JP6862767B2 - Triazine compounds, their production methods, production intermediates, and applications - Google Patents

Description

The present invention relates to a triazine compound useful as a constituent component of an organic electroluminescent device, a method for producing the triazine compound, a production intermediate thereof, and an application thereof.

The basic structure of an organic electroluminescent device is that a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside thereof, and the positive electroluminescence device is injected into the light emitting layer. It is an element that utilizes the emission of light (fluorescence or phosphorescence) associated with exciton deactivation caused by the recombination of holes and electrons, and is applied to displays and the like. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron block layer, a light emitting layer and a hole block layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. It may be configured.

Conventional organic electroluminescent devices have a higher drive voltage, lower emission brightness and luminous efficiency, and a significantly shorter element life than inorganic light emitting diodes, and have not been put into practical use. Although recent organic electroluminescent devices have been gradually improved, more excellent materials are required in terms of luminous efficiency characteristics, drive voltage characteristics, and long life characteristics.

Examples of the electron transport material having excellent long life for an organic electroluminescent device include triazine compounds (for example, Patent Documents 1-4 and Non-Patent Documents 1). However, further improvements have been required in terms of voltage, life and luminous efficiency of the organic electroluminescent device using the material.

Patent No. 4907090 Patent No. 4856882 Patent No. 4907192 Patent No. 5064053 Scientific Reports, Volume 3, 2127-2132, 2013

Although organic electroluminescent devices have begun to be used in various display devices, there is a demand for higher performance of the devices such as longer life, higher luminous efficiency, and lower drive voltage. More specifically, there is a demand for the development of carrier transport materials that achieve long life, high luminous efficiency, low drive voltage, and suppression of voltage rise during drive.

Among the carrier transport materials, the electron-injected material and the electron-transported material are new materials that drive the device at a low voltage due to its excellent electron-injecting property and electron-transporting characteristics, and have high luminous efficiency to drive the device for a long time. It is desired. In particular, in an organic electroluminescent device utilizing phosphorescence and TADF, a light emitting material having a high excited triplet level and a carrier transport material are desired in order to realize a long life, a low driving voltage and a high luminous efficiency. It is rare.

As a result of diligent studies to solve the above problems, the present inventors have found that the triazine compound represented by the general formula (1) of the present invention has electron durability and holes as compared with conventionally known compounds. We have found that the durability is significantly improved. Further, the inventors have found that the triazine compound represented by the general formula (1) of the present invention has an improved excited triplet level as compared with a conventionally known compound. Based on these findings, it was found that when the triazine compound is used as an electron transport layer in an organic electroluminescent device, the life of the organic electroluminescent device is extended as compared with the case where a known or general-purpose electron transport material is used. We have found and completed the present invention.

That is, the present invention relates to a triazine compound represented by the following general formula (1) of the present invention (hereinafter, also referred to as "compound (1)"), a method for producing the same, and an organic electroluminescent device containing the same. ..

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or 6 to 6 carbon atoms composed of only a 6-membered ring. It may have 30 monocyclic, linked, or condensed ring aromatic groups as substituents). }
The present invention also relates to a method for producing the compound (1), a production intermediate extremely useful for industrially producing the compound (1), and the use of the compound (1).

Hereinafter, the present invention will be described in detail.

Substituents in compound (1) of the present application are defined as follows.

In the present invention, Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, and 3 to 10 carbon atoms). Alkoxy group, halogenated alkoxy group having 1 to 3 carbon atoms, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, alkyl halide group having 1 to 3 carbon atoms, or monocycle having 6 to 30 carbon atoms. , Linked, or may have a fused ring aromatic group as a substituent.)

The ring skeleton of a monocyclic or condensed aromatic group having 6 to 30 carbon atoms may contain a complex atom other than a carbon atom. That is, the monocyclic or fused aromatic group having 6 to 30 carbon atoms is a monocyclic ring having 6 to 30 carbon atoms or a monocyclic aromatic hydrocarbon group having 6 to 30 carbon atoms and a monocyclic ring having 6 to 30 carbon atoms. Contains ring heteroaromatic groups.

In the monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms, 6 to 30 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 30 carbon atoms is not particularly limited as long as it is a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. Absent.

The monocyclic or fused aromatic group having 6 to 30 carbon atoms is not particularly limited, but for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, and a fluoranthenyl group. Group, perylenyl group, triphenylenyl group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, phenanthrolyl group, azaifluorenyl group, azafluolanthenyl group, azaperylenyl group, azatriphenyleni Examples thereof include a ru group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a dibenzofuranyl group, an azabenzothienyl group, an azadibenzothienyl group, an azabenzofuranyl group, and an azadibenzofuranyl group.

Regarding the monocyclic ring having 6 to 30 carbon atoms or the fused ring aromatic group (which may have the above-mentioned substituent), the monocyclic ring having 6 to 18 carbon atoms is excellent in terms of electron transport material properties. Alternatively, it is preferably a condensed ring aromatic group (which may have the above-mentioned substituent), and is a monocyclic ring having 6 to 14 carbon atoms or a condensed ring aromatic group (which may have the above-mentioned substituent). It is also preferable).

The ring skeleton of a monocyclic or condensed aromatic group having 6 to 18 carbon atoms may contain a complex atom other than a carbon atom. That is, the monocyclic or condensed ring aromatic group having 6 to 18 carbon atoms is a monocyclic ring having 6 to 18 carbon atoms, or a monocyclic ring having a condensed ring aromatic hydrocarbon group and a monocyclic ring having 6 to 30 carbon atoms, or reduced. Contains ring heteroaromatic groups.

In the monocyclic or condensed ring aromatic group having 6 to 18 carbon atoms, 6 to 18 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 18 carbon atoms is not particularly limited as long as it is a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. Absent.

The monocyclic or fused aromatic group having 6 to 18 carbon atoms is not particularly limited, but for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, and a fluoranthenyl group. Group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenyltridinyl group, phenanthrolyl group, azaifluorenyl group, azafluolanthenyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, dibenzo Examples thereof include a furanyl group, an azabenzothienyl group, an azadibenzothienyl group, an azabenzofuranyl group, an azadibenzofuranyl group and the like.

The ring skeleton of a monocyclic or condensed aromatic group having 6 to 14 carbon atoms may contain a complex atom other than a carbon atom. That is, the monocyclic or fused aromatic group having 6 to 14 carbon atoms is a monocyclic ring having 6 to 14 carbon atoms, or a monocyclic aromatic hydrocarbon group having 6 to 14 carbon atoms and a monocyclic ring having 6 to 14 carbon atoms. Contains ring heteroaromatic groups.

In the monocyclic or condensed ring aromatic group having 6 to 14 carbon atoms, 6 to 14 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 14 carbon atoms is not particularly limited as long as it is a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. Absent.

The monocyclic or fused aromatic group having 6 to 14 carbon atoms is not particularly limited, but for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a quinolyl group, an isoquinolyl group, and the like. Acridinyl group, phenanthridinyl group, phenanthrolic group, azafluorenyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, dibenzofuranyl group, azabenzothienyl group, azadibenzothienyl group, azabenzofuranyl group, azadibenzofla Nyl group and the like can be mentioned.

The alkoxy group having 3 to 10 carbon atoms in Ar ^{1 to} Ar ⁴ includes a linear, branched or cyclic group, and is not particularly limited, but for example, a propoxy group (n-propoxy group, isopropoxy). Group), butoxy group (n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group), pentyloxy group (n-pentyloxy group, sec-pentyloxy group, isopentyloxy group, cyclopentyloxy group) , Hexyloxy group (n-hexyloxy group, cyclohexyloxy group), n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, phenethyloxy group and the like. ..

The halogenated alkoxy group having 1 to 3 carbon atoms in Ar ^{1 to} Ar ⁴ includes a linear, branched or cyclic group, and is not particularly limited, but for example, a chloromethyloxy group or a dichloromethyloxy group. Group, trichloromethyloxy group, fluoromethyloxy group, difluoromethyloxy group, trifluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, Examples thereof include a difluoroethyloxy group, a trifluoroethyloxy group, a pentafluoroethyloxy group, a chloropropyloxy group, a fluoropropyloxy group and the like.

The alkyl groups having 3 to 10 carbon atoms in Ar ^{1 to} Ar ⁴ include linear, branched or cyclic groups, and are not particularly limited, but for example, propyl groups (n-propyl groups, isopropyl groups). , Butyl group (n-butyl group, sec-butyl group, isobutyl group, tert-butyl group), pentyl group (n-pentyl group, sec-pentyl group, isopentyl group, cyclopentyl group), hexyl group (n-hexyl group) , Cyclohexyl group), n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, benzyl group, phenethyl group and the like.

The ^{alkyl halide groups having 1 to 3 carbon atoms in Ar 1 to} Ar ⁴ include linear, branched or cyclic groups, and are not particularly limited, but for example, chloromethyl group, dichloromethyl group and trichloro. Methyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, pentachloroethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group, chloropropyl group, Alternatively, a fluoropropyl group or the like can be mentioned.

The ring skeleton of the monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms may contain a complex atom other than the carbon atom. That is, the monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms is a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms and a single ring having 6 to 30 carbon atoms. Includes ring, linked, or fused ring heteroaromatic groups.

In the monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms, 6 to 30 defines the carbon number of the ring skeleton of the aromatic group.

Regarding the monocyclic, linked, or fused aromatic group having 6 to 30 carbon atoms, the monocyclic aromatic group, the aromatic group in which the monocyclic aromatic groups are fused, or the monocyclic aromatic group and / Alternatively, the group is not particularly limited as long as it is a group aromatic group to which condensed aromatic groups are linked.

The monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms is not particularly limited, but is not particularly limited, for example, a phenyl group, a biphenylyl group, a naphthyl group, or an anthryl group. , Phenyltril group, pyridyl group, pyrenyl group, fluorenyl group, fluoranthenyl group, perylenelyl group, triphenylenyl group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, phenanthrolyl group, azaiflu Olenyl group, azafluolanthenyl group, azaperylenyl group, azatriphenylenyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, dibenzofuranyl group, azabenzothienyl group, azadibenzothienyl group, azabenzofuranyl group , Azadibenzofuranyl group and the like.

The monocyclic, linked, or fused ring aromatic group having 6 to 30 carbon atoms (which may have the above-mentioned substituent) has a single ring number of 6 to 18 carbon atoms in that it has excellent properties of an electron transporting material. It is preferably a ring, linked, or fused ring aromatic group (which may have the above-mentioned substituent), and is preferably a monocyclic, linked, or condensed ring aromatic group having 6 to 14 carbon atoms (the above-mentioned substituent). It may have a group).

The ring skeleton of the monocyclic, linked, or condensed ring aromatic group having 6 to 18 carbon atoms may contain a complex atom other than the carbon atom. That is, the monocyclic, linked, or condensed ring aromatic group having 6 to 18 carbon atoms is a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 18 carbon atoms and a single ring having 6 to 18 carbon atoms. Includes ring, linked, or fused ring heteroaromatic groups.

In the monocyclic, linked, or condensed ring aromatic group having 6 to 18 carbon atoms, 6 to 18 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic, linked, or condensed ring aromatic group having 6 to 18 carbon atoms is particularly limited as long as it is a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are linked or fused. It is not something that is done.

The monocyclic, linked, or condensed ring aromatic group having 6 to 18 carbon atoms is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyridyl group, and a pyrenyl group. Group, fluorenyl group, fluoranthenyl group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, phenanthrolyl group, azafluorenyl group, azafluoranthenyl group, benzothienyl group, dibenzothienyl group , Benzofuranyl group, dibenzofuranyl group, azabenzothienyl group, azadibenzothienyl group, azabenzofuranyl group, azadibenzofuranyl group and the like.

The ring skeleton of the monocyclic, linked, or condensed ring aromatic group having 6 to 14 carbon atoms may contain a complex atom other than the carbon atom. That is, the monocyclic, linked, or condensed ring aromatic group having 6 to 14 carbon atoms is a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 14 carbon atoms and a single ring having 6 to 14 carbon atoms. Includes ring, linked, or fused ring heteroaromatic groups.

In the monocyclic, linked, or condensed ring aromatic group having 6 to 14 carbon atoms, 6 to 14 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic, linked, or condensed ring aromatic groups having 6 to 14 carbon atoms are particularly limited as long as they are monocyclic aromatic groups or aromatic groups in which monocyclic aromatic groups are linked or fused. It is not something that is done.

The monocyclic, linked, or condensed ring aromatic group having 6 to 14 carbon atoms is not particularly limited, and is, for example, a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyridyl group, and a pyrenyl group. Group, fluorenyl group, fluoranthenyl group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, phenanthrolyl group, azafluolenyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, dibenzofura Nyl group, azabenzothienyl group, azadibenzothienyl group, azabenzofuranyl group, azadibenzofuranyl group and the like can be mentioned.

In the present invention, Ar ⁵ is a monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group has a fluorine atom, a methoxy group, an ethoxy group, and 3 to 10 carbon atoms). An alkoxy group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon composed of only a 6-membered ring. It may have a monocyclic, linked, or condensed ring aromatic group of numbers 6 to 30 as a substituent).

A monocyclic ring having 6 to 30 carbon atoms or a fused ring aromatic group composed of only a 6-membered ring may contain a complex atom other than a carbon atom in its ring skeleton. That is, the monocyclic or condensate aromatic group having 6 to 30 carbon atoms composed only of the 6-membered ring is a monocyclic or condensate aromatic group having 6 to 30 carbon atoms composed only of the 6-membered ring. It contains a monocyclic or condensed heteroaromatic group having 6 to 30 carbon atoms and is composed only of a group hydrocarbon group and a 6-membered ring.

In the monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring, 6 to 30 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring may be a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. For example, it is not particularly limited.

The monocyclic or fused aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring is not particularly limited, and is, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and pyrenyl. Examples thereof include a group, a perylenyl group, a triphenylenyl group, a tetrasenyl group, a chrysenyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a phenanthrolyl group, an azaperylenyl group and an azatriphenylenyl group.

For a monocyclic ring having 6 to 30 carbon atoms or a condensed ring aromatic group (which may have the above-mentioned substituent) composed of only the 6-membered ring, the number of carbon atoms composed of only the 6-membered ring It is preferably a monocyclic ring of 6 to 18 or a condensed aromatic group (which may have the above-mentioned substituent), and is a monocyclic ring having 6 to 14 carbon atoms composed of only a 6-membered ring, or a monocyclic ring having 6 to 14 carbon atoms. More preferably, it is a fused ring aromatic group (which may have the above-mentioned substituent).

A monocyclic ring having 6 to 18 carbon atoms or a condensed ring aromatic group composed of only a 6-membered ring may contain a complex atom other than a carbon atom in its ring skeleton. That is, the monocyclic or condensate aromatic group having 6 to 18 carbon atoms composed only of the 6-membered ring is a monocyclic or condensate aromatic group having 6 to 18 carbon atoms composed only of the 6-membered ring. It contains a monocyclic or condensed heteroaromatic group having 6 to 18 carbon atoms and is composed only of a group hydrocarbon group and a 6-membered ring.

In the monocyclic or condensed ring aromatic group having 6 to 18 carbon atoms composed of only the 6-membered ring, 6 to 18 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 18 carbon atoms composed of only the 6-membered ring may be a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. For example, it is not particularly limited.

The monocyclic or fused aromatic group having 6 to 18 carbon atoms composed of only the 6-membered ring is not particularly limited as described above, and is not particularly limited, for example, a phenyl group, a naphthyl group, an anthryl group, and the like. Examples thereof include a phenanthryl group, a triphenylenyl group, a tetrasenyl group, a chrysenyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a phenanthrolyl group and an azatriphenylenyl group.

A monocyclic ring having 6 to 14 carbon atoms or a fused ring aromatic group composed of only a 6-membered ring may contain a complex atom other than a carbon atom in its ring skeleton. That is, the monocyclic or condensate aromatic group having 6 to 14 carbon atoms composed only of the 6-membered ring is a monocyclic or condensate aromatic group having 6 to 14 carbon atoms composed only of the 6-membered ring. It contains a monocyclic or condensed heteroaromatic group having 6 to 14 carbon atoms and is composed only of a group hydrocarbon group and a 6-membered ring.

In the monocyclic or condensed ring aromatic group having 6 to 14 carbon atoms composed of only the 6-membered ring, 6 to 12 defines the carbon number of the ring skeleton of the aromatic group.

The monocyclic or condensed aromatic group having 6 to 14 carbon atoms composed of only the 6-membered ring may be a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused. For example, it is not particularly limited.

The monocyclic or condensate aromatic group having 6 to 14 carbon atoms composed of only the 6-membered ring is not particularly limited as described above, but for example, a phenyl group, a naphthyl group, a quinolyl group, and the like. Examples thereof include an isoquinolyl group and a phenylanthrolyl group.

The alkoxy group having 3 to 10 carbon atoms in Ar ⁵ includes a linear, branched or cyclic group, and is not particularly limited, but for example, a propoxy group (n-propoxy group, isopropoxy group), butoxy. Group (n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group), pentyloxy group (n-pentyloxy group, sec-pentyloxy group, isopentyloxy group, cyclopentyloxy group), hexyloxy group (N-hexyloxy group, cyclohexyloxy group), n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, phenethyloxy group and the like can be mentioned.

The halogenated alkoxy group having 1 to 3 carbon atoms in Ar ⁵ includes a linear, branched or cyclic group, and is not particularly limited, but for example, a chloromethyloxy group, a dichloromethyloxy group, or a trichloromethyl group. Oxy group, fluoromethyloxy group, difluoromethyloxy group, trifluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group Examples thereof include a group, a trifluoroethyloxy group, a pentafluoroethyloxy group, a chloropropyloxy group, a fluoropropyloxy group and the like.

The alkyl group having 3 to 10 carbon atoms in Ar ⁵ includes a linear, branched or cyclic group, and is not particularly limited, but for example, a propyl group (n-propyl group, isopropyl group) or a butyl group. (N-butyl group, sec-butyl group, isobutyl group, tert-butyl group), pentyl group (n-pentyl group, sec-pentyl group, isopentyl group, cyclopentyl group), hexyl group (n-hexyl group, cyclohexyl group) ), N-Heptyl group, n-octyl group, n-nonyl group, n-decyl group, benzyl group, phenethyl group and the like.

The ^{alkyl halide group having 1 to 3 carbon atoms in Ar 5} includes a linear, branched or cyclic group, and is not particularly limited, but for example, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and the like. Fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, pentachloroethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group, chloropropyl group, or fluoropropyl Group etc. can be mentioned.

For a monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring in ^{Ar 5, the ring skeleton may contain a complex atom other than a carbon atom.} That is, the monocyclic, linked, or fused ring aromatic group having 6 to 30 carbon atoms composed only of the 6-membered ring is the monocyclic, linked, or linked aromatic group having 6 to 30 carbon atoms composed only of the 6-membered ring. Alternatively, it contains a monocyclic, linked, or fused heteroaromatic group having 6 to 30 carbon atoms composed only of a fused aromatic hydrocarbon group and a 6-membered ring.

In the monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring, 6 to 30 defines the carbon number of the ring skeleton of the aromatic group.

Regarding a monocyclic, linked, or fused aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring, a monocyclic aromatic group or an aromatic group in which monocyclic aromatic groups are fused to each other, Alternatively, the group is not particularly limited as long as it is a group aromatic group in which a monocyclic aromatic group and / or a fused ring aromatic group is linked.

The monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms composed of only the 6-membered ring is not particularly limited, but is not particularly limited, for example, a phenyl group. Biphenylyl group, naphthyl group, anthryl group, phenanthryl group, pyridyl group, pyrenyl group, fluorenyl group, peryleneyl group, triphenylenyl group, tetrasenyl group, chrysenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenylanthridinyl group, phenanthrolyl group , Azaperylenyl group, azatriphenylenyl group and the like.

The ^{substituent represented by Ar 1 to} Ar ⁴ which may be possessed by a monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms is a fluorine atom in that it is excellent in electron transport material properties. , Methyl group, butyl group, methoxy group, butoxy group, methyl halide group, methoxy halide group, or aromatic group having 6 to 30 carbon atoms which may be fused, preferably a methyl group or a fluorine atom. preferable.

As a ^{substituent represented by Ar 5} which may be possessed by a monocyclic ring having 6 to 30 carbon atoms composed of only a 6-membered ring or a fused ring aromatic group, it is excellent in electron transport material properties. In terms of points, a monocyclic, linked or reduced carbon number of 6 to 30 consisting only of a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, a methoxy halide group, or a 6-membered ring A ring aromatic group is preferable, and a phenyl group, a methyl group or a fluorine atom is more preferable.

^{Further, regarding Ar 1 to} Ar ⁴ in the general formula (1), a monocyclic group having 6 to 18 carbon atoms or a fused ring aromatic group (these groups are independent of each other) in that they are excellent in electron transport characteristics. It has a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, a methoxy halide group, or an aromatic group having 6 to 30 carbon atoms which may be fused as a substituent. It is preferable that it is a monocyclic or fused aromatic group having 6 to 14 carbon atoms (these groups are independently a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, and the like. It may have a methyl halide group, a methoxy halide group, or an aromatic group having 6 to 30 carbon atoms which may be condensed as a substituent), more preferably a phenyl group or a naphthyl group. , Or a phenanthryl group (these groups are independently fluorine atoms, methoxy groups, butoxy groups, methyl halide groups, methoxy halide groups, or aromatics having 6 to 30 carbon atoms which may be fused. It is preferably a group (which may have a group as a substituent), and is preferably a phenyl group or a phenanthryl group (each of these groups may independently have a fluorine atom or a condensed ring number of 6 to carbon atoms). It may have 30 aromatic groups as a substituent), and more preferably a phenyl group or a phenanthryl group.

^{Further, regarding Ar 5} in the general formula (1), a monocyclic or condensed ring aromatic group having 6 to 18 carbon atoms is excellent in that it has excellent electron transport characteristics (these groups are independently fluorine atoms, respectively. Substitutes a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, a methoxy group halide, or a monocyclic, linked, or fused aromatic group having 6 to 30 carbon atoms consisting of only a 6-membered ring. It is preferably a monocyclic or fused aromatic group having 6 to 14 carbon atoms (these groups may independently have a fluorine atom, a methyl group, a butyl group, etc.). It has a methoxy group, a butoxy group, a methyl halide group, a methoxy halide group, or a monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring as a substituent. It is more preferable that it is a phenyl group, a naphthyl group, or a phenanthryl group (these groups are independently a fluorine atom, a methyl group, a butyl group, a methoxy group, a butoxy group, a methyl halide group, and the like. It is preferably a methoxy group halide or a monocyclic, linked or condensed aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring as a substituent), preferably a phenyl group. , Or a phenanthryl group (each of these groups independently has a monocyclic, linked, or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a fluorine atom or a 6-membered ring as a substituent. It is more preferable that it is a phenyl group or a phenanthryl group.

Further, the triazine compound represented by the general formula (1) is described in the following general formula (2).

(In the formula, ^{the definitions and preferable ranges of Ar 1 to} Ar ⁵ are the same as those in the general formula (1).)
It is preferably a triazine compound represented by the following general formula (3).

(In the formula, ^{the definitions and preferable ranges of Ar 1 to} Ar ⁵ are the same as those in the general formula (1).)
It is more preferable that it is a triazine compound represented by.

Specific examples of the triazine compound represented by the general formula (1) include the following compounds 1 to 554, but the present invention is not limited thereto.

Next, the production method of the present invention will be described.

The triazine compound (1) of the present invention can be produced by the method represented by the following reaction formula (1) in the presence of a metal catalyst or in the presence of a base and a metal catalyst.

In addition, hereinafter, the compound represented by the general formula (4) is abbreviated as the compound (4). In addition, other compounds including compound (5) have the same meaning.

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or 6 to 6 carbon atoms composed of only a 6-membered ring. It may have 30 monocyclic, linked, or condensed ring aromatic groups as substituents).
X and Y each independently represent a leaving group. }
Compound (4) can be produced, for example, by using the method disclosed by Hiroshi Yamanaka, "New Heterocyclic Compound Basics", Kodansha, 2004.

Compound (5) is described, for example, in J. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, Volume 60, 7508-7510, 1995, Journal of Organic Chemistry, Volume 16 , 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008. Further, any hydrogen atom in the compound (5) may be substituted with a deuterium atom.
The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent. The aromatic group having 6 to 30 carbon atoms is not particularly limited as long as it is monocyclic or condensed.

That is, an aromatic group having 6 to 30 carbon atoms has a total carbon number of 6 to 30 in the ring skeleton, and by linking with the compound (4), it forms a constituent component necessary for forming the compound (1). If possible, it represents an aromatic group that may be fused. The aromatic group having 6 to 30 carbon atoms does not include the carbon number of the substituent which may be separately contained. The aromatic group having 6 to 30 carbon atoms is not particularly limited as long as it is monocyclic or condensed.

The leaving group represented by X and Y represents a group that is eliminated during the reaction, and is not particularly limited, but for example, a hydrogen atom, a chlorine atom, a bromine atom, a trifurate, an iodine atom, or a metal-containing group. (For example, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl ₂ , AlBr ₂ , Al (Me) ₂ , Al (Et) ₂ , Al ( ⁱ Bu) ₂ , Sn (Me) ₃ , Sn (Bu) ₃ , SnF ₃ , ZnR ²⁴ (R ²⁴ represents a halogen atom. Examples of ZnR ²⁴ include ZnCl, ZnBr, ZnI, etc.), Si (R ²¹ ) ₃ (for example, SiMe ₃ , SiPh). ₃ , SiMePh ₂ , SiCl ₃ , SiF ₃ , Si (OMe) ₃ , Si (OEt) ₃ , Si (OMe) ₂ OH, etc.), BF ₃ K, B (OR ²² ) ₂ (for example, B (OH) _{2) ^{, B (OMe) 2, B}} (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the _like), ^{B (OR} 23) _3, etc.) and the like.

Ligs such as ethers and amines may be coordinated to the metal-containing groups represented by X and Y, and the type of ligand may not inhibit the reaction formula (1). There is no limit.

Further, as B (OR ²² ) ₂ , those represented by the following (I) to (VII) can be exemplified, and those represented by (II) are preferable in terms of good yield.

Examples of the B (OR ²³ ) ₃ include those shown in the following (I) to (III).

Of these leaving groups, chlorine atom, bromine atom, triflate, iodine atom, B (OR ²² ) ₂ or B (OR ²³ ) ₃ are selected in terms of ease of post-reaction treatment and ease of raw material procurement. preferable.

Of the compound (4), the triazine compound represented by the following general formula (4-1) is preferable as a production intermediate for producing the compound (1).

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
X represents a leaving group. }
^{Regarding Ar 1 to} Ar ⁴ of the compound (5), a phenyl group, a naphthyl group, or a phenanthryl group (these groups) can be efficiently produced under a low environmental load. Are independently halogen atoms, methyl groups, butyl groups, methoxy groups, butoxy groups, methyl halide groups, methoxy halide groups, or monocyclic, linked, or fused aromatic groups having 6 to 30 carbon atoms. (May have a substituent as a substituent), preferably a phenyl group or a phenanthryl group (each of these groups is independently a halogen atom or a monocycle having 6 to 30 carbon atoms. , Linked or having a fused ring aromatic group as a substituent), more preferably a phenyl group or a phenanthryl group.

Next, the reaction formula (1) will be described.

As shown in the reaction of the reaction formula (1), the compound (1) of the present invention is a compound represented by the general formula (4) in the presence of a metal catalyst or a base and a metal catalyst, and a general formula. It can be synthesized by performing a coupling reaction with the compound represented by (5).

In the reaction of the reaction formula (1), the metal catalyst is preferably a palladium catalyst, a nickel catalyst, an iridium catalyst, a rhodium catalyst or a copper catalyst in terms of excellent coupling reaction efficiency and the like, and is easy to handle. In some respects, palladium catalysts, nickel catalysts or copper catalysts are more preferred.

In the reaction of the reaction formula (1), it is possible to add a base to carry out the reaction, and it is preferable to add a base from the viewpoint of improving the reaction yield. However, when X and Y are B (OR ²² ) ₂ or Si (R ²¹ ) ₃ , it is essential to add a base.

Further, a phase transfer catalyst can be added in the reaction of the reaction formula (1). The correlation transfer catalyst is not particularly limited, but for example, 18-crown-6-ether or the like can be used. The amount to be added is an arbitrary amount within a range that does not significantly inhibit the reaction.

The metal catalyst used in the reaction of the reaction formula (1) is not particularly limited, and examples thereof include a palladium catalyst, a nickel catalyst, an iridium catalyst, a rhodium catalyst, and a copper catalyst.

The palladium catalyst is not particularly limited, and examples thereof include salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate. In addition, π-allyl palladium chloride dimer, palladium acetylacetonato, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert). Examples thereof include −butyl) phosphine palladium and dichloro (1,1′-bis (diphenylphosphino) ferrocene) palladium. Among them, a palladium complex having a tertiary phosphine as a ligand, such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tri (tert-butyl) phosphine palladium, is preferable in terms of good yield and can be obtained. Tri (tert-butyl) phosphine palladium is further preferred in that it is easy.

The nickel catalyst is not particularly limited, but for example, nickel chloride, nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel. , Dichloro [1,3-bis (diphenylphosphino) propane] nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro [1,1'-bis (diphenylphosphino) ferrocene] nickel, [1,2-Bis (dicyclohexylphosphino) ethane] Dicarbonyl nickel (the above five are examples of nickel complexes having tertiary phosphine as a ligand), dichloro (N, N, N', N'- Tetramethylethylenediamine) Nickel can be mentioned. Among them, dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, and dichloro (N, N, N', N'-tetramethylethylenediamine) nickel have excellent coupling reaction results. Dichloro (dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable in terms of preference and availability.

The iridium catalyst is not particularly limited, but is, for example, iridium (III) chloride, (2,2'-bipyridine) bis (2-phenylpyridinato) iridium (III) hexafluorophosphate, bis (triphenyl). Hosphin) Iridium (I) carbonyl chloride, tris (triphenylphosphine) iridium (I) carbonyl hydride, di-μ-chlorobis (cyclooctene) iridium (I), dichlorotetra (ethylene) diiridium (I), bis (1) , 5-Cyclooctadien) Diiridium (I) dichloride, bis (1,5-cyclooctadien) di-μ-methoxydiiridium (I), (1,5-cyclooctadien) (pyridine) (tricyclohexyl) Examples thereof include phosphine) iridium (I) hexafluorophosphate and dichloro (pentamethylcyclopentadienyl) iridium (III) (dimer).

The rhodium catalyst is not particularly limited, but is limited to tris (triphenylphosphine) rhodium (I) chloride, tetrakis (triphenylphosphine) rhodium (I) hydride, and bis (1,5-cyclooctadien) dilodium (I). ) Dichloride, chlorobis (cyclooctene) rhodium (I) (dimer), tris (triphenylphosphine) rhodium (I) carbonyl hydride, bis (triphenylphosphine) carbonyl rhodium (I) chloride, bis [η- (2,5) -Norbornadiene] Rhodium (I) tetrafluoroborate, bis (1,5-cyclooctadiene) rhodium (I) tetrafluoroborate, (acetylacetonato) (norbornadiene) rhodium (I), bis (ethylene) ( 2,4-Pentandionato) Rhodium (I) can be mentioned.

The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper trifurate. Among them, copper oxide and copper iodide are preferable in terms of excellent coupling reaction results, and copper iodide or copper oxide is more preferable in that they are easily available.

For the above-mentioned palladium complex having a tertiary phosphine as a ligand and a nickel complex having a tertiary phosphine as a ligand, a tertiary phosphine is added to a palladium salt, a nickel salt or a complex compound thereof. Can be adjusted. The adjustment can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.

The tertiary phosphine is not particularly limited, but for example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl. -4,5-bis (diphenylphosphine) xanthene, 2- (diphenylphosphine) -2'-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphine) biphenyl, 2- ( Dicyclohexylphosphine) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphine) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-kisilyl) phosphine, (±) -2,2'-bis (±) -2,2'-bis ( Diphenylphosphine) -1,1'-binaphthyl, 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl and the like can be exemplified. Of these, (tert-butyl) phosphine or 2-dicyclohexylphosphine-2', 4', 6'-triisopropylbiphenyl is preferable because it is easily available and the yield is good.

When tertiary phosphine is added to a palladium salt, nickel salt or a complex compound thereof, the amount of the tertiary phosphine added is 1 mol (palladium or nickel atom equivalent) of the palladium salt, nickel salt or a complex compound thereof. On the other hand, it is preferably 0.1 to 10 times mol, and more preferably 0.3 to 5 times mol from the viewpoint of good yield.

It is also possible to separately add a ligand to the above-mentioned copper catalyst. The ligand to be added to the copper catalyst is not particularly limited, but for example, 2,2'-bipyridine, 1,10-phenanthroline, N, N, N', N'-tetramethylethylenediamine, triphenyl. Examples thereof include phosphine and 2- (dicyclohexylphosphino) biphenyl. Of these, 1,10-phenanthroline is preferable because it is easily available and the yield is good.

The base that can be used in the reaction formula (1) is not particularly limited, but for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate. , Potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride, silver carbonate and the like can be exemplified. Of these, potassium carbonate, potassium phosphate or sodium hydroxide is preferable in terms of good yield.

The reaction of reaction formula (1) is preferably carried out in a solvent. The solvent is not particularly limited, but for example, water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, xylene and the like. Can be exemplified, and these may be used in combination as appropriate. Of these, a mixed solvent of THF, 1,4-dioxane, xylene, toluene and butanol, or a mixed solvent of xylene and butanol is preferable in terms of good yield.

The compound (5) in the reaction formula (1) is not particularly limited, and for example, the compounds represented by the following 3 to 3 to 24 can be exemplified.

(These substituents are independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and 1 to 3 carbon atoms. May have a methyl halide group of 1 to 3 or a methoxy halide group having 1 to 3 carbon atoms as a substituent.
Further, Y has the same definition as Y in the above general formula (5). )
The reaction formula (1) is a method for producing the compound (1) of the present invention by reacting the compound (4) with the compound (5) in the presence of a metal catalyst or a base and a metal catalyst. -By applying the reaction conditions of the Miyaura reaction, the desired product can be obtained in good yield.

The amount of the metal catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1 with respect to 1 mol of the compound (10) or (11) in terms of good yield. It is preferably ~ 0.01 times the molar amount (in terms of metal atoms).

The amount of the base used is not particularly limited, but is preferably 0.1 to 10 times the molar amount of 1 mol of the compound (5), and is 1 to 4 times the molar amount in terms of good yield. Is even more preferable.

The molar ratio of the compound (4) to the compound (5) used in the reaction formula (1) is not particularly limited, but the compound (5) having a molar ratio of 1 to 10 times that of 1 mol of the elimination group of the compound (4). ), And it is more preferable to use 1 to 3 times the molar amount of the compound (5) in terms of good yield.

The compound (4) is an excellent material for industrially supplying a compound such as the compound (1), which is remarkably excellent in low drive voltage property, high luminous efficiency, and long life of an organic electroluminescent device. It is industrially very valuable.

The purity of compound (1) of the present invention can be increased by performing treatments such as reprecipitation, concentration, filtration, and purification after completion of each reaction. In order to further purify the product, it may be purified by recrystallization, silica gel column chromatography, sublimation or the like, if necessary.

Next, the reaction formula (2) will be described.

The triazine compound (1) of the present invention couples a compound represented by the general formula (6) and a compound represented by the general formula (7) in the presence of a metal catalyst or a base and a metal catalyst. A method for producing a cyclic azine compound represented by the general formula (1), which comprises reacting.

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or condensed ring aromatic group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or 6 to 6 carbon atoms composed of only a 6-membered ring. It may have 30 monocyclic, linked, or condensed ring aromatic groups as substituents).
X and Y each independently represent a leaving group. }
Compound (6) can be produced and obtained in the same manner as compound (4). Compound (7) can be produced, for example, by the following reaction.

{In the formula,
Ar ³ and Ar ⁴ are independently monocyclic or condensed aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Each of the Xs independently represents a leaving group, and the two Xs may be the same or different from each other. }
As the leaving group represented by X and Y, the same one as described in the above reaction formula (1) is applied.

The present invention is an organic electroluminescent device containing a triazine compound represented by the general formula (1), and the triazine compound is preferably used for an electron transport layer, an electron injection layer, or a light emitting layer.

The triazine compound represented by the general formula (1) can be preferably used as an electron transporting material (electron transporting material, electron injecting material, etc.) of the organic electroluminescent device. At this time, for the anode, hole injection layer, hole transport layer, electron blocking layer, light emitting layer, light emitting layer dopant, light emitting layer host, cathode and the like used in combination, generally known materials can be selected by those skilled in the art. Can be used in.

The configuration of the organic electroluminescent device may be any conventionally known one, and is not particularly limited.

The method for producing a thin film for an organic electroluminescent device containing the compound (1) of the present invention is not particularly limited, and a preferable example thereof is film formation by a vacuum vapor deposition method. The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. The degree of vacuum in the vacuum chamber when forming a film by the vacuum vapor deposition method is that the manufacturing tact time for manufacturing organic electric field light emitting elements is short and the manufacturing cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, and cryopumps ^{It is preferably about 1 × 10 −2} to 1 × 10 ⁻⁶ Pa that can be reached by a pump or the like, and the vapor deposition rate is preferably 0.005 to 10 nm / sec depending on the thickness of the film to be formed. A thin film for an organic electroluminescent device made of compound (1) can also be produced by a solution coating method. For example, the compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, an inkjet method, a casting method or a general-purpose device is used. It is also possible to form a film by the dip method or the like.

Since the triazine compound represented by the general formula (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran and the like, spinco-using a general-purpose device is used. It is also possible to form a film by the trimethyl acetate method, the inkjet method, the casting method, the dip method or the like.

Typical structures of an organic electroluminescent device from which the effects of the present invention can be obtained include a substrate, an anode, a hole injection layer, a hole transport layer light emitting layer, an electron transport layer, and a cathode.

The anode and cathode of the organic electroluminescent device are connected to a power source via an electrical conductor. The organic electroluminescent device operates by applying an electric potential between the anode and the cathode. Holes are injected into the organic electroluminescent device from the anode, and electrons are injected into the organic electroluminescent device at the cathode.

The organic electroluminescent device is typically overlaid on the substrate and the anode or cathode can be in contact with the substrate. The electrodes that come into contact with the substrate are called lower electrodes for convenience. Generally, the lower electrode is an anode, but the organic electroluminescent device of the present invention is not limited to such a form.

The substrate may be light transmissive or opaque, depending on the intended emission direction. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is adopted as the substrate. The substrate may have a composite structure that includes multiple material layers.

When the electroluminescence emission is confirmed through the anode, the anode is formed by passing or substantially passing the emission.

Common transparent anode materials used in the present invention include indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide. Further, other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also preferably used. In addition to these oxides, metal nitrides such as gallium nitride, metal serene products such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode. The anode can be modified with plasma-deposited fluorocarbons.

If electroluminescence emission is confirmed only through the cathode, the transmission properties of the anode are not important and any transparent, opaque or reflective conductive material can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

The hole injection layer can be provided between the anode and the hole transport layer. The material of the hole injecting layer helps to improve the film forming properties of the organic material layer such as the hole transporting layer and the hole injecting layer and facilitate the injection of holes into the hole transporting layer. Examples of materials suitable for use in the hole-injected layer include porphyrin compounds, plasma-deposited fluorocarbon polymers, and amines with aromatic rings such as biphenyl and carbazole groups, such as m-MTDATA (4,4'). , 4''-Tris [(3-methylphenyl) phenylamino] triphenylamine), 2T-NATA (4,4', 4''-Tris [(N-naphthalen-2-yl) -N-phenylamino) ] Triphenylamine), triphenylamine, tritrilamine, trildiphenylamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N, N'N'-tetrakis (4-methylphenyl) -1,1'-biphenyl-4,4'-diamine, MeO-TPD (N, N, N'N'-tetrakis (4-methoxyphenyl) ) -1,1'-biphenyl-4,4'-diamine), N, N'-diphenyl-N, N'-dinaphthyl-1,1'-biphenyl-4,4'-diamine, N, N'- Bis (methylphenyl) -N, N'-bis (4-normalbutylphenyl) phenanthrene-9,10-diamine, N, N'-diphenyl-N, N'-bis (9-phenylcarbazole-3-yl) -1,1'-biphenyl-4,4'-diamine and the like can be mentioned.

The hole transport layer of the organic electroluminescent device preferably contains one or more hole transport compounds (hole transport materials), for example, an aromatic tertiary amine. Aromatic tertiary amines are compounds containing one or more trivalent nitrogen atoms, the trivalent nitrogen atoms being bonded only to carbon atoms, and one or more of these carbon atoms forming an aromatic ring. Is forming. Specifically, the aromatic tertiary amine may be an arylamine, such as a monoarylamine, a diarylamine, a triarylamine, or a high molecular weight arylamine.

As the hole transport material, an aromatic tertiary amine having one or more amino groups can be used. In addition, polymeric hole transport materials can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and the like can be used.

Specifically, NPD (N, N'-bis (naphthalen-1-yl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), α-NPD (N, N) '-Di (1-naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), TPBi (1,3,5-tris (1-phenyl-1H-benzimidazole-) 2-yl) benzene), TPD (N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine) and the like can be mentioned.

Dipyrazino [2,3-f: 2', 3'-h] quinoxalin-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer between the hole injection layer and the hole transport layer (HAT-CN), 7,7', 8,8'-Tetracyanoquinodimethane (TCNQ), 2,3,5,6-Tetrafluoro-7,7', 8,8'-Tetracyanoquinodimethane methane (F ₄ -TCNQ) or the like may be provided a layer containing, or may be doped with these compounds in the hole-transporting layer.

The light emitting layer of the organic electroluminescent device contains a phosphorescent material or a fluorescent material, in which case light emission occurs as a result of the recombination of electron-hole pairs in this region. The light emitting layer may be formed from a single material containing both small molecules and polymers, but more generally it is formed from a host material doped with a guest compound and the light emission originates primarily from the dopant. It can emit any color.

As the host material of the light emitting layer, a triazine compound represented by the general formula (1) can be used, and as other materials, for example, a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group and a pyrenyl group can be used. , Or a compound having an anthranyl group, and these materials can be used alone or mixed with a triazine compound represented by the general formula (1).

Specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazovinylene) 1,1 '-Biphenyl), TBADN (2-talshalbutyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis (4,4'-bis) Carbazole-9-yl) biphenyl), CDBP (4,4'-bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like. Further, a compound that expresses Thermally Activated Delayed Fluorescence (TADF) or the like can also be used.

The host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole-electron recombination, or a combination of these materials.

Examples of fluorescent dopants include pyrene, anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylenepyrane compounds, thiopyran compounds, polymethine compounds, pyrylium, or thiapyrylium compounds, fluorene derivatives, perifrantene derivatives, indeno Examples thereof include perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostylyl compounds, and compounds expressing thermally activated delayed fluorescence (TADF).

Examples of useful phosphorescent dopants include organometallic complexes of transition metals such as iridium, platinum, palladium and osmium.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4'-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples thereof include tris (2-phenylpyridine) iridium (III) and FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)).

As the thin film forming material used for forming the electron transport layer of the organic electroluminescent device of the present invention, a triazine compound represented by the general formula (1) of the present invention can be used. The electron transport layer may contain other electron transport materials. Examples of other electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes and the like.

Desirable alkali metal complexes, alkaline earth metal complexes, or earth metal complexes include, for example, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinate) zinc, bis (8-hydroxyquinolinate). ) Copper, bis (8-hydroxyquinolinate) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium , Bis (10-hydroxybenzo [h] quinolinate) berylium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) Examples thereof include (o-cresolate) gallium, bis (2-methyl-8-quinolinate) -1-naphtholate aluminum, and bis (2-methyl-8-quinolinate) -2-naphtholate gallium.

A hole blocking layer may be provided between the light emitting layer and the electron transporting layer for the purpose of improving the carrier balance. As the hole blocking layer, a triazine compound represented by the general formula (1) can be used, and as another material, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline). , Bphenyl (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2-methyl-8-quinolinolate) -4- (phenylphenanthroline) aluminum), bis (10-hydroxybenzo [h] quinolinate) Berylium) and the like.

In the organic electroluminescent device of the present invention, an electron injection layer may be provided for the purpose of improving the electron injection property and the device characteristics (for example, luminous efficiency, low voltage drive, or high durability).

Desirable compounds for the electron injection layer include triazine compounds represented by the general formula (1), fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, and the like. Examples thereof include fraolenilidene methane, anthraquinodimethane, and antron. Also, metal complexes and the alkali metal oxides noted above, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth _{halides, SiO X, AlO X, SiN} X, SiON, Inorganic compounds such as various oxides, nitrides, and oxide nitrides such as AlON, GeO _X , LiO _X , LiON, TiO _X , TiON, TaO _X , TaON, TaN _{X, C can also be used.}

If the luminescence is seen only through the anode, the cathode used in the present invention can be formed from almost any conductive material. Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium. , Lithium / aluminum mixture, rare earth metals and the like.

It is sectional drawing of the cross section of the organic electroluminescent element produced in the evaluation Example 1-1 and the like. It is sectional drawing of the cross section of the organic electroluminescent element produced in the evaluation Example 2-1 and the like. It is sectional drawing of the cross section of the organic electroluminescent element produced in the evaluation Example 3-1 and the like.

11. Glass substrate with ITO transparent electrode 12. Hole injection layer 13. First hole transport layer 14. Second hole transport layer 15. Light emitting layer 16. Electron transport layer 17. Cathode layer 21. Glass substrate with ITO transparent electrode 22. Hole injection layer 23. First hole transport layer 24. Second hole transport layer 25. Light emitting layer 26. First electron transport layer 27. Second electron transport layer 28. Cathode layer 31. Glass substrate with ITO transparent electrode 32. Hole injection layer 33. First hole transport layer 34. Second hole transport layer 35. Light emitting layer 36. Electron transport layer 37. Cathode layer

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, Comparative Examples and Reference Examples, but the present invention is not construed as being limited thereto.

Synthesis Example-1

Under an argon stream, 2- [3-chloro-5- (9-phenanthryl) phenyl] -4,6-diphenyl-1,3,5-triazine (5.20 g, 10 mmol), bispinacolato diboron (3. 81 g, 15 mmol), palladium acetate (22.5 mg, 0.10 mmol), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (95.4 mg, 0.20 mmol), and potassium acetate (2). .95 g, 30 mmol) was suspended in 1,4-dioxane (200 mL) and stirred at 100 ° C. for 4 hours. After allowing to cool, the precipitated component was removed by filtration. Chloroform (200 mL) and water (100 mL) were added and stirred, and then the aqueous layer and the organic layer were separated. Further, the aqueous layer was extracted 3 times with chloroform (50 mL) and combined with the organic layer. The low boiling point component was concentrated under reduced pressure from the organic layer and dried to obtain a crude product. Hexane was added, and the mixture was stirred and suspended while cooling to 0 ° C., and the obtained solid was collected by filtration. The obtained solid was dried under reduced pressure to give 2- [3-{(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)} -5- (9-phenyl). Phenyl] -4,6-diphenyl-1,3,5-triazine milky white powder (yield 6.07 g, yield 99%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.43 (s, 12H), 7.51-7.75 (m, 10H), 7.82 (s, 1H), 7.89-7. 98 (m, 2H), 8.23 (brs, 1H), 8.75-8.81 (m, 5H), 8.83 (brd, J = 8.2Hz, 1H), 9.01 (brs, brs, 1H), 9.24 (brs, 1H).
Synthesis Example-1

2- [3-{(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)} -5- (9-phenanthryl) obtained in Synthesis Example-1 under a nitrogen stream ) Phenyl] -4,6-diphenyl-1,3,5-triazine (1.00 g, 1.64 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (569 mg, 2.13 mmol) ), Palladium acetate (7.34 mg, 0.0327 mmol), and 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (31.2 mg, 0.0654 mmol) suspended in tetrahydrofuran (20 mL). , 2.0M-potassium phosphate aqueous solution (2.45 mL, 4.91 mmol) was added dropwise to the obtained suspension. The resulting mixture was stirred at 65 ° C. for 24 hours. The obtained reaction solution was allowed to cool to room temperature, and the precipitate was collected by filtration. The precipitate collected by filtration was washed successively with pure water, methanol and hexane to obtain a gray powder. The obtained gray powder was purified by recrystallization with toluene, and the desired product, 9- {3,5-bis (4,6-diphenyl-1,3,5-triazine-2-yl) phenyl} phenanthrene. A gray powder of (B-1) (yield 696 mg, yield 59%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.55-7.82 (m, 16H), 7.99-8.08 (m, 3H), 8.82-8.94 (m, 10H) ), 9.19 (s, 2H), 10.41 (s, 1H).
Synthesis Example-2

Compound A-2 (6.00 g), bis (pinacolato) diboron (3.17 g), potassium acetate (2.46 g), palladium acetate (23.4 mg), and 2-dicyclohexylphosphino-2'under an argon stream. , 4', 6'-triisopropylbiphenyl (99.5 mg) was suspended in THF (104 mL) and refluxed by heating for 91 hours. After allowing the reaction mixture to cool, the solid was filtered off and the solvent was evaporated under reduced pressure. When the obtained mixture was purified by column chromatography (developing solvent: chloroform, hexane), the desired 1- (4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) was obtained. A gray powder (yield 5.78 g, yield 83%) of -3,5-bis (4,6-diphenyl-1,3,5-triazine-2-yl) benzene (A-3) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 1.50 (s, 12H), 7.63-7.68 (m, 12H), 8.90-8.93 (m, 8H), 9. 37 (s, 2H), 10.36 (s, 1H).
Compound A-3 (5.72 g), bromobenzene (989 μL), and bis (triphenylphosphine) palladium dichloride (121 mg) were suspended in THF (86 mL) under an argon stream, and a 3M-potassium carbonate aqueous solution (6) was suspended therein. .3 mL) was added, and the mixture was heated under reflux for 72 hours. After allowing the reaction mixture to cool, water was added and the precipitate was collected by filtration. The sample was washed with water, MeOH, and hexane, and then recrystallized (xylene) to obtain the desired 3,5-bis (4,6-diphenyl-1,3,5-triazine-2-yl) biphenyl. A white powder of (B-2) (yield 4.04 g, yield 76%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.52 (t, J = 7.4Hz, 1H), 7.61-7.70 (m, 14H), 7.91-7.93 (m) , 2H), 8.89-8.92 (m, 8H), 9.22 (s, 2H), 10.24 (s, 1H).
Fabrication and Performance Evaluation of Organic Electroluminescent Device Containing the Triazine Compound of the Present Invention The present invention will be described with reference to the following test examples, but the present invention is not limited thereto. The structural formulas of the compounds used and their abbreviations are shown below.

Evaluation Example 1-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. After cleaning this substrate with isopropyl alcohol, surface treatment was performed by oxygen plasma cleaning. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light emitting area of 4 mm 2 as shown in FIG. 3 in a schematic cross-sectional view.}

First, the glass substrate was introduced into a vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 12, the first hole transport layer 13, the second hole transport layer 14, the light emitting layer 15, and the electron transport are used as the organic compound layer on the glass substrate with the ITO transparent electrode shown in FIG. The layers 16 were sequentially formed, and then the cathode layer 17 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 12, HIL-1 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 65 nm.

As the first hole transport layer 13, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec and a film thickness of 5 nm.

As the second hole transport layer 14, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 10 nm.

As the light emitting layer 15, EML-H1 and EML-D1 have a film thickness of 25 nm (EML-1 / EML-2 = 95.4 / 4.6 (weight ratio)) at a film thickness rate of 0.18 nm / sec. Vacuum vapor deposition was performed by vapor deposition).

As the electron transport layer 16, the compound B-1 and Liq synthesized in Synthesis Example-1 of the present invention have a film thickness of 30 nm at a film formation rate of 0.15 nm / sec (B-1 / Liq = 50/50 (B-1 / Liq = 50/50). Vacuum-deposited by co-evaporation) (weight ratio).

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and a cathode layer 17 was formed. In the cathode layer 37, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Comparison Example 1-1
In the electron transport layer 16 of Evaluation Example 1-1, organic electroluminescence is carried out in the same manner as in Evaluation Example 1-1 except that ETL-1, which is a known electron transport material, is used instead of Compound B-1. The device was manufactured.

A direct current was applied to the organic electroluminescent devices manufactured in Evaluation Example 1-1 and Evaluation Comparative Example 1-1, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. .. As the life characteristic, the brightness attenuation time at the time of continuous lighting when a current density of 10 mA / cm ^{2 was passed was measured.} The time when the brightness (cd / m ² ) was reduced by 10% was measured. The element life (h) of each evaluation example is a relative value, with the time (h) when the ^{brightness (cd / m 2) of the element in Comparative Example 1-1 is reduced by 10% from the initial stage as 100.} Indicated.

It was found that the organic electroluminescent device using the triazine compound of the present invention has excellent life characteristics as compared with Evaluation Comparative Example 1-1.

Evaluation Example 2-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. After cleaning this substrate with isopropyl alcohol, surface treatment was performed by oxygen plasma cleaning. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light emitting area of 4 mm 2 as shown in FIG. 2 in a schematic cross-sectional view.}

First, the glass substrate was introduced into a vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 22, the first hole transport layer 23, the second hole transport layer 24, the light emitting layer 25, and the first electron are formed as organic compound layers on the glass substrate with the ITO transparent electrode shown in FIG. The transport layer 26 and the second electron transport layer 27 were sequentially formed, and then the cathode layer 28 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 22, HIL-1 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 60 nm.

As the first hole transport layer 23, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec and a film thickness of 10 nm.

As the second hole transport layer 24, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 10 nm.

As the light emitting layer 25, mCBP and 4Cz-IPN, which is a TADF light emitting material known as mCBP, have a film thickness of 30 nm (mCBP / 4Cz-IPN = 85.0 / 15.0 (weight ratio) at a film formation rate of 0.18 nm / sec. ) Co-deposited) was vacuum-deposited.

As the first electron transport layer 26, the compound B-2 synthesized in Synthesis Example-2 of the present invention was vacuum-deposited at a film thickness of 0.15 nm / sec to a film thickness of 10 nm.

As the second electron transport layer 27, ETL-2 and Liq were vacuum-deposited at a film forming rate of 0.15 nm / sec with a film thickness of 40 nm (co-deposited with ETL-2 / Liq = 50/50 (weight ratio)). ..

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and a cathode layer 28 was formed. In the cathode layer 28, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Comparative Example 2-1
An organic electroluminescent device was produced in the same manner as in Evaluation Example 2-1 except that T2T was used in place of Compound B-2 in the first electron transport layer 26 of Evaluation Example 2-1.

A direct current was applied to the organic electroluminescent devices manufactured in Evaluation Example 2-1 and Evaluation Comparative Example 2-1 and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. .. As the life characteristic, the brightness attenuation time at the time of continuous lighting when a current density of 10 mA / cm ^{2 was passed was measured.} The time when the brightness (cd / m ² ) was reduced by 10% was measured. The element life (h) of each evaluation example is a relative value, with the time (h) when the ^{brightness (cd / m 2) of the element in Comparative Example 1-1 is reduced by 10% from the initial stage as 100.} Indicated.

It was found that the organic electroluminescent device using the triazine compound of the present invention has excellent life characteristics as compared with Evaluation Comparative Example 2-1.

Evaluation Example 3-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. After cleaning this substrate with isopropyl alcohol, surface treatment was performed by oxygen plasma cleaning. Each layer was vacuum-deposited on the washed substrate by a vacuum-film deposition method to produce an organic electroluminescent device having ^{a light emitting area of 4 mm 2 as shown in FIG. 3 in a schematic cross-sectional view.}

First, the glass substrate was introduced into a vacuum vapor deposition tank, and the pressure was reduced to ^{1.0 × 10 -4 Pa.}
After that, the hole injection layer 32, the first hole transport layer 33, the second hole transport layer 34, the light emitting layer 35, and the electron transport as organic compound layers on the glass substrate with the ITO transparent electrode shown in FIG. The layers 36 were sequentially formed, and then the cathode layer 37 was formed.

The materials forming each layer of the organic electroluminescent device were vacuum-deposited by a resistance heating method.

As the hole injection layer 32, HIL-1 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 60 nm.

As the first hole transport layer 33, HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / sec to a film thickness of 10 nm.

As the second hole transport layer 34, HTL-2 was vacuum-deposited at a film thickness of 0.15 nm / sec and a film thickness of 10 nm.

As the light emitting layer 35, mCBP and 4Cz-IPN, which is a TADF light emitting material known as mCBP, have a film thickness of 30 nm (mCBP / 4Cz-IPN = 85.0 / 15.0 (weight ratio) at a film formation rate of 0.18 nm / sec. ) Co-deposited) was vacuum-deposited.

As the electron transport layer 36, the compound B-2 synthesized in Synthesis Example-2 of the present invention was vacuum-deposited at a film thickness of 10 nm at a film formation rate of 0.15 nm / sec. Next, compounds B-2 and Liq were vacuum-deposited at a film forming rate of 0.15 nm / sec with a film thickness of 40 nm (co-deposited with B-2 / Liq = 50/50 (weight ratio)).

Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and a cathode layer 37 was formed. In the cathode layer 37, magnesium / silver (weight ratio 80/20) and silver are vacuum-deposited in this order at a film formation rate of 0.5 nm / sec and 0.2 nm / sec, respectively, at a film thickness of 80 nm and 20 nm. It has a two-layer structure.

Each film thickness was measured with a stylus type film thickness measuring meter (DEKTAK, manufactured by Veeco). Further, this element was sealed in a nitrogen atmosphere glove box having an oxygen and water concentration of 1 ppm or less. For sealing, a glass sealing cap and the film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Comparative Example 3-1
An organic electroluminescent device was produced in the same manner as in Evaluation Example 3-1 except that T2T was used in place of Compound B-2 in the electron transport layer 36 of Evaluation Example 3-1.

A direct current was applied to the organic electroluminescent devices manufactured in Evaluation Example 3-1 and Evaluation Comparative Example 3-1 and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. .. As a voltage characteristic, the drive voltage when a current density of 10 mA / cm ^{2 was passed was measured.} As a life characteristic, the brightness attenuation time at the time of continuous lighting when a current density of 10 mA / cm ^{2 was passed was measured.} The time when the brightness (cd / m ² ) was reduced by 10% was measured. The drive voltage (V) of each evaluation example is shown as a relative value with the drive voltage of the element in Comparative Example 3-1 as 100. The element life (h) is shown as a relative value, with the time (h) when the ^{brightness (cd / m 2} ) of the element in Comparative Example 3-1 is reduced by 10% from the initial stage as 100.

Compared with Evaluation Comparative Example 3-1 it was found that the organic electroluminescent device using the triazine compound of the present invention can be driven at a low voltage and has excellent life characteristics.

The organic electroluminescent device using the triazine compound of the present invention can be driven for a longer time than the organic electroluminescent device using an existing material. Further, the triazine compound of the present invention can be applied not only to the electron transport layer of the present embodiment but also to a light emitting host layer and the like. Further, it can be applied not only to an element using a fluorescent light emitting material but also to various organic electroluminescent devices using a phosphorescent light emitting material. Further, the triazine compound of the present invention has high solubility, and it is possible to fabricate an element using not only a vacuum deposition method but also a coating method. Further, it is useful not only for applications such as flat panel displays, but also for lighting applications that require low power consumption.

Claims (7)

General formula (1)

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, and an alkoxy having 3 to 10 carbon atoms. A group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon number consisting of only a 6-membered ring. It may have 6 to 30 monocyclic, linked, or condensed ring aromatic groups as substituents). }
A triazine compound represented by. General formula (2)

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, and an alkoxy having 3 to 10 carbon atoms. A group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon number consisting of only a 6-membered ring. It may have 6 to 30 monocyclic, linked, or condensed ring aromatic groups as substituents). }
The triazine compound according to claim 1, which is represented by. General formula (3)

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, and an alkoxy having 3 to 10 carbon atoms. A group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon number consisting of only a 6-membered ring. It may have 6 to 30 monocyclic, linked, or condensed ring aromatic groups as substituents). }
The triazine compound according to claim 1 or 2. A general, characterized in that a compound represented by the general formula (4) and a compound represented by the general formula (5) are coupled in the presence of a metal catalyst or a base and a metal catalyst. A method for producing a cyclic azine compound represented by the formula (1).

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a link, or a linking group. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, and an alkoxy having 3 to 10 carbon atoms. A group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon number consisting of only a 6-membered ring. It may have 6 to 30 monocyclic, linked, or condensed ring aromatic groups as substituents).
X and Y represent leaving groups. } A general, characterized in that a compound represented by the general formula (6) and a compound represented by the general formula (7) are coupled in the presence of a metal catalyst or a base and a metal catalyst. A method for producing a cyclic azine compound represented by the formula (1).

{In the formula,
Ar ^{1 to} Ar ⁴ are independently monocyclic or fused aromatic groups having 6 to 30 carbon atoms (the groups are a fluorine atom, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and the like. A halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a single ring having 6 to 30 carbon atoms, a linking group, or an alkyl group having 6 to 30 carbon atoms. It may have a fused ring aromatic group as a substituent.)
Ar ⁵ is a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms composed of only a 6-membered ring (the group is a fluorine atom, a methoxy group, an ethoxy group, and an alkoxy having 3 to 10 carbon atoms. A group, a halogenated alkoxy group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a carbon number consisting of only a 6-membered ring. It may have 6 to 30 monocyclic, linked, or condensed ring aromatic groups as substituents).
X and Y represent leaving groups. } A material for an organic electroluminescent device containing the triazine compound according to any one of claims 1 to 3. An electron injection material, an electron transport material, or a light emitting material for an organic electroluminescent device containing the triazine compound according to any one of claims 1 to 3.

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