group, 4- (3′-ethoxypropyloxy) A phenyl group and the like are included.

  Examples of phenyl groups having an alkenyloxy group (including alkenyloxyalkyl groups and alkenyloxyalkyloxy groups) include 4-vinyloxyphenyl group, 4-allyloxyphenyl group, 3-allyloxyphenyl group, 4- (4'-pentenyloxy) phenyl group, 4-allyloxymethylphenyl group, 4- (2'-allyloxyethyloxy) phenyl group and the like are included.

  Examples of phenyl groups having an aralkyloxy group (including aralkyloxyalkyl groups and aralkyloxyalkyloxy groups) include 4-benzyloxyphenyl group, 2-benzyloxyphenyl group, 4-phenethyloxyphenyl group, 4- (4′-chlorobenzyloxy) phenyl group, 4- (4′-methylbenzyloxy) phenyl group, 4- (4′-methoxybenzyloxy) phenyl group, 4- (3′-ethoxybenzyloxy) phenyl group, 4- (benzyloxymethyl) phenyl group and 4- (2′-benzyloxyethyloxy) phenyl group are included.

  Examples of a phenyl group having an aryloxy group (including an aryloxyalkyl group and an aryloxyalkyloxy group) include 4-phenyloxyphenyl group, 3-phenyloxyphenyl group, 2-phenyloxyphenyl group, 4- (4′-methylphenyloxy) phenyl group, 4- (4′-methoxyphenyloxy) phenyl group, 4- (4′-chlorophenyloxy) phenyl group, 4-phenyloxymethylphenyl group, 4- (2′- Phenyloxyethyloxy) phenyl group, 4- [2 ′-(4′-methylphenyloxy) ethyloxy] phenyl group, 4- [2 ′-(4′-methoxyphenyloxy) ethyloxy] phenyl group, 4- [2 '-(4'-chlorophenyloxy) ethyloxy] phenyl group and the like are included.

  Examples of the phenyl group having an alkylcarbonyl group, an alkenylcarbonyl group, an aralkylcarbonyl group, or an arylcarbonyl group include a 4-acetylphenyl group, a 3-acetylphenyl group, a 2-acetylphenyl group, a 4-ethylcarbonylphenyl group, 2-ethylcarbonylphenyl group, 4-n-butylcarbonylphenyl group, 4-n-hexylcarbonylphenyl group, 4-n-octylcarbonylphenyl group, 4-cyclohexylcarbonylphenyl group, 4-allylcarbonylphenyl group, 4- Benzylcarbonylphenyl group, 4- (4′-methylbenzyl) carbonylphenyl group, 4-phenylcarbonylphenyl group, 4- (4′-methylphenyl) carbonylphenyl group, 4- (4′-chlorophenyl) carbonylphenyl group, etc. Is included.

  Examples of the phenyl group having an oxycarbonyl group include 4-methoxycarbonylphenyl group, 2-methoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-n-propoxycarbonylphenyl group, 4 -n-butoxycarbonylphenyl group, 4-n-hexyloxycarbonylphenyl group, 4-n-decyloxycarbonylphenyl group, 4-cyclohexyloxycarbonylphenyl group, 4-allyloxycarbonylphenyl group, 4-benzyloxycarbonylphenyl group 4- (4′-chlorobenzyl) oxycarbonylphenyl group, 4-phenethyloxycarbonylphenyl group, 4-phenyloxycarbonylphenyl group, 4- (4′-ethylphenyl) oxycarbonylphenyl group, 4- (4 '-Chlorophenyl) oxyca Bonirufeniru group, and the like 4- (4'-ethoxyphenyl) oxycarbonyl phenyl group.

  Examples of the phenyl group having a carbonyloxy group include 4-acetyloxyphenyl group, 3-acetyloxyphenyl group, 2-acetyloxyphenyl group, 4-ethylcarbonyloxyphenyl group, 2-ethylcarbonyloxyphenyl group, 4 -n-propylcarbonyloxyphenyl group, 4-n-pentylcarbonyloxyphenyl group, 4-n-octylcarbonyloxyphenyl group, 4-cyclohexylcarbonyloxyphenyl group, 3-cyclohexylcarbonyloxyphenyl group, 4-allylcarbonyloxy Phenyl group, 4-benzylcarbonyloxyphenyl group, 4-phenethylcarbonyloxyphenyl group, 4-phenylcarbonyloxyphenyl group, 4- (4′-methylphenyl) carbonyloxyphenyl group, 4- (2′-methylphenyl) Carbonyloxy Eniru group, 4- (4'-chlorophenyl) carbonyloxy phenyl group, and the like 4- (2'-chlorophenyl) carbonyloxy phenyl group.

  Examples of the phenyl group having a thio group include 4-methylthiophenyl group, 2-methylthiophenyl group, 2-ethylthiophenyl group, 3-ethylthiophenyl group, 4-n-propylthiophenyl group, 2-isopropylthio group. Phenyl group, 4-n-butylthiophenyl group, 2-isobutylthiophenyl group, 2-neopentylphenyl group, 4-n-hexylthiophenyl group, 4-n-octylthiophenyl group, 4-cyclohexylthiophenyl group 4-benzylthiophenyl group, 3-benzylthiophenyl group, 2-benzylthiophenyl group, 4- (4′-chlorobenzylthio) phenyl group, 4-phenylthiophenyl group, 3-phenylthiophenyl group, 2 4-phenylthiophenyl group, 4- (4′-methylphenylthio) phenyl group, 4- (3′-methylphenylthio) phenyl group, 4- (4′-methoxyphene) Nylthio) phenyl group, 4- (4′-chlorophenylthio) phenyl group and the like are included.

  Examples of phenyl groups having an amino group include 4-aminophenyl group, 3-aminophenyl group, 2-aminophenyl group, 4- (N-methylamino) phenyl group, 3- (N-methylamino) phenyl group 4- (N-ethylamino) phenyl group, 2- (N-isopropylamino) phenyl group, 4- (Nn-butylamino) phenyl group, 2- (Nn-butylamino) phenyl group, 4 -(Nn-octylamino) phenyl group, 4- (Nn-dodecylamino) phenyl group, 4- (N-benzylamino) phenyl group, 4- (N-phenylamino) phenyl group, 2- ( N-phenylamino) phenyl group, 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 2- (N , N-dimethylamino) phenyl group, 2- (N, N-diethylamino) ) Phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n-hexylamino) phenyl group, 4- (N-cyclohexyl-N-methylamino) Phenyl group, 4- (N, N-diethylamino) -1-naphthyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4- [N -Phenyl-N- (4-methylphenyl) amino] phenyl group, 4- [N, N-di (3'-methylphenyl) amino] phenyl group, 4- [N, N-di (4'-methylphenyl) ) Amino] phenyl group, 4- [N, N-di (4′-methoxyphenyl) amino] phenyl group, 2- (N, N-diphenylamino) phenyl group and the like.

  Examples of other phenyl groups include 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, 4-formylphenyl group, 3-formylphenyl group, 2-formyl Phenyl group, 4-pyrrolidinophenyl group, 4-piperidinophenyl group, 4-morpholinophenyl group, 4- (N-ethylpiperazino) phenyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 2-hydroxy A phenyl group, 4-methyl-3-hydroxyphenyl group, 6-methyl-3-hydroxyphenyl group, 4-cyanophenyl group, 2-cyanophenyl group and the like are included.

A second example of the aryl group of R _{1 to} R ₆ is an unsubstituted naphthyl group and a naphthyl group having a substituent. Examples of naphthyl groups include 1-naphthyl group, 2-naphthyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 1,2,3,4-tetrahydro-5-naphthyl group. 1,2,3,4-tetrahydro-6-naphthyl group, 4-allyloxy-1-naphthyl group, 4-benzyloxy-1-naphthyl group, 5- (4′-methylbenzyloxy) -1-naphthyl group Group, 6-benzyloxy-2-naphthyl group, 6- (4′-methylbenzyloxy) -2-naphthyl group, 7-benzyloxy-2-naphthyl group, 2-methoxy-1-naphthyl group, 4-methoxy -1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n- Hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 4-chloro-1-naphthyl group 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group, 4-phenyloxy-1-naphthyl group, 6-phenyloxy-2-naphthyl group, 7-phenyloxy-2-naphthyl group, 4-acetyl-1-naphthyl group, 6-acetyl-2-naphthyl group, 6-n-butylcarbonyl-2-naphthyl group, 4-phenylcarbonyl-1-naphthyl group, 4-ethoxycarbonyl-1-naphthyl group, 6-methoxycarbonyl-2-naphthyl group, 6-n-butoxycarbonyl-2-naphthyl group, 6-phenyloxycarbonyl-2- Naphthyl group, 6-benzyloxycarbonyl-2-naphthyl group, 4-acetyloxy-1-naphthyl group, 4-n-butylcarbonyloxy-1-naphthyl group, 5-acetyloxy-1-naphthyl group, 6-ethyl Carbonyloxy-2-naphthyl Group, 7-acetyloxy-2-naphthyl group, 6-benzylcarbonyloxy-2-naphthyl group, 4-phenylcarbonyloxy-1-naphthyl group, 6-phenylcarbonyloxy-2-naphthyl group, 7-phenylcarbonyloxy -2-naphthyl group, 2-ethylthio-1-naphthyl group, 4-methylthio-1-naphthyl group, 6-ethylthio-2-naphthyl group, 6-phenylthio-2-naphthyl group, 4-nitro-1-naphthyl group 4-formyl-1-naphthyl group, 1-formyl-2-naphthyl group, 4-pyrrolidino-1-naphthyl group, 2-hydroxy-1-naphthyl group, 8-hydroxy-1-naphthyl group, 4-hydroxy- 1-naphthyl group, 1-hydroxy-2-naphthyl group, 6-hydroxy-2-naphthyl group, 4-cyano-1-naphthyl group, 6-cyano-2-naphthyl group are included.

Other examples of the aryl group of R _{1 to} R ₆ include 2-anthracenyl group, 9-anthracenyl group, fluorenyl group, 4-quinolyl group, 5-pyridyl group, 4-pyridyl group, 3-pyridyl group, 2- Pyridyl group, 2-pyrimidyl group, 4-pyrimidine group, 5-pyrimidyl group, 2-pyridazinyl group, 2-pyrazinyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2- An oxazolyl group, 2-thiazolyl group, 2-benzothiophenyl group, 2-benzofuryl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzoimidazolyl group, 5-indanyl group are included.

Specific examples of the substituted or unsubstituted aryloxy group for R _{1 to} R ₆ are a substituted or unsubstituted aryloxy group derived from the above aryl group.

N < ₁ > -n < ₆ > in General formula (1) represents the integer of 0-3, respectively. When n _{1 to} n ₆ are 2 or more, each R _{1 to} R ₆ may be the same or different. n _{1 to} n ₆ are preferably 0 to 2, and more preferably 0 to 1.

  A and B in the fluorene compound represented by the general formula (1) represent a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

  A and B are substituted or unsubstituted linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 20 carbon atoms, and substituted groups having 4 to 20 carbon atoms. Or an unsubstituted aromatic heterocyclic group or an aralkyl group having 7 to 20 carbon atoms; a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or 6 carbon atoms; A substituted or unsubstituted aromatic hydrocarbon group having 15 to 15 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 4 to 15 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms. More preferred.

Specific examples of the alkyl group represented by A and B are the same as the specific examples of the linear, branched or cyclic alkyl group of R _{1 to} R ₆ , for example. Specific examples of the aryl group represented by A and B are the same as the specific examples of the substituted or unsubstituted aryl group of R _{1 to} R ₆ , for example. Specific examples of the aralkyl group represented by A and B are the same as, for example, specific examples of the substituted or unsubstituted aralkyl group of R _{1 to} R ₆ .

However, A and B are not the same group but different groups. The combination of A and B is preferably, for example, as shown below, but is not particularly limited.
1. A is a linear, branched or cyclic alkyl group, B is a combination of linear, branched or cyclic alkyl groups different from A 1-1. A is a linear or branched alkyl group, B is a cyclic alkyl Combination of groups 1-2. A is a cyclic alkyl group, B is a linear or branched alkyl group combination 1-3. A is a linear alkyl group, B is a branched alkyl group combination 1-4.A Is a branched alkyl group, B is a linear alkyl group combination 2. A is a linear, branched or cyclic alkyl group, B is a substituted or unsubstituted aryl group 3 A is a substituted or unsubstituted aryl group , B is a linear, branched or cyclic alkyl group combination 4. A is a linear, branched or cyclic alkyl group, B is a substituted or unsubstituted aralkyl group 5. A is a substituted or unsubstituted aralkyl group , B is a group of linear, branched or cyclic alkyl groups 6. A is a combination of a substituted or unsubstituted aralkyl group, B is a combination of a substituted or unsubstituted aryl group 7. A is a combination of a substituted or unsubstituted aryl group, B is a combination of a substituted or unsubstituted aralkyl group 8.A Is a substituted or unsubstituted aralkyl group, and B is a combination of a substituted or unsubstituted aralkyl group different from A

  Among the above combinations, a combination of 1, 1-1, 1-2, 2, 3, 4, 5, 6 or 7 is preferable, and 1-1, 1-2, 2, 3, 4 or 5 is more preferable. .

  In the compound represented by the general formula (1), n represents 1 or 2, preferably 1.

  Specific examples of the compound represented by the general formula (1) of the present invention include the following compounds (Chemical Formula 6 to Chemical Formula 40), but the present invention is limited to these specific examples. is not.

  The compound represented by General formula (1) can be manufactured with reference to Unexamined-Japanese-Patent No. 2004-277368. For example, it can be manufactured by the following steps. That is, the boronic acid derivative represented by the general formula (B) at 2 times mole or more is added to the compound represented by the general formula (A) with a base (for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide). Reaction in the presence of an inorganic base such as pyridine, triethylamine, etc.) and a palladium catalyst (for example, palladium / carbon, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium) A compound represented by the formula (1) can be produced.

R _{1 to} R ₆ , n _{1 to} n ₆ , A, B, and n in the above scheme are defined in the same manner as in general formula (1). X represents a leaving group such as a halogen atom or a trifluoromethanesulfonyloxy group.

  On the other hand, the compound represented by General formula (1) can be manufactured also by the process shown below. That is, a boronic acid derivative represented by the general formula (C) and a compound represented by the general formula (D) having a molar ratio of 2 times or more are converted into a base (for example, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate) , Inorganic bases such as sodium hydroxide and potassium hydroxide, organic bases such as pyridine and triethylamine), and palladium catalysts [eg, palladium / carbon, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium] By reacting in the presence, the compound represented by the general formula (1) can be produced.

R _{1 to} R ₆ , n _{1 to} n ₆ , A, B, and n in the above scheme are defined in the same manner as in general formula (1). X represents a leaving group such as a halogen atom or trifluoromethanesulfonyloxy group.

  As described above, the organic electroluminescent element has a pair of electrodes and a functional layer sandwiched between the electrode pairs. The functional layer includes at least a light emitting layer, and may further include a hole injection transport layer, an electron injection transport layer, and the like.

  For each component of the organic electroluminescent element, an (EL-1) type element having the substrate 1 / anode 2 / hole injection transport layer 3 / light emitting layer 4 / electron injection transport layer 5 / cathode 6 shown in FIG. Will be described with reference to FIG. In FIG. 1, reference numeral 7 denotes a power source.

  The organic electroluminescent element of the present invention is preferably supported on the substrate 1. The substrate is preferably transparent or translucent. Examples of the material of the substrate include glass such as soda lime glass and borosilicate glass, and transparent polymers such as polyester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethylmethacrylate, polypropylene, and polyethylene.

  The substrate may be a substrate made of a translucent plastic sheet, quartz, transparent ceramics, or a composite sheet combining these. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.

The electrode material of the anode 2 is preferably a metal, alloy or conductive compound having a relatively large work function. Examples of the electrode material of the anode 2 include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide, and ITO (indium). -Tin oxide (Indium Tin Oxide), polythiophene, polypyrrole, etc. are included. These electrode materials may be used alone or in combination.

  Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably set to several hundred Ω / □ or less, more preferably about 5 to 50 Ω / □. The thickness of the anode is generally about 5 to 1000 nm, preferably about 10 to 500 nm, although it depends on the material of the electrode material used.

  The anode 2 can be formed on the substrate by an electrode material such as a vapor deposition method or a sputtering method.

  The hole injection / transport layer 3 has a function of facilitating injection of holes from the anode and a function of transporting the injected holes. The hole injecting and transporting layer 3 of the electroluminescent element of the present invention contains a compound represented by the general formula (1) and / or another compound having a hole injecting and transporting function. Examples of compounds having other hole injecting and transporting functions include phthalocyanine derivatives, triarylamine derivatives, triarylmethane derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and its derivatives, polythiophene And derivatives thereof, poly-N-vinylcarbazole and the like. The compounds having a hole injecting and transporting function may be used alone or in combination.

  Specific examples of the compound having a hole injecting and transporting function other than the compound represented by the general formula (1) include triarylamine derivatives, polythiophene and derivatives thereof, and poly-N-vinylcarbazole and derivatives thereof.

  Examples of triarylamine derivatives include 4,4′-bis [N-phenyl-N- (4 ″ -methylphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl]. -N- (3 ″ -methylphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl-N- (3 ″ -methoxyphenyl) amino] -1,1′- Biphenyl, 4,4′-bis [N-phenyl-N- (1 ″ -naphthyl) amino] -1,1′-biphenyl, 3,3′-dimethyl-4,4′-bis [N-phenyl- N- (3 ″ -methylphenyl) amino] -1,1′-biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9 , 10-Bis [N- (4′-methylphenyl) -N- (4 ″ -n-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthate Lysine, 4-me Tyl-N, N-bis [4 ″, 4 ′ ″-bis [N ′, N′-di (4-methylphenyl) amino] biphenyl-4-yl] aniline, N, N′-bis [4 -(Diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,4-diamino Benzene, 5,5 ″ -bis [4- (bis [4-methylphenyl] amino] phenyl-2,2 ′: 5 ′, 2 ″ -terthiophene, 1,3,5-tris (diphenylamino) Benzene, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, 4,4 ′, 4 ″ -tris [N, N-bis (4 ′ ″-tert-butylbiphenyl-4 ′) '' '-Yl) amino] triphenylamine, 1,3,5-tris [N- (4'-diphenylamino] benzene and the like.

  When the compound represented by the general formula (1) and another compound having a hole injection function are used in combination, the content of the compound represented by the general formula (1) in the hole injection transport layer is 0.1 wt% or more, preferably 0.5 to 99.9 wt%, more preferably 3 to 97 wt%.

  The light emitting layer 4 is a layer containing a compound having a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons.

  The light emitting layer contains at least one of the above phosphorescent materials (compounds having a phosphorescent function). Furthermore, a light emitting layer contains either or both of the compound represented by General formula (1), or the compound which has light emission functions other than the compound represented by General formula (1). It is preferable that the light emitting layer of the organic electroluminescent element of this invention contains the compound represented by General formula (1).

  In the light emitting layer, the phosphorescent light emitting material functions as a dopant material (or guest material). On the other hand, a compound having a light emitting function other than the compound represented by the general formula (1) and / or the compound represented by the general formula (1) functions as a host material.

  Examples of compounds having a light emitting function other than the compound represented by the general formula (1) include triarylamine derivatives, organometallic complexes, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, and cinnamic acid esters. Derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof, polyfluorene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polybiphenylene vinylene and derivatives thereof, polyterphenylene vinylene and derivatives thereof, poly Examples include naphthylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and the like.

  The compound having a light emitting function other than the compound represented by the general formula (1) is preferably a triarylamine derivative or an organometallic complex. Examples of the triarylamine derivative include the compounds exemplified as the compound having a hole injecting and transporting function. Examples of organometallic agents include tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, zinc salt of 2- (2′-hydroxyphenyl) benzothiazole.

  When the light emitting layer of the organic electroluminescent element contains both an aromatic hydrocarbon compound represented by the general formula (1) and a compound having a light emitting function other than the compound represented by the general formula (1) The ratio of the compound represented by the general formula (1) to the total of both compounds is preferably 60 to 99.999% by weight.

  An electron injecting and transporting layer is formed on the cathode side of the light emitting layer of the organic electroluminescent device of the present invention. The electron injecting and transporting layer may be formed adjacent to the light emitting layer, or an electron transporting layer (hole blocking layer) may be formed between the light emitting layer and the electron injecting and transporting layer.

  The hole blocking layer efficiently accumulates holes injected into the light emitting layer in the light emitting layer. Thereby, the establishment of the recombination of holes and electrons is improved, and high efficiency of light emission is achieved. The hole blocking layer includes, for example, a phentroline derivative, a triazole derivative, bis (2-methylquinolinolato) (4-phenylphenolate) aluminum, and the like.

  The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating injection of electrons from the cathode and / or a function of transporting injected electrons.

  The electron injecting and transporting layer of the organic electroluminescence device of the present invention may contain the compound of the general formula (1) or may contain other compounds having an electron injecting and transporting function. Examples of other compounds having an electron injecting and transporting function include organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandi. Oxide derivatives and the like are included. The electron injecting and transporting layer may contain one type of compound having an electron injecting function, or may contain a plurality of types.

  Examples of organometallic complexes include organoaluminum complexes such as tris (8-quinolinolato) aluminum, organoberyllium complexes such as bis (10-benzo [h] quinolinolato) beryllium, beryllium salts of 5-hydroxyflavone, 5-hydroxyflavone Of aluminum salts.

  The electron injecting and transporting layer preferably contains a compound represented by the general formula (1) or an organoaluminum complex. Here, the organoaluminum complex is an organoaluminum complex having a substituted or unsubstituted 8-quinolinolato ligand. Examples of the organoaluminum complex having a substituted or unsubstituted 8-quinolylate ligand include compounds represented by general formula (a) to general formula (c).

(Q) ₃ -Al (a)
(Q in formula (a) represents a substituted or unsubstituted 8-quinolinolato ligand)
(Q) ₂ -Al-OL- (b)
(Q in the formula (b) represents a substituted or unsubstituted 8-quinolinolate ligand, OL ′ represents a phenolate ligand, and L ′ represents a hydrocarbon having 6 to 24 carbon atoms having a phenyl group. Represents a group)
(Q) ₂ -Al-O-Al- (Q) ₂ (c)
(Q in the formula (c) represents a substituted or unsubstituted 8-quinolinolato ligand)

  Specific examples of organoaluminum complexes having a substituted or unsubstituted 8-quinolinolato ligand contained in the electron injecting and transporting layer include tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris. (5-methyl-8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) ) Aluminum, bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3- Methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-methyl) Enolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8- Quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum, bis (2-methyl) -8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinate) Lat) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2, 4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (1-naphtholate) ) Aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2,4-dimethyl-8) -Quinolinolate) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) a Minium, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis ( 2-Methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-sia) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum and the like are included.

  The electrode material of the cathode 6 is preferably a metal, alloy or conductive compound having a relatively small work function. Examples of the electrode material of the cathode 6 include lithium, lithium-indium alloy, lithium fluoride, organic acid lithium salt (lithium benzoate, lithium acetate, etc.), sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy. , Magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, aluminum, aluminum-lithium alloy, aluminum-calcium alloy, aluminum-magnesium alloy, graphite thin and the like. These electrode materials may be used alone or in combination.

  The cathode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the cathode is preferably several hundred Ω / □ or less. Although the thickness of a cathode is based also on the electrode material to be used, it is 5-1000 nm normally, Preferably it is 10-500 nm. In order to efficiently extract light emitted from the organic electroluminescence device, at least one of the anode and the cathode is preferably transparent or translucent. It is preferable to set the electrode material and the electrode thickness so that the transmittance of the emitted light of the anode or the cathode is 70% or more.

  The cathode can be produced by forming a layer of these electrode materials on the electron injecting and transporting layer by vapor deposition, sputtering, ion vapor deposition, ion plating, cluster ion beam, or the like.

  The hole injecting and transporting layer, the light emitting layer or the electron injecting and transporting layer can be formed by vacuum deposition, ionization deposition, solution coating (for example, spin coating, casting, dip coating, bar coating, roll coating, Langmuir However, the present invention is not particularly limited to these means.

When forming each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer by a vacuum deposition method, the conditions for vacuum deposition are usually a boat temperature (deposition source temperature) under a vacuum of about 10 ⁻³ Pa or less. ) Is preferably about 50 to 500 ° C., the substrate temperature is about −50 to 300 ° C., and the deposition rate is about 0.005 to 50 nm / sec, but is not particularly limited.

  When forming each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer by a vacuum deposition method, it is preferable to form each layer continuously under vacuum. It becomes possible to manufacture an organic electroluminescent element excellent in various characteristics by forming continuously. When each layer such as a hole injection transport layer, a light emitting layer, an electron injection transport layer, etc. is formed by vacuum deposition using a plurality of compounds, each boat containing the compounds is individually temperature controlled and deposited. Is preferred.

  When each layer is formed by a solution coating method, the components for forming each layer and, if necessary, a binder resin or the like are dissolved or dispersed in a solvent to obtain a coating solution.

  The solvent may be an organic solvent or water. Examples of organic solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; dichloromethane, chloroform, tetra Halogenated hydrocarbon solvents such as chloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and ethyl lactate; methanol, propanol, butanol, pen Alcohol solvents such as butanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; dibutyl ether, tetrahydrofuran, Ether solvents such as dioxane, dimethoxyethane, anisole; N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, etc. A polar solvent is included. A solvent may be used independently and may be used together.

  In order to disperse the components of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer in the solvent, use a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, or the like to disperse each component into fine particles. be able to.

  Examples of the binder resin contained in the coating solution used in the solution coating method include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, polymethyl acrylate, polyether, polycarbonate, polyamide, Polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylene vinylene and its derivatives, polyfluorene and its derivatives, polythienylene vinylene and its derivatives Molecular compounds are included. Binder resins may be used alone or in combination.

The solid component concentration of the coating solution is not particularly limited, and is set to a concentration range suitable for obtaining a desired thickness. Usually, it is 0.1 to 50% by weight, preferably 1 to 30% by weight.
When using binder resin, the content in a coating liquid is not specifically limited. The content of the binder resin with respect to the total of the components forming each layer such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is usually 5 to 99.9% by weight, preferably 10 to 99% by weight. is there.

  The film thickness of each layer such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

  The organic electroluminescent element preferably has a protective layer (sealing layer) for the purpose of preventing intrusion of oxygen, moisture and the like. The material of the protective layer is an organic polymer material or an inorganic material. Examples of organic polymer materials include fluorine resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, etc., photocuring Resin may be used. Examples of the inorganic material include diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide, metal sulfide and the like. The material used for the protective layer may be used alone or in combination. The protective layer may have a single layer structure or a multilayer structure.

  The organic electroluminescent element may be protected by being enclosed in an inert material. Examples of the inert substance include paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite-containing fluorocarbon oil, and the like.

  A metal oxide film (for example, an aluminum oxide film) or a metal fluoride film may be provided as a protective film on the electrode of the organic electroluminescent element.

  An interface layer (intermediate layer) may be provided on the surface of the anode of the organic electroluminescent element. Examples of the material for the interface layer include organophosphorus compounds, polysilanes, aromatic amine derivatives, phthalocyanine derivatives, and the like. Further, the surface of the electrode (eg anode) may be treated with acid, ammonia / hydrogen peroxide, or plasma.

  The organic electroluminescent element can be usually used as a direct current drive type element, but may be used as an alternating current drive type element. Further, the organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or an MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. Organic electroluminescent elements include panel-type light sources (for example, backlights for watches, liquid crystal panels, etc.), various light-emitting elements (for example, alternatives to light-emitting elements such as LEDs), lighting devices (planar lighting, special lighting, etc.), various types Display elements [for example, information display elements (personal computer monitors, mobile phone / mobile terminal display elements)], various signs, various sensors, and the like.

[Example 1]
A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was subjected to ultrasonic cleaning using a neutral detergent, Semicoclean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa.

  First, bis [N-phenyl-N- (1-naphthyl)]-4,4′-diamino-1,1′-biphenyl was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec. A hole injection layer was provided.

  Next, 1,3-bis (N-carbazolyl) benzene (hereinafter abbreviated as m-CP) was deposited at a deposition rate of 0.1 nm / sec to provide a 10 nm-thick hole transport layer.

Exemplified Compound A-4 and a tris (phenylpyridyl) iridium complex [hereinafter abbreviated as Ir (ppy) ₃ ], which is a phosphorescent material represented by the formula (a1-1), are each deposited at a deposition rate of 0.2 nm / sec. The light emitting layer having a film thickness of 25 nm was formed by vapor deposition on the hole transport layer at 0.016 nm / sec.

  Further, 4,7-diphenyl-1,10-phenanthroline (hereinafter abbreviated as BPhen) is vapor-deposited on the light-emitting layer at a vapor deposition rate of 0.1 nm / sec to form a 15 nm-thick hole blocking layer (electron). Transport layer) was provided.

  Further, tris (8-quinolinolato) aluminum was deposited on the hole blocking layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer having a thickness of 25 nm. The substrate temperature during vapor deposition was room temperature.

  Subsequently, lithium fluoride was deposited to a thickness of 0.5 nm at a deposition rate of 0.02 nm / sec. Finally, aluminum was deposited as a cathode to a thickness of 100 nm at a deposition rate of 2.0 nm / sec to produce an organic electroluminescent device. Vapor deposition was carried out while maintaining the vacuum state of the vapor deposition tank.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.4 V, and green light emission with a luminance of 2100 cd / m ² was confirmed. The luminance half-life was 3900 hours.

[Comparative Example 1]
In Example 1, an organic electroluminescent element was produced according to the procedure described in Example 1 except that the following compound (CBP) was used instead of the compound of Illustrative Compound A-4 when forming the light emitting layer. did.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.2 V, and green light emission with a luminance of 1800 cd / m ² was confirmed. The half life of luminance was 600 hours.

[Example 2]
In Example 1, instead of using the compound of exemplary compound A-4, an organic electroluminescent device was produced according to the procedure described in Example 1, except that the compound of exemplary compound A-9 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.5 V, and green light emission with a luminance of 2200 cd / m ² was confirmed. The half life of luminance was 3800 hours.

[Comparative Example 2]
In Example 1, the following 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was used instead of using the compound of Exemplary Compound A-4 in forming the light emitting layer. The organic electroluminescent element was produced according to the operation described in Example 1 except that.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.1 V, and green light emission with a luminance of 900 cd / m ² was confirmed. The half life of the brightness was 120 hours.

[Example 3]
In Example 1, instead of using the compound of exemplary compound A-4, an organic electroluminescent device was produced according to the procedure described in Example 1, except that the compound of exemplary compound A-21 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.5 V, and green light emission with a luminance of 2100 cd / m ² was confirmed. The luminance half-life was 3900 hours.

[Example 4]
In Example 1, instead of using the compound of exemplary compound A-4, an organic electroluminescent device was produced according to the procedure described in Example 1, except that the compound of exemplary compound A-26 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.4 V, and green light emission with a luminance of 2000 cd / m ² was confirmed. The half life of luminance was 3700 hours.

[Example 5]
A glass substrate having an ITO transparent electrode (anode) having a thickness of 150 nm was subjected to ultrasonic cleaning using a neutral detergent, Semicoclean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa.

  First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec to form a 10 nm-thick hole injection layer. Bis [N-phenyl-N- (1-naphthyl)]-4,4′-diamino-1,1′-biphenyl was deposited at a deposition rate of 0.1 nm / sec to provide a 30 nm-thick hole injection layer. .

  Next, m-CP was deposited at a deposition rate of 0.1 nm / sec to provide a 10 nm-thick hole transport layer.

  Exemplified Compound B-9 and an iridium complex which is a phosphorescent material represented by the above formula (a1-13) were deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.016 nm / sec, respectively. A light emitting layer having a thickness of 25 nm was provided.

  Further, BPhen was deposited on the light emitting layer at a deposition rate of 0.1 nm / sec to provide a hole blocking layer (electron transport layer) having a thickness of 15 nm.

  Further, tris (8-quinolinolato) aluminum was deposited on the hole blocking layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer having a thickness of 25 nm. The substrate temperature during vapor deposition was room temperature.

  Subsequently, lithium fluoride was deposited at a deposition rate of 0.02 nm / sec to a thickness of 0.5 nm, and finally aluminum was deposited as a cathode at a deposition rate of 2.0 nm / sec to a thickness of 100 nm to form an organic electroluminescent device. Was made. Vapor deposition was carried out while maintaining the vacuum state of the vapor deposition tank.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.5 V, and red light emission with a luminance of 1100 cd / m ² was confirmed. The luminance half-life was 3200 hours.

[Example 6]
In Example 5, instead of using the compound of Exemplified Compound B-9, an organic electroluminescent device was produced according to the procedure described in Example 5 except that the compound of Illustrated Compound B-31 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.4 V, and red light emission with a luminance of 1200 cd / m ² was confirmed. The luminance half-life was 3100 hours.

[Example 7]
In Example 5, instead of using the compound of exemplary compound B-9, an organic electroluminescent device was produced according to the procedure described in Example 5 except that the compound of exemplary compound A-61 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.3 V, and red light emission with a luminance of 1100 cd / m ² was confirmed. The luminance half-life was 3200 hours.

[Example 8]
In Example 5, instead of using the compound of exemplary compound B-9, an organic electroluminescent device was produced according to the procedure described in Example 5 except that the compound of exemplary compound A-36 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.4 V, and red light emission with a luminance of 1000 cd / m ² was confirmed. The half life of luminance was 3000 hours.

[Example 9]
In Example 5, instead of using the compound of exemplary compound B-9, an organic electroluminescent device was produced according to the procedure described in Example 5 except that the compound of exemplary compound A-2 was used.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.5 V, and red light emission with a luminance of 1200 cd / m ² was confirmed. The luminance half-life was 3100 hours.

[Example 10]
A glass substrate having an ITO transparent electrode (anode) having a thickness of 110 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa.

  First, bis [N-phenyl-N- (1-naphthyl)]-4,4′-diamino-1,1′-biphenyl was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec. Next, m-CP was deposited at a deposition rate of 0.1 nm / sec to provide a 10 nm-thick hole transport layer.

The CBP and Ir (ppy) ₃ which is a phosphorescent material represented by the formula (a1-1) are deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.016 nm / sec, respectively. A light emitting layer having a thickness of 25 nm was provided.

  Exemplified Compound A-61 was deposited on the light emitting layer at a deposition rate of 0.1 nm / sec to provide a hole blocking layer (electron transport layer) having a thickness of 15 nm.

  Further, tris (8-quinolinolato) aluminum was deposited on the hole blocking layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer having a thickness of 25 nm. The substrate temperature during vapor deposition was room temperature.

  Subsequently, lithium fluoride was deposited at a deposition rate of 0.02 nm / sec to a thickness of 0.5 nm, and finally aluminum was deposited as a cathode at a deposition rate of 2.0 nm / sec to a thickness of 100 nm to form an organic electroluminescent device. Was made. Vapor deposition was carried out while maintaining the vacuum state of the vapor deposition tank.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.8 V, and green light emission with a luminance of 2100 cd / m ² was confirmed. The half life of luminance was 1300 hours.
By using the compound of the present invention in the hole blocking layer as compared with the organic electroluminescence device of Comparative Example 1, it can be seen that the driving voltage is lowered, the emission luminance is improved, and the half life of the luminance is prolonged. .

[Example 11]
In Example 10, in forming the hole blocking layer (electron transport layer), the compound of Exemplified Compound B-31 was used instead of using the compound of Exemplified Compound A-61, as described in Example 10. According to the operation, an organic electroluminescent device was produced.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 5.7 V, and red light emission with a luminance of 2000 cd / m ² was confirmed. The half life of luminance was 1300 hours.

[Example 12]
A glass substrate having an ITO transparent electrode (anode) having a thickness of 110 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and isopropanol. The substrate was dried with nitrogen gas, further UV / ozone cleaned, fixed to the substrate holder of the vapor deposition apparatus, and the vapor deposition tank was depressurized to 1 × 10 ⁻⁵ Pa.

  First, bis [N-phenyl-N- (1-naphthyl)]-4,4′-diamino-1,1′-biphenyl was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / sec. A hole injection layer was provided.

  Next, exemplary compound A-36 was deposited at a deposition rate of 0.1 nm / sec to provide a 10 nm thick hole transport layer.

The CBP and Ir (ppy) ₃ which is a phosphorescent material represented by the formula (a1-1) are deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.016 nm / sec, respectively. A light emitting layer having a thickness of 25 nm was provided.

  Thereafter, BPhen was deposited on the light emitting layer at a deposition rate of 0.1 nm / sec to provide a hole blocking layer (electron transport layer) having a thickness of 15 nm.

  Further, tris (8-quinolinolato) aluminum was deposited on the hole blocking layer at a deposition rate of 0.1 nm / sec to provide an electron transport layer having a thickness of 25 nm. The substrate temperature during vapor deposition was room temperature.

  Subsequently, lithium fluoride was deposited at a deposition rate of 0.02 nm / sec to a thickness of 0.5 nm, and finally aluminum was deposited as a cathode at a deposition rate of 2.0 nm / sec to a thickness of 100 nm to form an organic electroluminescent device. Was made. Vapor deposition was carried out while maintaining the vacuum state of the vapor deposition tank.

A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at room temperature. Initially, the voltage value was 6.0 V, and green light emission with a luminance of 2200 cd / m ² was confirmed. The half life of luminance was 1300 hours.
By using the compound of the present invention in the hole transport layer as compared with the organic electroluminescence device of Comparative Example 1, it can be seen that the driving voltage is lowered, the emission luminance is improved, and the luminance half-life is prolonged. .

  According to the present invention, the light emission efficiency, stability, and durability of an organic electroluminescence device using light emission from a phosphorescent material can be enhanced.

It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element. It is the schematic which shows an example of the layer structure of an organic electroluminescent element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection transport layer 3 'Hole injection layer 3 "Hole transport layer 3a Hole injection transport component 4 Light emission layer 4a Light emission component 5 Electron injection transport layer 5' Hole blocking layer (electron transport layer)
5a Electron injection transport component 6 Cathode 7 Power supply

Claims (9)

An organic electroluminescence device comprising a functional layer including a light emitting layer , a hole injection transport layer, and an electron injection transport layer between a pair of electrodes,
The light emitting layer contains a phosphorescent material represented by the following general formula (a-1),
The light-emitting layer, the hole injection transport layer, and any layer selected from the group consisting of the electron injecting and transporting layer contains at least one of the fluorene compounds represented by the following general formula (1), organic Electroluminescent device.

[In Formula (a-1),
M ₁ represents an m-valent metal atom,
A ₁ represents an atomic group for forming a 5-membered or 6-membered nitrogen-containing heterocycle,
A ₂ represents an atomic group for forming a 5-membered or 6-membered cyclic structure;
L and L ′ represent an atom capable of coordinating to M ₁ , and a dotted line connecting L and L ′ represents that a bond may be formed or separated,
n _d represents an integer of 1 to m. ]

[In Formula (1),
R _{1 to} R ₆ each independently represent a substituent, and R _{1 to} R ₆ may form a ring together with adjacent groups,
n _{1 to} n ₆ represent 0 or an integer of 1 to 3,
A and B represent a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, but A and B are not the same group, and n is 1 or 2 (Provided that A and B are both aryl groups). ] Formula metal atom represented by (a-1) M ₁ in is iridium or platinum, the organic electroluminescent device according to claim 1.   The organic electroluminescent device according to claim 1, wherein in general formula (1), one of A and B is a linear, branched or cyclic alkyl group, and the other is a substituted or unsubstituted aralkyl group. .   2. The organic electroluminescent device according to claim 1, wherein in General Formula (1), one of A and B is a linear or branched alkyl group, and the other is a cyclic alkyl group.   The organic electroluminescent element as described in any one of Claims 1-4 whose layer containing the fluorene compound represented by General formula (1) is a light emitting layer.   The organic electroluminescent element as described in any one of Claims 1-4 whose layer containing the fluorene compound represented by General formula (1) is a positive hole injection transport layer.   The organic electroluminescent element as described in any one of Claims 1-4 whose layer containing the fluorene compound represented by General formula (1) is an electron injection transport layer.   The organic electroluminescent element according to claim 1, wherein the functional layer sandwiched between the pair of electrodes further includes a hole injection transport layer. The organic electroluminescent element according to claim 1, wherein the functional layer sandwiched between the pair of electrodes further includes an electron injecting and transporting layer.

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