JP2013144675A - Anthracene derivative, organic el material, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anthracene derivative in which a specific solubility radical is introduced into an anthracene skeleton, thereby improving solubility, and that is suitable to be used for film production in a solution process, and further to provide an anthracene derivative in which a specific solution radical of the anthracene derivative is desorbed by an external stimulation, and that is as an organic EL material excellent in characteristics.SOLUTION: For instance, anthracene derivatives (HTL1) and (HTL2) are exemplified to be synthesized by reaction formula (A). The anthracene derivative excellent in organic EL characteristics is obtained by the desorption of an ester group by an external stimulation.

Description

  The present invention relates to a novel anthracene derivative, and more particularly to an anthracene derivative having a detachable soluble group and useful as a constituent material of an organic EL device having excellent solubility, film-forming property, and various photoelectric characteristics.

In recent years, organic semiconductor materials have attracted a great deal of attention as optoelectronic materials due to their various optical and electrical properties, and are actively researched and developed. In particular, an organic electroluminescence (hereinafter referred to as organic EL) element, which is a light emitting device using a light emitting organic semiconductor, recombines holes and electrons injected by applying an electric field to an organic substance on an organic molecule. It is a device that utilizes the phenomenon of generating excitons and emitting light by its radiation deactivation, and is expected to be applied to display devices such as televisions and mobile terminals, and further to illumination light sources.
For this reason, development of a technique for driving the organic EL element at a low voltage and various techniques for increasing the light emission efficiency of the organic EL element are in progress.
The organic EL element is configured by, for example, forming a plurality of organic thin film layers between a transparent electrode such as indium-tin oxide (hereinafter referred to as ITO) and a metal electrode such as aluminum.
The organic layer includes a light emitting material (light emitting layer), and the light emitting material has a structure in which a voltage is applied via a transparent electrode and a metal electrode. When a voltage is applied between the transparent electrode and the metal electrode, holes are injected from the transparent electrode and electrons are injected from the metal electrode according to the direction of the applied electric field. The electrons and holes recombine in the light emitting material. Light emission occurs.

  The theoretical light emission efficiency of an organic EL element is given by the product of light extraction efficiency, carrier recombination efficiency, exciton generation efficiency, and light emission quantum yield. It has become an important technical problem to increase the light emission quantum yield of the organic light emitting dye used as the light emitting layer. However, organic luminescent dyes show a significant decrease in luminescence quantum yield called concentration quenching at high concentration conditions. This is because excitation energy transfer and self-absorption of light occur between adjacent molecules. (See Non-Patent Document 1, Appl. Phys. Lett. 86, 071104 (2005)).

Accordingly, the light emitting layer in the organic EL element is generally used in a solid state in which an organic light emitting dye is dispersed at a low concentration in an optically inert medium (hereinafter referred to as a host). Here, as the host material, a material having an energy gap larger than that of the organic light-emitting dye is generally used.
For example, the following two types of methods can be considered as a method for producing the light-emitting organic thin film.
(1) Evaporation-dispersed thin film: An organic light emitting thin film is formed by dispersing an organic light emitting dye material as a guest material in a host material made of a low molecular material. The organic light-emitting thin film is formed by, for example, a vacuum deposition method (see Japanese Patent Application Laid-Open No. 2000-68057 of Patent Document 1 and Japanese Patent Application Laid-Open No. 2010-034484 of Patent Document 2).
(2) Polymer-dispersed thin film: An organic light-emitting thin film is formed by dispersing an organic light-emitting dye material as a guest material in a host material made of a polymer material. The organic light-emitting thin film is formed by, for example, a coating method. (See Japanese Patent Application Laid-Open No. 2007-305783 in Patent Document 3)
However, all of the above technical methods have problems. First, in order to appropriately control the doping concentration of guest molecules, the deposition-dispersed thin film requires an advanced deposition rate control technique for strictly adjusting the deposition rates of guest molecules and host molecules. Furthermore, in order to obtain white light as an illumination light source, it is necessary to simultaneously dope a plurality of organic light emitting dye materials exhibiting red, green and blue by vapor deposition. It is necessary to strictly control the deposition rate of the host molecules. This is very difficult, and it is difficult to say that practicality and productivity are high. In addition, the development cost and development time for that are large, and it does not meet the expectation for an organic semiconductor material that a thin film can be formed by a simple process such as coating or printing. On the other hand, in the polymer-dispersed thin film, since the coating method is used, it is not necessary to strictly adjust the deposition rates of the guest material and the host material, and the manufacturing process can be simplified. However, in the polymer-dispersed thin film, phase separation occurs between the polymer material and the low-molecular material due to heat treatment, etc., and uniform dispersion is difficult, and the light emission efficiency is an element using the low-molecular material. There was a problem that it was low compared with.

The wet film formation method such as the polymer dispersion method does not require a vacuum process and can easily increase the area, and a plurality of materials having various functions can be mixed in one layer (coating liquid). There are advantages such as being easy. However, since these wet film forming methods are difficult to stack, the driving stability is inferior to that of an element formed by a vacuum vapor deposition method, and the present situation is that the practical level is not reached except for a part.
As a method of layering by a wet film formation method, a first layer is formed using a polymer insoluble in an organic solvent and an aqueous solvent, and a second layer is formed thereon using an organic solvent. However, it was difficult to laminate three or more layers.

Further, as the host or dopant, a condensed aromatic compound having an anthracene skeleton is often used. As an example, 9,10-di (2-naphthyl) anthracene well known by the abbreviation “ADN” (see, for example, US Pat. No. 5,935,721 of Patent Document 4), 9-naphthyl-10 -Phenylanthracene derivatives (for example, US Patent Application Publication No. 2006/0014046 of Patent Document 5) and 9-biphenyl-10-naphthylanthracene derivatives (for example, refer to WO2005 / 080527 of Patent Document 6, pamphlet) and the like Is used as a host of a light emitting layer, and a technique for improving the lifetime of an organic electroluminescent device using bis-anthracene as a light emitting layer is also disclosed (for example, US Pat. No. 6,534, Patent Document 7). No. 199).
However, the “ADN” compound has high crystallinity and insufficient solubility, and it has been difficult to form a suitable organic EL active layer using the above-described wet film-forming method.
In addition, efforts have been made to improve solubility by introducing ortho- or meta-substituted aromatic functional groups as spacers to the anthracene skeleton. (See Japanese Patent Application Laid-Open No. 2008-166629 of Patent Document 8)
However, in this method, since an ortho- or meta-substituted structure must be incorporated in the molecule, the degree of freedom in molecular design is limited, and there is a problem in improving characteristics.
By the way, as a means for solubilizing the condensed aromatic compound as described above, we have proposed a precursor system that imparts a detachable soluble substituent. (For example, Japanese Patent Application Laid-Open No. 2011-213705 of Patent Document 9 and Japanese Patent Application No. 2011-086973 of Patent Document 10)
In this case, a precursor material substituted at positions 2 and 6 of anthracene is mentioned, which is designed in pursuit of crystallinity and carrier mobility, and is particularly suitable as an organic EL material host in the present invention. Derivatives such as ADN having an aromatic substituent at the 9th and 10th positions of anthracene exhibiting luminescent properties are not disclosed.

  In order to solve the above problems, the present inventors provide an anthracene derivative suitable for use in film formation in a solution process by increasing the solubility by introducing a specific soluble group into the anthracene skeleton, In addition, an object of the present invention is to provide an anthracene derivative as an organic EL material having excellent characteristics by desorbing a specific dissolving group of the anthracene derivative by an external stimulus.

As a result of intensive investigations, the present inventors have found that “the new anthracene derivatives”, “materials for organic electroluminescence elements”, “light emitting materials for organic electroluminescence elements”, “organic electroluminescence elements” described in the following (1) to (10) The present invention including the “luminescent material ink”, “organic electroluminescent light emitting material ink”, “manufacturing method of an anthracene derivative-containing film” and “manufacturing method of an anthracene derivative” has found that the above-mentioned problems can be solved. It came.
(1) "Anthracene derivative represented by the following general formula (1);

（一般式（１）中、Ａｒ_１およびＡｒ_２は、それぞれ独立に、［下記一般式（１−１）および一般式（１−２）で示される部分構造を有する基、置換もしくは無置換の核炭素数１から３０の芳香族環またはヘテロ環から誘導される基］で形成される群から選択される基である。
Ｒ^１からＲ^８は、水素原子、下記一般式（１−１）または一般式（１−２）で示される部分構造を有する置換基、置換もしくは無置換の核炭素数６から５０のアリール基、置換もしくは無置換の核原子数５から５０のヘテロアリール基、置換もしくは無置換の炭素数１から５０のアルキル基、置換もしくは無置換の炭素数３から５０のシクロアルキル基、置換もしくは無置換の炭素数１から５０のアルコキシ基、置換もしくは無置換の炭素数６から５０のアラルキル基、置換もしくは無置換の核原子数５から５０のアリールオキシ基、置換もしくは無置換の核原子数５から５０のアリールチオ基、置換もしくは無置換のシリル基、カルボキシル基、ハロゲン原子、シアノ基、ニトロ基およびヒドロキシ基から選ばれる。
また、隣接する置換基同士は互いに結合して飽和または不飽和の環状構造を形成していてもよい。
ただし、Ａｒ_１およびＡｒ_２、Ｒ_１乃至Ｒ_８のうち少なくとも１つ以上は、下記一般式（１−１）または（１−２）で示される部分構造を有する置換基である。）

(In the general formula (1), Ar ₁ and Ar ₂ are each independently a group having a partial structure represented by the following general formula (1-1) or general formula (1-2), substituted or unsubstituted A group selected from the group formed by an aromatic ring or a heterocyclic ring having 1 to 30 nuclear carbon atoms].
R ¹ to R ⁸ are a hydrogen atom, a substituent having a partial structure represented by the following general formula (1-1) or general formula (1-2), a substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms. Substituted or unsubstituted heteroaryl group having 5 to 50 nucleus atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted From an alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted nuclear number 5 It is selected from 50 arylthio groups, substituted or unsubstituted silyl groups, carboxyl groups, halogen atoms, cyano groups, nitro groups and hydroxy groups.
Further, adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.
However, at least one of Ar ₁ and Ar ₂ and R _{1 to} R ₈ is a substituent having a partial structure represented by the following general formula (1-1) or (1-2). )

（一般式（１−１）、（１−２）中、ＸおよびＹ、（Ｘ_１とＸ_２）および（Ｙ_１とＹ_２）は水素原子もしくは脱離性置換基を表し、該ＸおよびＹのうち一方、（Ｘ_１とＸ_２）および（Ｙ_１とＹ_２）のうち一方は脱離性置換基であり、他方は水素原子である。Ｑ_１乃至Ｑ_６は水素原子、ハロゲン原子または前記脱離性置換基以外の有機基であり、それぞれ結合して環を形成していてもよい。）。」

(In the general formulas (1-1) and (1-2), X and Y, (X ₁ and X ₂ ) and (Y ₁ and Y ₂ ) represent a hydrogen atom or a leaving substituent, One of Y, (X ₁ and X ₂ ) and (Y ₁ and Y ₂ ) is a leaving substituent and the other is a hydrogen atom, Q _{1 to} Q ₆ are a hydrogen atom, a halogen atom Or an organic group other than the above-mentioned leaving substituent, which may be bonded to each other to form a ring). "

(2) “In the general formulas (1-1) and (1-2), the leaving substituents X or Y, (X ₁ and X ₂ ) or (Y ₁ and Y ₂ ) are substituted. The anthracene derivative according to item (1), which is an [ether group or acyloxy group] having 1 or more carbon atoms, and the other is a hydrogen atom.
(3) “The anthracene derivative according to (1) or (2), wherein R ₂ , R ₃ , R ₆ and R ₇ are all hydrogen atoms”
(4) Said R ₁ , R _4, R _{5 and} R ₈ are groups selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group ( The anthracene derivative according to any one of items 1) to (3). "
(5) “Anthracene derivative according to any one of Items (1) to (4), which is a material for an organic electroluminescence device”.
(6) “The anthracene derivative according to item (5), wherein the organic electroluminescent element material is a light emitting material for an organic electroluminescent element.”
(7) “An organic electroluminescent material ink containing at least the solvent and the anthracene derivative according to any one of (1) to (4)”.
(8) The organic electroluminescence emission according to item (7) above, comprising a solvent, the anthracene derivative according to any one of items (1) to (4), and a luminescent dye. Material ink. "
(9) “The film formed using the ink according to the item (7) or (8) is given an external stimulus to desorb a desorbing component and desorb the desorbable substituent. , A method for producing an anthracene derivative-containing film characterized by forming a double bond. "
(10) “Anthracene derivative characterized by applying an external stimulus to the anthracene derivative according to the above (1) to (4) to eliminate the leaving substituent and form a double bond Manufacturing method. "

  As will be well understood from the following detailed and specific description, the present invention provides an anthracene derivative that has a specific solubility group and is highly soluble and can form a suitable thin film by a solution process. it can. In addition, the dissolving group can be eliminated and removed by applying an external stimulus as needed, and as a result, an anthracene derivative as an organic EL material having more excellent characteristics is provided. The effect is played.

It is a schematic diagram which shows suitable embodiment of an organic EL element. It is a measurement result of TG-DTA of the anthracene derivative (HTL1) of the present invention. It is a result of TG-DTA of the anthracene derivative (HTL5) of the present invention. The relationship between the voltage and current density of an organic EL device using a precursor type host / guest type organic light emitting thin film comprising the anthracene derivative heat conversion film of the present invention and a light emitting dye (D-1) as the light emitting layer is shown. It is a graph. It is the graph which showed the relationship between the voltage of an organic electroluminescent element using the host-guest type organic light emitting thin film which consists of an anthracene derivative heat conversion film | membrane of this invention, and a luminescent pigment | dye (D-1) as a light emitting layer, and a luminance. is there. EL spectrum when the current density of the organic EL device using the host-guest type organic light-emitting thin film comprising the anthracene derivative heat conversion film of the present invention and the light-emitting dye (D-1) as the light-emitting layer is 10 mA / cm ² It is the graph which showed.

  Hereinafter, the present invention will be described in detail and specifically with reference to embodiments, but the present invention is not limited to the following embodiments, and may be arbitrarily modified and implemented without departing from the scope of the present invention. be able to.

[Anthracene derivatives]
As described above, the anthracene derivative in the present invention is represented by the following general formula (1).

In general formula (1), Ar ₁ and Ar ₂ are each independently [a group having a partial structure represented by the following general formula (1-1) or general formula (1-2), a substituted or unsubstituted nucleus A group selected from the group formed by a group derived from an aromatic ring or heterocycle having 1 to 30 carbon atoms].
R ¹ to R ⁸ are a hydrogen atom, a substituent having a partial structure represented by the following general formula (1-1) or general formula (1-2), a substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms. Substituted or unsubstituted heteroaryl group having 5 to 50 nucleus atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted From an alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted nuclear number 5 It is selected from 50 arylthio groups, substituted or unsubstituted silyl groups, carboxyl groups, halogen atoms, cyano groups, nitro groups and hydroxy groups.
Further, adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.
However, at least one of Ar ₁ and Ar ₂ and R _{1 to} R ₈ is a substituent having a partial structure represented by the following general formula (1-1) or (1-2).

The substituents having the partial structures represented by the general formulas (1-1) and (1-2) in Ar ₁ and Ar ₂ will be described later. Examples of the group derived from a substituted or unsubstituted aromatic ring or heterocyclic ring having 1 to 30 nuclear carbon atoms in Ar ₁ and Ar ₂ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 6-chrenyl group, 1-benzo [c] phenanthryl group, 2-benzo [c] phenanthryl group, 3-benzo [c] phenanthryl group, 4-benzo [C] Phenanthryl group, 5-benzo [c] phenanthryl group, 6-benzo [c] phenanthryl group, 1-benzo [ ] Chrysenyl group, 2-benzo [g] chrysenyl group, 3-benzo [g] chrysenyl group, 4-benzo [g] chrysenyl group, 5-benzo [g] chrysenyl group, 6-benzo [g] chrysenyl group, 7 -Benzo [g] chrysenyl group, 8-benzo [g] chrysenyl group, 9-benzo [g] chrysenyl group, 10-benzo [g] chrysenyl group, 11-benzo [g] chrysenyl group, 12-benzo [g] Chrysenyl group, 13-benzo [g] chrysenyl group, 14-benzo [g] chrysenyl group, 1-triphenyl group, 2-triphenyl group, 2-fluorenyl group, 9,9-dimethylfluoren-2-yl group, Benzofluorenyl group, dibenzofluorenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-ter Phenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl Group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4 In addition to -methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 "-t-butyl-p-terphenyl-4-yl group, 1,3,5-triphenylbenzene 2,4,6 -The substituent etc. which substituted arbitrary hydrogen of triphenyl l-1,3,5-triazine are mentioned.

The groups represented by general formulas (1-1) and (1-2) in R ¹ to R ⁸ will be described later. The substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms in R ¹ to R ⁸ is a substituted or unsubstituted heteroaryl group having 5 to 50 nuclear atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. Group, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted Examples of aryloxy groups having 5 to 50 nucleus atoms, substituted or unsubstituted arylthio groups having 5 to 50 nucleus atoms, substituted or unsubstituted silyl groups, carboxyl groups, halogen atoms, cyano groups, nitro groups and hydroxy groups Is included in the same range as Q _{1 to} Q ₆ described later. Further, adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.

[Specific substituents including leaving substituents]
A group having a partial structure represented by the following general formula (1-1) or (1-2) in Ar ₁ and Ar ₂ and R _{1 to} R ₈ will be described.

These specific substituents are characterized by having a cyclohexene skeleton or a cyclohexadiene skeleton and a leaving substituent (the entire structural site is referred to as a soluble substituent).
The so-called soluble substituent portion of the structure consisting of this cyclohexene skeleton or cyclohexadiene skeleton and a leaving substituent is not rigid and sterically bulky, so that the crystallinity is poor, and molecules having such a structure are dissolved. The film has good properties and has a property that an amorphous film having low crystallinity or amorphousness can be easily obtained when applied using a solution in which a substituent-elimination compound is dissolved.

In the formulas (1-1) and (1-2), X and Y, (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) represent a hydrogen atom or a leaving substituent, and the X and Y, One of (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is a leaving substituent, and the other is a hydrogen atom. Q _{2 to} Q ₅ are each independently a hydrogen atom, a halogen atom or an organic group, Q ₁ and Q ₆ are an organic group excluding a hydrogen atom or the above-mentioned leaving substituent, and Q _{1 to} Q ₆ are adjacent to each other. Bonded groups may be bonded to each other to form a ring.

In the formulas (1-1) and (1-2), the groups represented by X and Y, (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) are a hydrogen atom or a leaving substituent. Such groups include halogen atoms, hydrosyl groups, optionally substituted ether groups or optionally substituted acyloxy groups, optionally substituted sulfonyloxy groups, nitroxyl groups, substituted Examples include a group capable of withdrawing hydrogen on the β-carbon, such as a good phosphooxy group, an optionally substituted alkylamine oxide group, and an optionally substituted polyalkyl quaternary ammonium salt. From the viewpoints of stability, solubility in organic solvents, and conditions for elimination of substituents (whether or not a catalyst is added, reaction temperature, etc.), an ether group which may be substituted or a substituted group is preferable. And an optionally substituted acyloxy group and an optionally substituted sulfonyloxy group. Particularly preferred is an ether group which may be substituted or an acyloxy group which may be substituted.

At least one of X and Y, (X ₁ , X ₂ ) and (Y ₁ , Y ₂ ) is a leaving substituent (that is, an optionally substituted ether group having 1 or more carbon atoms or a substituted substituent). And the other is a hydrogen atom.
The ether group having 1 or more carbon atoms which may be substituted is derived from an alcohol such as a linear or cyclic aliphatic alcohol having 1 or more carbon atoms or an aromatic alcohol having 4 or more carbon atoms. Of ether groups. Further, a thioether group in which an oxygen atom in the ether is replaced with a sulfur atom can also be included. The carbon number of the ether group is usually C1 to C38, preferably C2 to C22, and more preferably C3 to C18 in consideration of various effects such as solubility and the boiling point of the leaving component.
Specifically, for example, methoxy group, ethoxy group, propoxy group, butoxy group, isobutoxy group, pivaloyl group, pentoxy group, hexyloxy group, lauryloxy group, trifluoromethoxy group, 3,3,3-trifluoropropoxy group, Pentafluoropropoxy group, cyclopropoxy group, cyclobutoxy group, cyclohexyloxy group, trimethylsilyloxy group, triethylsilyloxy group, tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group, etc. Corresponding thioethers in which oxygen is replaced with sulfur are also included.

Examples of the acyloxy group having 1 or more carbon atoms which may be substituted include a formyloxy group, a linear or cyclic aliphatic carboxylic acid and carbonic acid half ester which may contain a halogen atom having 2 or more carbon atoms, carbon Examples thereof include acyloxy groups derived from carboxylic acids and carbonic acid half esters such as aromatic carboxylic acids having a number of 4 or more. Moreover, thiocarboxylic acid in which the oxygen atom of the carboxylic acid is replaced with sulfur can also be included. The carbon number of the acyloxy group is usually C1 to C38, preferably C2 to C22, and more preferably C3 to C18 in consideration of various effects such as solubility and boiling point of the leaving component.
Specifically, for example, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, pentanoyloxy, hexanoyloxy, lauroyloxy group, stearoyloxy group, trifluoroacetyloxy 3,3,3-trifluoropropionyloxy, pentafluoropropionyloxy, cyclopropanoyloxy, cyclobutanoyloxy, cyclohexanoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, pentafluorobenzoyloxy group Etc.
In addition, a carbonic acid ester derived from a carbonic acid half ester in which an oxygen atom or a sulfur atom is inserted between the carbonyl group of the acyloxy group exemplified above and an alkyl group or an aryl group can also be mentioned. In addition, corresponding acylthiooxy compounds and thioacyloxy compounds in which one or more of oxygen at the ether bond site and the carbonyl site are replaced with sulfur are also included.

  Some preferred examples of the leaving substituents X and Y of the above concept are exemplified below.

Introduction of an optionally substituted ether group having 1 or more carbon atoms or an acyloxy group (group having a leaving property) in the present invention, while maintaining high solubility in an organic solvent and stability of the compound, compared with conventional ones. The elimination reaction of the leaving group can be enabled with low energy (heating).
For example, as the leaving group, a substituted or unsubstituted ether group having 1 or more carbon atoms and a sulfonyloxy group having 1 or more carbon atoms may be introduced instead of an acyloxy group.
Examples of the optionally substituted sulfonyloxy group include sulfonyloxy groups derived from sulfonic acids such as linear or cyclic aliphatic sulfonic acids having 1 or more carbon atoms and aromatic sulfonic acids having 4 or more carbon atoms. It is done. Specifically, for example, methylsulfonyloxy group, ethylsulfonyloxy group, isopropylsulfonyloxy group, pivaloylsulfonyloxy group, pentanoylsulfonyloxy group, hexanoylsulfonyloxy group, trifluoromethanesulfonyloxy group, 3, 3 , 3-trifluoropropionylsulfonyloxy group, phenylsulfonyloxy group, p-toluenesulfonyloxy group, and the like, and a sulfonylthiooxy group in which the oxygen atom of the ether moiety is replaced with a sulfur atom can also be included. The carbon number of the sulfonyloxy group is usually C1 to C38, preferably C2 to C22, more preferably C3 to C18 in consideration of various effects such as solubility and the boiling point of the leaving component.

In addition, as described above, the organic group represented by Q _{1 to} Q ₆ in the present invention is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or an organic group ( However, in Q _{1 to} Q ₆ , an optionally substituted ether group or monovalent organic group other than an acyloxy group having 1 or more carbon atoms is used. Examples of the organic group include an alkyl group, an alkenyl group, Alkynyl, aryl, heteroaryl, aralkyl, alkoxyl, thioalkoxyl, aryloxy, thioaryloxy, heteroaryloxy, heteroarylthiooxy, cyano, hydroxyl, nitro, carboxyl Group, thiol group, amino group and the like.

The alkyl group represents a linear or branched or cyclic substituted or unsubstituted alkyl group.
Examples thereof include an alkyl group [preferably a substituted or unsubstituted alkyl group having 1 or more carbon atoms [eg, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group]. Group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group, cycloalkyl group (preferably substituted or Unsubstituted alkyl group having 3 or more carbon atoms (for example, cyclopentyl group, cyclobuty Group, a cyclohexyl group, pentafluoro cyclohexyl group), 1-adamantyl group, and a 2-adamantyl group.
In other organic groups described below, the alkyl group represents an alkyl group of the above concept.

  The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Examples thereof include an alkenyl group [preferably a substituted or unsubstituted alkenyl group having 2 or more carbon atoms, and one or more double bonds of any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. [For example, ethenyl group (vinyl group), propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group Group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 1-octenyl group, 2-octenyl group Group, 3-octenyl group, 4-octenyl group, 1,1,1-trifluoro-2-butenyl group]. ], A cycloalkenyl group [which includes one or more double bonds of any carbon-carbon single bond of the cycloalkyl group having 2 or more carbon atoms described above [for example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group]. ] Etc. are mentioned. The alkenyl group may be any of stereoisomers such as trans (E) isomer and cis (Z) isomer, and may be a mixture composed of any ratio thereof. .

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 or more carbon atoms, wherein one or more triple bonds are formed from any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. Can be mentioned. Examples of such alkynyl groups include ethynyl group, propargyl group, trimethylsilylethynyl group, and triisopropylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 or more carbon atoms [for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluoro. Phenyl, naphthyl, etc.].

  The heteroaryl group is preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound [for example, 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl. , 2-benzothienyl, 2-pyrimidyl, etc.].

  Examples of the aralkyl group (the aryl moiety has 6 to 49 carbon atoms and the alkyl moiety has 1 to 44 carbon atoms) include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, and 2-phenylisopropyl. Group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthyl Methyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chloro Benzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group O-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m -Cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group, etc.

  The alkoxyl group and thioalkoxyl group are preferably substituted or unsubstituted alkoxyl groups and thioalkoxyl groups, and an oxygen atom or a sulfur atom is inserted at the bonding position of the alkyl group, alkenyl group, and alkynyl group exemplified above. Specific examples thereof include alkoxy groups or thioalkoxy groups.

  The aryloxy group and thioaryloxy group are preferably a substituted or unsubstituted aryloxy group and an arylthiooxy group, and an aryl or oxygen atom is inserted into the aryl group binding site exemplified above. Specific examples include an oxy group or a thioalkoxy group.

  The heteroaryloxy group and heterothioaryloxy group are preferably a substituted or unsubstituted heteroaryloxy group and heteroarylthiooxy group, and an oxygen atom or a sulfur atom at the binding site of the heteroaryl group exemplified above. Specific examples include those in which a heteroaryloxy group or a heteroarylthioaryloxy group is inserted.

  The amino group is preferably an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group [for example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group. Group, diphenylamino group], acylamino group [preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, [for example, formylamino, acetylamino, pivaloylamino group, lauroyl Amino, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group]], aminocarbonylamino group [preferably a carbon-substituted or unsubstituted aminocarbonylamino group (for example, carbamoylamino group, N, N-dimethyl Aminocarbonylamino group, N, N-diethylamino carbonyl amino group, a morpholinocarbonylamino group)], and the like.

The organic group represented by Q _{1 to} Q ₆ can be represented in the above-described range, but is preferably an aryl group or a heteroaryl group which may have a substituent, or adjacent to it. That is, the matching groups form a ring structure. More preferably, the cyclic structure comprises an optionally substituted aryl group or heteroaryl group.
As an example of the ring bond or condensed ring form, the following structures I- (1) to I- (42) are exemplified by taking the structure derived from the general formula (1-2) as an example.

Specific examples of the aryl group or heteroaryl group which may have a substituent forming the cyclic structure include a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine. A ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a furan ring, a thiophene ring, a selenophene ring, and a silole ring are preferable, and the following (i) and (ii) are more preferable.
(I): one or more aryl and heteroaryl groups, or a cyclic compound residue in which the rings are condensed (ii): a ring in which the rings in (i) are linked via a covalent bond Compound residue

Further, a π-conjugated compound residue selected from a combination selected from at least one selected from the group formed by (i) and (ii) above is preferred, and the aromatic hydrocarbon ring or aromatic heterocycle thereof is It is preferable that each π electron has a structure that is delocalized in the condensed ring or the entire linking ring by the interaction by the connection via the condensed ring and the covalent bond.
Examples of the covalent bond here include a carbon-carbon single bond, a carbon-carbon double bond, a carbon-carbon triple bond, an oxyether bond, a thioether bond, an amide bond, and an ester bond. , Either a double bond or a triple bond.

[Conversion of specific substituents including leaving substituents]
The above-mentioned soluble substituent (substituent having a specific structure including a detachable substituent) is characterized in that the structure can be converted by eliminating the detachable substituent.
That is, as shown in the following formula, X and Y or (X ₁ , X ₂ ) and (Y ₁ ) composed of a leaving substituent and a hydrogen atom from the soluble substituent (Ia) or (Ib). , Y ₂ ) are eliminated in the form of compound XY (IIIa) or compound X1-Y1 (IIIb1) and compound X2-Y2 (IIIb2) and converted into the corresponding benzene structure (II) (soluble substitution) In the case of the group (Ib), a part of X and Y is eliminated and a compound (II-1) or a compound (II-2) having a photoelectric property similar to that of the compound (II) coexists. In this case as well, it is described as “benzene structure (II)” together with the case where all X and Y are eliminated.

Usually, the elimination reaction depends on the structure of the functional group, but it is often necessary to apply external energy from the viewpoint of reaction rate and reaction rate.
For this purpose, the energy to be applied (applied) includes heat, light, and electromagnetic waves. From the viewpoint of reactivity, yield, and post-treatment, thermal energy or light energy is desirable, and thermal energy is particularly preferable. Moreover, you may apply the said energy in presence of an acid or a base. The heating method for carrying out the elimination reaction includes a method of heating on a support, a method of heating in an oven, a method of irradiation with microwaves, a method of heating by converting light into heat using a laser, Although various methods, such as using a photothermal conversion layer, can be used, it is not limited to these.

  Regarding the heating temperature, it is possible to use a range of room temperature (approximately 25 ° C.) to 500 ° C., and the lower limit temperature considers the thermal stability of the material and the boiling point of the desorbing component. In consideration of the abundance of unconverted molecules, decomposition of the compound after conversion, sublimation, etc., a range of 40 ° C. to 500 ° C. is preferable, and more preferably in consideration of thermal stability during the synthesis of the substituent elimination compound. It is the range of 60 to 500 degreeC, Most preferably, it is 80 to 400 degreeC.

  Regarding the heating time, the higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the time required for the elimination reaction. Further, although depending on the reactivity and amount of the substituent-eliminating compound, it is usually 0.5 minutes to 120 minutes, preferably 1 minute to 60 minutes, and particularly preferably 1 minute to 30 minutes.

  When light is used as an external stimulus, an infrared lamp, irradiation with light having a wavelength absorbed by the compound (for example, exposure to a wavelength of 405 nm or less), and the like may be used. At that time, a semiconductor laser may be used. For example, near-infrared laser light (usually laser light having a wavelength of around 780 nm), visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and laser light having a wavelength of 390 to 440 nm can be mentioned. Laser light having a wavelength of 390 to 440 nm is particularly preferable, and semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. Among them, as a preferable light source, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 390 to 440 (more preferably 390 to 415 nm) and an infrared semiconductor laser light having a central oscillation wavelength of 850 nm are half wavelength using an optical waveguide device. And blue-violet SHG laser light having a central oscillation wavelength of 425 nm.

In the elimination reaction of the detachable substituent, the acid or base acts as a catalyst, and conversion at a lower temperature is possible. The method of using these is not particularly limited, but it may be added as it is to the substituent-eliminating compound, or it may be dissolved in any solvent and added as a solution, or it is vaporized in the atmosphere. Heat treatment may be performed, and a photoacid generator and a photobase generator may be added to obtain an acid and a base in the system by light irradiation.
Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, 3,3,3-trifluoropropionic acid, formic acid, phosphoric acid, 2-butyloctanoic acid, and the like. it can.
As the photoacid generator, ionic generators such as sulfonium salts and iodonium salts and nonionic generators such as ionic photoacid generator imide sulfonate, oxime sulfonate, disulfonyldiazomethane, and nitrobenzyl sulfonate can be used. .
Examples of the base include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium hydrogen carbonate, sodium carbonate and potassium carbonate, amines such as triethylamine and pyridine, diazabicycloundecene, diazabicyclo Amidines such as nonene can be used.
As the photobase generator, carbamates, acyl oximes, ammonium salts and the like can be used.
Of these, it is preferable to carry out the reaction in an atmosphere of a volatile acid or base in view of ease of removal of the acid-base after the reaction.
The atmosphere for the desorption reaction can be performed in the air with or without the above catalyst. However, in order to eliminate side effects such as oxidation and the influence of moisture, a system of further desorbed components is used. In order to promote the exclusion to the outside, it is desirable to carry out under an inert gas atmosphere or under reduced pressure.

As the leaving component XY, X ₁ -Y ₁ , X ₂ -Y ₂ , the —O— bond or —S— bond site of the substituent constituting the ether group or acyloxy group which may be substituted may be used. Corresponding alcohols and carboxylic acids and carbonic acid half esters which have been cleaved and substituted with hydrogen at the ends are mentioned.
Examples of the alcohol include methanol, ethanol, propanol group, isopropanol, butanol, isobutanol, tertbutyl alcohol, pentanol, hexanol, trifluoromethanol, 3,3,3-trifluoropropanol, 3,3,3-trifluoro. Examples include fluoropropoxy group, pentafluoropropanol, cyclopropanol, cyclobutanol, cyclohexanol, trimethylsilanol, triethylsilanol, tert-butyldimethylsilanol, tert-butyldiphenylsilanol, etc., replacing oxygen at the ether bond site with sulfur Corresponding thiols are also included.
Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, lauric acid, stearic acid, trifluoroacetic acid, 3,3,3-trifluoropropionic acid, Examples include pentafluoropropionic acid, cyclopropanoic acid, cyclobutanoic acid, cyclohexane acid, benzoic acid, p-methoxybenzoic acid, pentafluorobenzoic acid, and the like, and corresponding thiocarboxylic acids in which the oxygen at the ether bond site is replaced with sulfur are also the same. included.

  For reference, the above-mentioned substituted or unsubstituted sulfonyloxy group may also be mentioned. The corresponding sulfone obtained by cleaving the —O— bond or the —S— bond site of the substituent constituting the sulfonyloxy group and substituting hydrogen at the terminal. Acid and thiosulfonic acid, such as methanesulfonic acid, ethanesulfonic acid, isopropylsulfonic acid, pivaloylsulfonic acid, pentanesulfonic acid, hexanoylsulfonic acid, toluenesulfonic acid, phenylsulfonic acid, trifluoromethanesulfonic acid, 3,3,3-trifluoropropionylsulfonic acid group and the like are included, and corresponding thiosulfonic acids in which oxygen at the ether bond site is replaced with sulfur are also included.

[Preferred form of anthracene derivative]
A more preferable form of the anthracene derivative of the present invention is a structure represented by the following general formula (2).

In the formula, the definition of each substituent is as described above. That is, R ₂ , R ₃ , R ₆ and R ₇ are all anthracene derivatives which are hydrogen atoms. This is because when a substituent other than a hydrogen atom is present at these substitution positions, the luminous efficiency and the lifetime are often lowered.

In a more preferred form, R ₁ , R _4, R _{5 and} R ₈ are groups selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted cycloalkyl group. This is because even when a hydrogen atom, an alkyl group, or a cycloalkyl group is present at these substitution positions, a decrease in luminous efficiency and a significant decrease in lifetime are often not observed.

  Although the preferable form of the anthracene derivative of this invention is illustrated concretely based on the above description below, it is not limited to these, unless the summary of this invention is exceeded.

A plurality of anthracene skeletons may be bonded at the substitution position of Ar ₁ or Ar ₂ . That is, the following structure is mentioned.

  Since the anthracene derivative of the present invention has high solubility, it can be dissolved in various solvents to form an ink. Ink formation will be described below.

  In the present invention, the solvent is selected from an aromatic solvent, a halogen solvent, and an ether solvent, and the solvent further includes an alcohol solution, a ketone solution, a paraffin solvent, and an alkyl substituted group having 4 or more carbon atoms. It is preferable to add a viscosity adjusting liquid selected from aromatic solutions.

  The solvent and the viscosity adjusting liquid in ink formation will be described.

  The solvent is selected from an aromatic solvent, a halogen solvent, and an ether solvent, and the solvent further includes an alcohol solution, a ketone solution, a paraffin solvent, and an alkyl-substituted aromatic solution having 4 or more carbon atoms. It is preferable to add a viscosity adjusting liquid selected from:

Examples of the solvent include an aromatic solvent which may have an alkoxy group such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, anisole, chlorobenzene, dichlorobenzene and chlorotoluene, and halogen. In addition, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane are also used as the solvent.
In addition, ether solvents such as dibutyl ether, tetrahydrofuran, and dioxane are also used as the solvent.

Examples of viscosity adjusting liquids include linear or branched alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, and benzyl alcohol. As mentioned.
Further, an alkyl-substituted aromatic solvent having 4 or more carbon atoms, which may have a linear or branched alkyl group, such as butylbenzene, cyclohexylbenzene, tetralin, butylbenzene, and dodecylbenzene, is also used as the viscosity adjusting liquid. Here, if an alcohol-based solution is used as a viscosity adjusting solution, the alcohol-based solution easily absorbs water, so care must be taken for storage management of the solution. Therefore, there is an advantage that storage is simple. Further, an alkyl-substituted aromatic solution having 4 or more carbon atoms has an advantage that the viscosity can be adjusted by changing the structure of the alkyl group (for example, lengthening the alkyl chain).
In addition, since the alcohol-based solution has a high viscosity, it is suitable for preparing a solution suitable for a film forming process (for example, an ink jet method) that requires a high solution viscosity.

  These solvents and viscosity adjusting liquids may be used alone or in combination.

In addition, the kind, mixing amount, etc. of a viscosity adjustment liquid can be suitably selected according to the viscosity required for various film-forming processes. The alkyl-substituted aromatic solution having 4 or more carbon atoms means an aromatic solution having an alkyl substituent having 4 or more carbon atoms. The upper limit of the carbon number of the alkyl substituent is not particularly defined, but for example, an upper limit of about 50 is given as an example.
Thus, by selecting a solvent from an aromatic solvent, a halogen solvent and an ether solvent, the organic EL material of the present invention can be dissolved in a necessary amount (for example, 1 wt%) or more in a solvent.
In addition, when a solution selected from an alcohol solution, a ketone solution, a paraffin solution and an alkyl-substituted aromatic solution having 4 or more carbon atoms is added as a viscosity adjusting solution, the viscosity of the organic EL material-containing solution is increased. It can be adjusted to a viscosity suitable for various application means (inkjet, nozzle printing, spin coating).
The solvent is at least one selected from an aromatic solvent, a halogen solvent, and an ether solvent, and of course, two or more may be mixed.
Similarly, the viscosity adjusting liquid is at least one selected from an alcohol solution, a ketone solution, a paraffin solution, and an alkyl-substituted aromatic solution having 4 or more carbon atoms. Of course it is good.

[Organic EL device]
The anthracene derivative of the present invention is suitable as an organic EL material. Below, the organic EL element as the application example is demonstrated.

The form of the organic EL element is not particularly limited, and FIG. 1 shows a schematic diagram of a preferred embodiment of a laminated structure in the organic EL element of the present invention.
In the organic EL element (8) shown in FIG. 1 (a), an anode (2), a light emitting layer (4) and a cathode (7) are laminated on a substrate (1).
A conducting wire (not shown) is connected to the anode (2) and the cathode (7), respectively, and the other end of the conducting wire is connected to a power source (not shown).
The organic EL element (10) shown in FIG. 1 (b) is the same as FIG. 1 (a) except that the hole transport layer (3) is laminated between the anode (2) and the light emitting layer (4). is there. The organic EL element (8) shown in FIG. 1 (c) is the same as FIG. 1 except that the electron transport layer (6) is laminated between the light emitting layer (4) and the cathode (7). The organic EL device (8) shown in FIG. 1 (d) has an anode (2), a hole transport layer (3), a light emitting layer (4), an electron transport layer (6) and a cathode on a substrate (1). (7) is laminated.
The organic EL element (8) shown in FIG. 1 (e) has an anode (2), a hole transport layer (3), a light emitting layer (4), an exciton blocking layer (5), and a substrate (1). An electron transport layer (6) and a cathode (7) are laminated.
The substrate of the organic EL element shown in FIG. 1 can be one generally used for organic EL elements, and is not particularly limited, but is a glass excellent in surface smoothness, waterproofness, etc. Substrates, silicon substrates and plastic substrates are preferred.
The anode (2) is not particularly limited, but the role of the anode is to inject holes into an organic layer such as a hole transport layer, and those having a high work function are preferable. As anode materials, nickel, gold, platinum, palladium and alloys thereof, tin oxide (SnO 2), zinc oxide containing acceptor impurities (ZnO 2), metals having a large work function such as copper iodide, and alloys thereof, Compounds, and further conductive polymers such as poly (3-methylthiophene) and polypyrrole can be used. As the transparent conductive material that can be used for the anode 2, for example, a transparent electrode formed of indium tin oxide (ITO) is preferable in consideration of conductivity, light transmission, etching processability, and the like. Can be used for In addition, indium zinc oxide (IZO: In2O3-ZnO) can also be used. Further, for example, a structure in which the transparent conductive material is stacked on a reflective electrode such as a silver electrode may be used. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm.

  The cathode (7) is not particularly limited, but the role of the cathode (7) is to inject electrons into the organic layer, and those having a small work function are preferable. For example, a magnesium-silver alloy electrode, a magnesium-indium alloy electrode, an aluminum electrode, or a combination of a thin interface layer and an aluminum electrode can be suitably used. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm.

  The application example of the organic EL element in the present invention includes a film containing an anthracene derivative as a guest material and a host material in at least one of the layers sandwiched between the anode (2) and the cathode (7). It is preferable that the fluorescent or phosphorescent guest molecule and the anthracene derivative of the present invention are the light emitting layer (4), but there is no particular limitation, and the other layers are the fluorescent or phosphorescent material of the present invention and the anthracene. Derivatives may be included and may exhibit luminescence derived from fluorescent or phosphorescent materials.

The fluorescent or phosphorescent material used as the guest material is not particularly limited, and examples of the fluorescent material include perylene derivatives, rubrene derivatives, coumarin derivatives, stilbene derivatives, tristyrylarylene derivatives, distyrylarylene derivatives, and the like. Can be mentioned.
Among these, a distyrylarylene derivative can be preferably used, and an example of this derivative is diphenylaminovinylarylene. As the phosphorescent material, an iridium complex can be suitably used. Examples of the iridium complex include tris- (2-phenylpyridine) iridium (Ir (ppy) 3) capable of obtaining a green emission color, and bis (2- (2- (2- (2-pyro))) capable of obtaining a red emission color. Benzo 4,5-thienylpyridinato-N, C3) iridium acetylacetonate (Btp2Iracac), bis (3,5-difluoro-2- (2-pyridyl) phenyl- ( 2-Carboxypyridyl) iridium III (FIrpic).

  As the hole transport material, those generally used for organic EL elements can be used, and are not particularly limited. For example, aromatic amines, particularly triarylamine derivatives can be preferably mentioned. Specifically, N, N′-di (1-naphthyl) -N, N′-diphenylbenzylididine (α-NPD), 4,4 ′, 4 ″ -tris [3-methylphenyl (phenyl) ) -Amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ″ -tris [2-naphthyl (phenyl) amino] triphenylamine (2-TNATA), 4,4 ′, 4 ″- Tris (carbazol-9-yl) -triphenylamine (TCTA), 2,2 ′, 7,7′-tetrakis (N, N-diphenylamino) -9,9′-spirobifluorene (spiro-TAD), N , N′-diphenyl-p-phenylenediamine (DPPD) and the like. These hole transport materials may be used alone or in combination of two or more.

  As the electron transport material, those generally used for organic EL elements can be used, and are not particularly limited. Examples of the electron transport material include tris (8-hydroxyquinolinato) aluminum (III) (Alq3). Further, as an electron transport material, in addition to Alq3, an oxadiazole derivative (for example, 2- (4′-t-butylphenyl) -5- (4 ″ -phenylyl) -1,3,4-oxadiazole ( tBu-PBD)), dimerized and starburst oxadiazole derivatives. These compounds may be used alone or in combination of two or more.

  In addition to the light emitting layer, the carrier transport layer and the injection layer may be doped. For example, by doping rubrene in the hole transport layer, light emission is observed from rubrene, and the light emission efficiency of the device is improved. Further, by doping the carrier transport layer and the injection layer, it is possible to obtain effects such as an increase in device life and an improvement in durability.

  The organic EL device schematically shown in FIG. 1 can be manufactured by a known manufacturing method, and the manufacturing method is not particularly limited. For example, a vacuum vapor deposition method (thermal vapor deposition method), a coating by a spin cast method (spin coating method), a solvent cast method and the like can be suitably used.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.
First, synthesis examples of soluble substituents and anthracene intermediates used in the examples are described below.

[Synthesis of Compound Intermediate 1]
[Synthesis of Compound 1]

In a 500 mL beaker, put 1,2,3,4-tetrahydro-6-aminonaphthalene (manufactured by Aldrich, 10 g, 65.3 mmol) and 15% HCl (60 mL). A sodium nitrate aqueous solution (5.41 g, 78.36 mmol in Water 23 mL) was gradually added dropwise.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, an aqueous potassium iodide solution (13.0 g, 78.36 mmol in Water 50 mL) was added at once, the ice bath was removed and the mixture was stirred for 3 hours, and then nitrogen was generated at 60 ° C. It was heated for 1 hour until.
After cooling to room temperature, the reaction solution was extracted three times with diethyl ether. The organic layer was washed with 5% aqueous sodium thiosulfate solution (100 mL × 3 times) and further with saturated brine (100 mL × 2 times). Furthermore, it dried with sodium sulfate and the red oil was obtained by concentrating a filtrate.
This was purified by silica gel column chromatography (solvent: hexane) to obtain Compound 1 as a colorless oil. (Yield 12.0 g, Yield 71.2%)
The analysis results of Compound 1 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.73-1.81 (m, 4H), 2.70 (quant, 4H, J = 4.85 Hz), 6.80 (d, 1H, J = 8.0 Hz), 7.38 (dd, 1H, J ₁ = 8.0 Hz J ₂ = 1.75 Hz), 7.41 (s, 1H)
Mass spectrometry (GC-MS): m / z = 258 (M +) (actual measured value); 258.099 (molecular weight theoretical value)

[Synthesis of Compound 2]
J. et al. Org. Chem. The target compound 2 was synthesized by applying the method described in 1999, 64, 9365-9373.

Compound 2 (3.1 g, 12 mmol), azobisisobutyronitrile (59 mg, 0.36 mmol), carbon tetrachloride (50 mL), N-bromosuccinimide (4.7 g, 26.4 mmol) in a 100 mL round bottom flask After replacing with argon gas, the mixture was gently heated to 80 ° C., stirred for 1 hour as it was, and cooled to room temperature. The precipitate was filtered, and the filtrate was concentrated under reduced pressure to obtain Compound 2 as a pale yellow solid. (Yield 4.99 g, 100% yield)
Used in the next reaction without further purification.
The analysis results of Compound 2 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.31-2.41 (m, 2H), 2.70-2.79 (m, 2H), 5.65 (t, 2H, J = 2.0 Hz), 7.24-7.28 (m, 2H), 7.31-7.34 (m, 2H)
Mass spectrometry (GC-MS): m / z = 416 (100.0%), 414 (51.4%), 418 (48.6%) (actual value); 415.891 (theoretical molecular weight value)

[Synthesis of Compound 3]

In the synthesis of Compound 1, 1,2,3,4-tetrahydro-6-aminonaphthalene is used instead of 1,2,3,4-tetrahydro-6-aminonaphthalene, and 1,2,3,4 is similarly used. -Tetrahydro-5-iodonaphthalene was synthesized. In the synthesis of Compound 2, Compound 3 was synthesized in the same manner except that 1,2,3,4-tetrahydro-5-iodonaphthalene was used instead of Compound 1.
The analysis results of Compound 3 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.72-2.76 (m, 2H), 2.81-2.85 (m, 2H), 5.53-5.54 (m, H), 5.60-5.62 (m, H), 6.95-6.99 (m, H), 7.35 (d, H, J = 7.8 Hz), 7.83 (d, H, J = 7.8 Hz)
Mass spectrometry (GC-MS): m / z = 416 (100.0%), 414 (51.4%), 418 (48.6%) (actual value); 415.891 (theoretical molecular weight value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 3.

[Synthesis of Compound 4]

A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (3.62 g, 20 mmol), hexanoic acid (2.51 mL, 20 mmol), N, N-dimethylformamide (hereinafter DMF, 30 mL), and purged with argon. And then stirred at room temperature for 2.5 hours. Compound 2 (4.16 g, 10 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give an orange oil. This was purified by silica gel column chromatography (solvent: toluene → ethyl acetate / toluene (5/95, v / v)) to obtain Compound 4 as a colorless oil. (Yield 2.44 g, Yield 50.2%)
The analysis results of Compound 4 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.87-0.90 (m, 6H), 1.24-1.34 (m, 8H), 1.60-1.67 (m, 4H), 1.90-1.94 (m, 2H), 2.23-2.34 (m, 6H), 5.98 (d, 2H, J = 3.5 Hz), 7.06 (d, 2H, J = 8.0 Hz), 7.63-7.66 (m, 2H)
Mass spectrometry (GC-MS): m / z = 486 (M +) (actual value); 486.384 (theoretical molecular weight value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 4.

[Synthesis of Compound 5]

In a 100 mL round bottom flask were added tetramethylammonium hydroxide pentahydrate (6.8 g, 37.5 mmol), hexanoic acid (4.7 mL, 37.5 mmol), N, N-dimethylformamide (hereinafter DMF, 60 mL). The mixture was purged with argon and stirred at room temperature for 2.5 hours. Compound 3 (6.24 g, 15 mmol) was added thereto, and the mixture was further stirred at room temperature for 16 hours. The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give an orange oil. This was purified by silica gel column chromatography (solvent: toluene → ethyl acetate / toluene (5/95, v / v)) to obtain Compound 5 as a colorless oil. (Yield 2.00 g, Yield 27.0%)
The analysis results of Compound 5 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 to 0.89 (m, 6H), 1.25 to 1.35 (m, 8H), 1.58 to 1.62 (m, 4H), 1.63-1.69 (m, 2H), 1.94-1.96 (m, 2H), 2.24-2.38 (m, 4H), 5.89 (t, H, J = 2.9 Hz), 6.00 (t, H, J = 2.9 Hz), 7.04-7.07 (m, H), 7.36 (d, H, J = 8.0 Hz), 7.89 (d, H, J = 8.0 Hz)
Mass spectrometry (GC-MS): m / z = 486 (M +) (actual value); 486.384 (theoretical molecular weight value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 5.

[Synthesis of Compound Intermediate 2]
[Synthesis of Compound 6]

  Compound 6 was synthesized according to the following reaction formula (scheme).

  In the above formula, the starting material 6-amino-3,4-dihydro-1 (2H) -naphthalenone was purchased from SIGMA Aldrich.

In a 500 mL beaker, add 6-amino-3,4-dihydro-1 (2H) -naphthalenone (20 g, 119.0 mmol) and 15% HCl (96 mL), maintaining -5 ° C. or lower under ice cooling while maintaining nitrous acid. A sodium aqueous solution (9.9 g, 143.0 mmol + water 42 mL) was gradually added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 30 minutes, an aqueous potassium iodide solution (23.7 g, 143.0 mmol + 77 mL of water) was added at once, the ice bath was removed and the mixture was stirred for 2.5 hours, and then at 60 ° C. Heated for 0.5 hour until evolution stopped. After cooling to room temperature, the reaction solution was extracted three times with diethyl ether. The organic layer was washed with 5% aqueous sodium thiosulfate solution (100 mL × 3 times) and further with saturated brine (100 mL × 2 times).
Furthermore, it dried with sodium sulfate and the red oil was obtained by concentrating a filtrate.
This was purified by silica gel column chromatography (solvent: ethyl acetate / hexane = 9/1) to obtain a pale orange solid. Further, recrystallization from 2-propanol gave Compound 6 as pale orange crystals (yield 11.4 g, yield 35.2%).
The analysis results of Compound 6 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 2.13 (quant, 2H, J = 5.7 Hz), 2.64 (t, 2H, J = 6.3 Hz), 2.92 (t, 2H, J = 6.0 Hz), 7.66 (d, 1H, J = 8.0 Hz), 7.67 (s, 1H), 7.72 (d, 1H, J = 8.0 Hz)
Melting point: 74.0-75.0 ° C
Mass spectrometry (GC-MS): m / z = 272 (M +) (actual value); 272.082 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 6.

[Synthesis of Compound 7]
Compound 7 was synthesized according to the following reaction formula (scheme).

Compound 6 (4.1 g, 15 mmol) and methanol (100 mL) were placed in a 200 mL round bottom flask, and sodium borohydride (850 mg, 22.5 mmol) was gradually added at 0 ° C. under ice cooling. The mixture was stirred for 3 hours. Excess sodium borohydride was neutralized with dilute hydrochloric acid, saturated brine was added, and the mixture was extracted 5 times with ethyl acetate (50 mL). The extract was washed once with ammonium chloride (100 mL), then twice with brine (100 mL), and dried by adding sodium sulfate. The filtrate was concentrated to obtain compound 7 as a light red solid (yield 3.93 g, yield 95.5%). The product was used in the next reaction as it was without further purification.
The analysis results of Compound 7 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.71 (d, 1H, J = 5.8 Hz), 1.84 to 2.02 (m, 4H), 2.65-2.71 ( m, 1H,), 2.75-2.81 (m, 1H,), 4.72 (d, 1H, J = 4.6 Hz), 7.17 (d, 1H, J = 8.0 Hz), 7.47 (s, 1 H), 7.52 (d, t, ₁ H, J ₁ = 8.0 Hz, J ₂ = 1.2 Hz)
Mass spectrometry (GC-MS): m / z = 274 (M +) (actual measured value); 274.098 (calculated molecular weight)
Melting point: 82.0-84.0 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 7.

[Synthesis of Compound 8]
Compound 8 was synthesized according to the following reaction formula (scheme).

Compound 7 (3.70 g, 13.5 mmol), N, N-dimethylaminopyridine (hereinafter referred to as DMAP, 10 mg) was placed in a 50 mL round bottom flask, and after replacement with argon gas, dehydrated pyridine (8.1 ml), Acetic anhydride (6.2 ml) was added and stirred at room temperature for 6 hours. 50 mL of water was added to the reaction solution, and the mixture was extracted 5 times with ethyl acetate (20 mL). The combined organic layers were washed 3 times with dilute hydrochloric acid (100 ml), followed by 2 times with saturated sodium bicarbonate solution (100 ml), and finally The extract was washed twice with saturated brine (100 ml) and dried over magnesium sulfate.
The filtrate was concentrated to give compound 8 as a brown liquid (yield 4.28 g, yield 100%).
The product was used in the next reaction as it was without further purification.
The analysis results of Compound 8 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.76-1.83 (m, 1H,), 1.89-2.10 (m, 1H), 2.07 (s, 3H), 2.67-2.73 (m, 1H,), 2.79-2.84 (m, 1H,), 5.93 (t, 1H, J = 5.2 Hz), 7.01 (d, 1H) , J = 8.6 Hz), 7.49 (d, 1H, J = 2.3 Hz), 7.52 (s, 1H)
Mass spectrometry (GC-MS): m / z = 316 (M +) (actual value); 316.135 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 8.

[Synthesis of Compound 9]
Compound 9 was synthesized according to the following reaction formula (scheme).

In a 100 mL round bottom flask, compound 8 (4.27 g, 13.5 mmol), azobisisobutyronitrile (hereinafter AIBN, 25 mg), carbon tetrachloride (100 mL), N-bromosuccinimide (hereinafter NBS, 2.64 g, (14.8 mmol) was added, and after replacement with argon gas, the mixture was gently heated to 80 ° C., stirred as it was for 1 hour, and cooled to room temperature. The precipitate was filtered, and the filtrate was concentrated under reduced pressure to obtain a light yellow solid. This was purified by silica gel column chromatography (solvent: ethyl acetate / hexane = 8/2) to obtain Compound 9 as a pale red oil (yield 4.9 g, yield 92.0%). Compound (5) was obtained as a 10: 7 mixture of cis and trans isomers.
The analysis results of Compound 9 are shown below.
Accurate mass spectrometry (LC-TofMS): m / z = 393.9028 (100.0%), 395.9082 (actual value); 393.9065 (100.0%), 395.9045 (97.3%) (Theoretical value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 9.

[Synthesis of Compound 10]
Compound 10 was synthesized according to the following reaction formula (scheme).

Compound 9 (4.2 g, 10.6 mmol) was placed in a 500 mL round-bottom flask and replaced with argon gas. Then, THF (300 mL) was added, and sodium methoxide-methanol solution (25 wt%, 24 mL) was added and stirred at that temperature for 6 hours. Water (300 mL) was added, extracted four times with ethyl acetate (100 mL), washed twice with saturated brine (100 mL), dried over sodium sulfate, and the filtrate was concentrated to give a brown liquid. This was subjected to column purification to obtain Compound 10 as a colorless crystal (yield 1.2 g, yield 41.0%).
The analysis results of Compound 10 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 1.70 (d, 1H, J = 3.4 Hz), 2.58-2.61 (m, 2H), 4.76 (q, 1H, J = 6.3 Hz), 6.04 (q, 1H, J = 5.2 Hz), 6.47 (d, 1H, J = 9.8 Hz), 7.13 (d, 1H, J = 8.1 Hz) ), 7.47 (d, 1H, J = 1.7 Hz), 7.57 (J ₁ = 8.1 Hz J ₂ = 1.7 Hz)
Mass spectrometry (GC-MS): m / z = 272 (M +), 254 (M + -H ₂ O) (actual value); 272.082 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 10).

[Synthesis of Compound (11-1)]
Compound (11-1) was synthesized according to the following reaction formula (scheme).

Compound 10 (680 mg, 2.5 mmol) and DMAP (15.3 mg, 0.125 mmol) were placed in a 50 mL round-bottom flask and replaced with argon gas. Then, pyridine (15 mL) was added, and the mixture was cooled to 0 ° C. with ice cooling. Then, hexanoyl chloride (370 mg, 2.75 mmol) was added dropwise, and the mixture was stirred at the same temperature for 3 hours. Water was added to the reaction solution, followed by extraction three times with ethyl acetate (50 mL), and the organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. The liquid was dissolved in ethyl acetate / hexane (95/5), passed through a silica gel pad having a thickness of 3 cm, and the filtrate was concentrated to obtain a compound (11-1) as a colorless liquid (yield 560 g, yield 60). .5%).
The analysis result of the compound (11-1) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.2 Hz), 1.21-1.30 (m, 4H), 1.54-1.60 ( m, 2H), 2.23 (td, 2H, J ₁ = 7.5 Hz J ₂ = 2.3 Hz), 2.58-2.62 (m, 2H), 5.95 (t, 1H, J = 5 .2 Hz), 6.03 (quant, 1 H, J = 4.6 Hz), 6.48 (d, 1 H, J = 9.8 Hz), 7.10 (d, 1 H, J = 8.0 Hz), 7 .48 (d, 1H, J = 1.7 Hz), 7.54 (dd, 1H, J1 = 8.0 Hz, J2 = 1.8 Hz)
Mass spectrometry (GC-MS): m / z = 370 (M +), 254 (M + -C5H11COOH) (actual value); 370.225 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (11-1).

[Synthesis of Compound (11-2)]
Compound (11-2) was synthesized according to the following reaction formula (scheme).

Compound 10 (1.09 g, 4.0 mmol) and DMAP (24.5 mg, 0.200 mmol) were placed in a 50 mL round-bottomed flask and replaced with argon gas. Then, pyridine (20 mL) was added, and the mixture was cooled to 0 ° C. under ice-cooling. N-butyryl chloride (0.46 mL, 4.4 mmol) was added dropwise at 0 ° C., and the mixture was stirred at the same temperature for 3 hours. Water was added to the reaction solution, followed by extraction three times with ethyl acetate (50 mL), and the organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a brown liquid. By refine | purifying with a silica gel column, the compound (11-2) was obtained as a colorless liquid (yield 895 mg, yield 60.5%).
The analysis result of the compound (11-2) is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.893 (t, 3H, J = 7.5 Hz), 1.57-1.64 (m, 2H), 2.23 (td, 2H, J1 = 7.4 Hz, J2 = 2.3 Hz), 2.58-2.62 (m, 2H), 5.96 (t, 1H, J = 5.2 Hz), 6.03 (quint. J = 5 .2 Hz), 6.48 (d, 1 H, J = 9.9 Hz), 7.10 (d, 1 H, J = 8.0 Hz), 7.48 (d, 1 H, J = 1.7 H), 7 .54 (dd, 1H, J1 = 8.0 Hz, J2 = 1.7 Hz)
Mass spectrometry (GC-MS): m / z = 342 (M +), 254 (M + -C3H7COOH) (actual value); 342.172 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of compound (11-2).

[Synthesis of Compound 12]
Compound 12 was synthesized according to the following reaction formula (scheme).

The starting material, 1-cyclohexenyl trifluoromethanesulfonate, was purchased from Aldrich, and dibrominated in the same manner as the synthesis of Compound 2 to give 3,6-dibromo-1-cyclohexenyl trifluoromethanesulfonate. It was used as such in the next reaction without purification.
A 100 mL round bottom flask was charged with tetramethylammonium hydroxide pentahydrate (1.81 g, 10 mmol), hexanoic acid (1.25 mL, 10 mmol), N, N-dimethylformamide (hereinafter DMF, 30 mL), and purged with argon. And then stirred at room temperature for 2.5 hours. Thereto was added 3,6-dibromo-1-cyclohexenyl trifluoromethanesulfonate (1.8 g, 4.5 mmol), and the mixture was further stirred at room temperature for 16 hours.
The reaction solution was diluted with 100 mL of ethyl acetate, 200 mL of pure water was added, and the organic layer was separated. The aqueous layer was extracted four times with 30 mL of ethyl acetate, and the combined organic layer was washed with a saturated sodium hydrogen carbonate solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give an orange oil. This was purified by silica gel column chromatography to obtain Compound 12 as a colorless oil. (Yield 900 mg, Yield 43.2%)
The analysis results of Compound 12 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.90 (t, J = 7.5 Hz, 6H), 1.26 to 1.37 (m, 8H), 1.60 to 1.67 ( m, 4H), 1.76-1.92 (m, 2H), 1.96-2.08 (m, 2H), 2.29-2.36 (m, 4H), 5.48 (q, 1H, J = 4.6 Hz), 5.51 (t, 1H, J = 4.6 Hz), 6.12 (d, J = 5.2 Hz, 1H)
Accurate mass spectrometry (LC-TofMS): m / z = 458.1507 (actual value), 225.9980 (M + -2C ₅ H ₁₁ COOH); 458.1586, 225.9910 (theoretical value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 12.

[Synthesis of Compound 13]
Compound 13 was synthesized according to the following reaction formula (scheme).

A known 1,5-cyclohexadienyl trifluoromethanesulfonic acid ester was brominated in the same manner as in Compound 12 to synthesize 4-bromo-1,5-cyclohexadienyl trifluoromethanesulfonic acid ester.
Similarly to compound 12, bromine of 4-bromo-1,5-cyclohexadienyl trifluoromethanesulfonate ester was esterified to obtain compound 13 as a colorless oil. (Yield 800 mg, Yield 30%)
The analysis results of Compound 13 are shown below.
Accurate mass spectrometry (Tof-MS): m / z = 342.0766 (M +), 225.9998 (M + -C ₅ H ₁₁ COOH) (actual value); 342.0749 (M +), 225.9911 (M + −) C ₅ H ₁₁ COOH) (theory)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 13.

[Synthesis of Compound 14]
Compound 14 was synthesized according to the following reaction formula (scheme).

2-tert-butylanthracene (manufactured by Tokyo Chemical Industry Co., Ltd., 2.34 g, 10 mmol), DMF (150 mL), and NBS (4.27 g, 24 mmol) were placed in a round bottom flask and stirred at room temperature for 16 hours. A sodium sulfite aqueous solution was added, and the precipitated yellow precipitate was collected by filtration. The precipitate was washed with hot water followed by ethanol, and dried under vacuum to obtain a crude product.
This was recrystallized from toluene / ethanol to obtain Compound 14 as bright yellow crystals. (Yield 2.15 g, Yield 55%)
The analysis results of Compound 14 are shown below.
¹ H NMR (500 MHz, CDCl 3, TMS, δ): 1.49 (s, 9H), 7.59-7.63 (m, 2H), 7.73 (dd, 4H, J1 = 9.2 Hz, J2 = 2.3 Hz), 8.49 (d, 1H, J = 1.7 Hz), 8.52 (d, 1H, J = 9.2 Hz), 8.56-8.60 (m, 2H)
Mass spectrometry (GC-MS): m / z = 392 (100.0%), 390 (51.4%), 394 (48.6%); 392.128 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 14.

[Synthesis of Compound 15]
Compound 15 was synthesized according to the following reaction formula (scheme).

To a well-dried flask, 2-tert-butyl-9,10-dibromoanthracene (1.24 g, 3.16 mmol) was added, and after replacing with argon gas, THF (50 mL) was added, and acetone-dry ice was added. Cooled to −78 ° C. with a bath. n-Butyllithium 1.6M hexane solution (20 mL) was added, and the mixture was stirred at the same temperature for 2 hours. Subsequently, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (18 mL) was added in one portion, and the temperature was raised from −78 ° C. to room temperature over 1 hour. A saturated aqueous ammonium chloride solution and ethyl acetate were added, and the organic layer was separated. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were washed with water and then with saturated brine, and dried by adding sodium sulfate.
The desiccant was filtered off and the concentrated residue was purified by flash chromatography (stationary phase: silica gel, mobile phase: hexane / ethyl acetate = 9/1) to obtain the desired product as a pale yellow solid. Yield 400mg, Yield 26%
The analysis results of Compound 15 are shown below.
¹ H NMR (500 MHz, CDCl 3, TMS, δ): 1.43 (s, 9 H), 7.41-7.43 (m, 2 H), 7.56 (dd, 1 H, J 1 = 9.2 Hz, J 2 = 1.7 Hz), 8.21 (d, 1H, J = 1.7 Hz), 8.28-8.35 (m, 3H)
Mass spectrometry (GC-MS): m / z = 486 (M +) (actual value); 486.258 (calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of Compound 15.

[Example 1; Synthesis of anthracene derivative HTL1]

In a round bottom flask, 9,10-anthracene diboronic acid bispinacol ester (manufactured by Aldrich, 430 mg, 1 mmol), compound 11-1 (750 mg, 2.1 mmol), potassium phosphate (1.27 g, 6 mmol), tris ( Dibenzylideneacetone) dipalladium (hereinafter referred to as Pd2 (dba) 3) (18.2 mg), tri-tert-butylphosphine (9.7 mg) were added, and after replacement with argon gas, DMF (25 mL) was added, followed by room temperature. For 24 hours. A saturated aqueous ammonium chloride solution was added, and the mixture was stirred for 30 minutes. Then, ethyl acetate was added to separate the organic layer, and the aqueous layer was extracted four times with ethyl acetate. The combined organic layers were washed with a saturated aqueous sodium bicarbonate solution, followed by water and saturated brine, and dried over magnesium sulfate. The desiccant was filtered off. When the concentrated residue was analyzed by thin layer chromatography (developing solvent: toluene), two types of products were confirmed. Two components were separated and purified with a silica gel column (developing solvent: toluene) to obtain HTL1 as a main product as a pale yellow solid. HTL1 (yield 69 mg)
The analysis results of HTL1 are shown below.
HTL1: 1H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.907 (t, J = 6.7 Hz, 6H), 1.30-1.37 (m, 8H), 1.69 (quint, J = 7.5 Hz, 4H), 2.39 (t, J = 7.5 Hz, 4H), 6.11 (quint, J = 5.2 Hz, 2H), 6.22 (t, 2H, J = 5. 2 Hz), 6.62 (t, J = 9.8 Hz, 2H), 7.25 (s, 2H), 7.30-7.36 (m, 6H), 7.60 (d, J = 7. 5Hz, 2H), 7.68-7.70 (m, 2H), 7.73-7.77 (m, 2H)
Mass spectrometry (GC-MS): m / z = 663 (M +), 431 (M + -2C ₅ H ₁₁ COOH) (actual value); 662.855 (M +), 430.538 (M + -2C ₅ H ₁₁ COOH) ) (Calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL1.

[Example 2; Synthesis of anthracene derivative HTL2]

The same procedure as in Example 1 was performed except that the isolated and purified component was replaced with a component that was not HTL1, and HTL2 was obtained as a pale yellow solid in a yield of 16 mg.
The analysis results of HTL2 are shown below.
HTL2: 1H NMR (500 MHz, CDCl3, TMS, δ): 0.90 (t, J = 7.0 Hz, 3H), 1.21-1.38 (m, 4H), 1.66-1.72 ( m, 2H), 2.39 (t, J = 7.4 Hz, 2H), 6.12 (quint, J = 5.2 Hz, 1H), 6.23 (t, 2H, J = 5.7 Hz, 1H) ), 6.64 (d, J = 9.2 Hz, 1H), 7.28-7.39 (m, 6H), 7.59-7.63 (m, 4H),) 7.72 (d, J = 8.5 Hz, 2H), 7.79 (d, J = 8.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.98 (s, 1H), 8. 02 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H)
Mass spectrometry (GC-MS): m / z = 547 (M +), 431 (M + -C ₅ H ₁₁ COOH) (actual value); 546.697 (M +), 430.538 (M + -C ₅ H ₁₁ COOH) ) (Calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL2.

[Example 3; Synthesis of anthracene derivative HTL3]
HTL3 was synthesized and purified according to the following formula in the same manner as in Example 1 except that Compound 4 was used instead of Compound 11-1 and the reaction temperature was changed from room temperature to 50 ° C.

As a pale yellow solid, HTL3 was obtained in a yield of 105 mg and a yield of 65%.
The analysis results of HTL3 are shown below.
Mass spectrometry (GC-MS): m / z = 895 (M +), 431 (M + -4C ₅ H ₁₁ COOH) (actual value); 895.172 (M +), 430.538 (M + -4C ₅ H ₁₁ COOH) ) (Calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL3.

[Example 4; Synthesis of anthracene derivative HTL4]
In the same manner as in Example 1, except that compound 5 was used instead of compound 11-1, the reaction time was changed from 24 hours to 48 hours, and the reaction temperature was changed from room temperature to 50 ° C. Purification was performed.

HTL4 was obtained as a pale yellow waxy solid. (Yield 53 mg, Yield 33%)
The analysis results of HTL4 are shown below.
Mass spectrometry (GC-MS): m / z = 895 (M +), 431 (M + -4C ₅ H ₁₁ COOH) (actual value); 895.172 (M +), 430.538 (M + -4C ₅ H ₁₁ COOH) ) (Calculated molecular weight)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL4.

[Example 5: Synthesis of anthracene derivative HTL5]
Anthracene derivative HTL5 was synthesized according to the following reaction formula (scheme).

To a round bottom flask was added 2-tert-butyl-9,10-anthracene diboronic acid bispinacol ester (565 mg, 1.16 mmol), compound 11-2 (794 mg, 2.2 mmol), potassium phosphate (1.4 g, 6.6 mmol), bis (dibenzylideneacetone) palladium (hereinafter referred to as Pd (dba) 2) (127 mg), tri-tert-butylphosphine (120 mg), and after replacing with argon gas, DMF (15 mL) was added. And stirred for 24 hours at room temperature. A saturated aqueous ammonium chloride solution was added, and the mixture was stirred for 30 minutes. Then, ethyl acetate was added to separate the organic layer, and the aqueous layer was extracted four times with ethyl acetate. The combined organic layers were washed with a saturated aqueous sodium bicarbonate solution, followed by water and saturated brine, and dried over magnesium sulfate. The desiccant was filtered off, and the concentrated residue was separated and purified by a silica gel column (developing solvent: toluene) to obtain HTL5 as a pale yellow solid. (Yield 405 mg, Yield 56.4%)
The analysis results of HTL5 are shown below.
1H NMR (500 MHz, CDCl3, TMS, δ): 0.93-0.992. (M, 6H), 1.26 (t, 9H, J = 3.7 Hz), 1.65-1.75 (m, 4H), 2.34-2.39 (m, 4H), 2.71 -2.83 (m, 4H), 6.08-6.12 (m, 2H), 6.21-6.27 (m, 2H), 6.63 (t, 2H, J = 9.2 Hz) 7.24-7.25 (m, 2H), 7.29-7.36 (m, 4H), 7.44 (td, 1H, J1 = 5.3 Hz, J2 = 2.3 Hz), 7. 57-7.75 (m, 6H)
Mass spectrometry (GC-MS): 663 (M +), 487 (M + -2C ₅ H ₁₁ COOH) (actual value); 662.855 (M +), 486.645 (M + -2C ₃ H ₇ COOH) (molecular weight calculation) value)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL5.

[Synthesis of Compound Intermediate 3]
Prior to Examples 6 and 7, according to the following scheme, an existing method (see J. AM. CHEM. SOC. 9 VOL. 128, No. 39, 2006 12605) was followed by two-stage Suzuki coupling, 10- (2-Naphthyl) -anthracene-9- (4-phenyl) boronic acid was synthesized.

[Example 6: Synthesis of anthracene derivative HTL6]
According to the following formula, HTL6 was synthesized and purified in the same manner except that Compound 12 was used instead of Compound 11-1 in Example 1.

HTL6 was obtained as a pale yellow solid. (Yield 55 mg, 52% yield)
The analysis results of HTL6 are shown below.
Accurate mass (LC-TofMS): 688.3511 ( M +), 456.1822 ((M + -2C 5 H 11 COOH) ( Found); 688.3553 (M +), 456.1878 (M + -2C 5 H ₁₁ COOH) (theoretical value)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL6.

[Example 7; Synthesis of anthracene derivative HTL7]
According to the following formula, HTL6 was synthesized and purified in the same manner except that Compound 13 was used instead of Compound 11-1 in Example 1.

HTL7 was obtained as a pale yellow solid. (Yield 35 mg, Yield 24%)
The analysis results of HTL7 are shown below.
Accurate mass (LC-TofMS): 572.2767 ( M +), 456.1891 ((M + -C 5 H 11 COOH) ( Found); 572.2715 (M +), 456.1878 (M + -C 5 H ₁₁ COOH) (theoretical value)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL7.

  Prior to Example 8, dimerization of anthracene (for example, Journal of Organometallic Chemistry, 414 (1), 1991, 119-127) was carried out by an existing method according to the following scheme, followed by bromination, followed by Suzuki. A dichloro compound was synthesized by coupling. Subsequently, the boronic acid ester (compound 16) was derived by a known technique of Miyaura et al. (See, for example, Tetrahedron, 57, 2001, 9813-9816). The compound was identified by MS and NMR.

[Example 8: Synthesis of anthracene derivative HTL7]
According to the following formula, HTL14 was synthesized and purified in the same manner as in compound 16 except that compound 12 was used instead of compound 11-1 in Example 1.

Accurate mass spectrometry (LC-TofMS): 1122.601 (M +), 658.2669 ((M + -4C5H11COOH) (actual value); 1122.6010 (M +), 658.2661 (M + -4C5H11COOH) (theoretical value)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL14.

  Prior to Example 9, a Suzuki coupling reaction compound 17 of a known boronic acid derivative and 9,10-dibromoanthracene was synthesized according to the following reaction formula (scheme). The compound was identified by MALDI-TOF-MS.

[Example 9]
In a well-dried flask, compound 17 (1.07 g, 1 mmol), compound 4 (1.60 g, 3.3 mmol), potassium phosphate (1.4 g, 6.6 mmol), bis (dibenzylideneacetone) palladium (Hereafter, Pd (dba) 2) (127 mg) and tri-tert-butylphosphine (120 mg) were added and replaced with argon gas, DMF (30 mL) was added, and the mixture was stirred at room temperature for 24 hours.
A saturated aqueous ammonium chloride solution and ethyl acetate were added, and the organic layer was separated. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were washed with water and then with saturated brine, and dried by adding sodium sulfate. The desiccant was filtered off and the concentrated residue was purified by flash chromatography (stationary phase: silica gel, mobile phase: toluene / ethyl acetate) to obtain the desired product as a pale yellow solid. Yield 850 mg, Yield 45%
Accurate mass spectrometry (MALDI-TOFMS): 1908.9700 (M +), 1214.4840 ((M + -6C5H11COOH) (actual value); 1908.719 (M +), 1214.4852 (M + -6C5H11COOH) (theoretical value)
LC purity: 99.5% (peak area ratio)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL18.

  Prior to Example 10, a Suzuki coupling reaction compound 18 of a known boronic acid derivative and 9,10-dibromoanthracene was synthesized according to the following reaction formula (scheme). The compound was identified by MALDI-TOF-MS.

[Example 10]
In a well-dried flask, compound 17 (1.07 g, 1 mmol), compound 4 (1.60 g, 3.3 mmol), potassium phosphate (1.4 g, 6.6 mmol), bis (dibenzylideneacetone) palladium (Hereafter, Pd (dba) 2) (127 mg) and tri-tert-butylphosphine (120 mg) were added and replaced with argon gas, DMF (30 mL) was added, and the mixture was stirred at room temperature for 24 hours.
A saturated aqueous ammonium chloride solution and ethyl acetate were added, and the organic layer was separated. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were washed with water and then with saturated brine, and dried by adding sodium sulfate. The desiccant was filtered off and the concentrated residue was purified by flash chromatography (stationary phase: silica gel, mobile phase: toluene / ethyl acetate) to obtain the desired product as a pale yellow solid. Yield 950 mg, Yield 50%
Accurate mass spectrometry (MALDI-TOFMS): 191.99584 (M +), 1215.4456 ((M + -6C5H11COOH) (actual value); 19115.976 (M +), 1215.4552 (M + -6C5H11COOH) (theoretical value)
LC purity: 99.5% (peak area ratio)
From the above analysis results, it was confirmed that the synthesized products were consistent with the structure of HTL19.

[Example 11: Observation example 1 of thermal decomposition behavior of anthracene derivative]
The thermal decomposition behavior of HTL1 synthesized in Example 1 was measured using TG-DTA [reference Al ₂ O ₃ , under a nitrogen stream (200 mL / min), EXSTAR 6000 (trade name), Seiko Instruments Inc. The temperature was raised from 25 ° C. to 450 ° C. at a rate of 5 ° C./min.
The results are shown in FIG. In FIG. 2, the horizontal axis represents temperature [° C.], the vertical axis left represents weight change [ug], and the vertical axis right represents DTA signal [uV].
From FIG. 2, a weight reduction of 34.7% from the initial weight was confirmed from room temperature to around 250 ° C. This is almost the same as the weight loss (35.05%) which is considered that two molecules of hexanoic acid were eliminated from HTL1 and 9,10-di (2-naphthyl) anthracene was produced.
In addition, when a sample was taken out at a stage of 250 ° C. and subjected to accurate mass spectrometry, the actual measurement value of the m / z, 250 ° C. heated sample: 430.1760 was compared with 9,10-di (2-naphthyl) anthracene. Theoretical value: 430.1767 and the exact mass coincided with 3 decimal places.
From this, it was confirmed that HTL1 desorbs two molecules of hexanoic acid from the molecule by heating and quantitatively converts it to 9,10-di (2-naphthyl) anthracene.

[Example 12: Observation example 2 of thermal decomposition behavior of anthracene derivative]
The thermal decomposition behavior by TG-DTA was observed in the same manner as in Example 11 except that HTL5 synthesized in Example 5 was used instead of HTL1. The results are shown in FIG.
From FIG. 3, a weight reduction of 26.58% from the initial weight was confirmed from room temperature to around 250 ° C. This almost coincides with the weight loss (%) that is considered that two molecules of hexanoic acid are eliminated from HTL5 and 2-tert-butyl-9,10-di (2-naphthyl) anthracene is produced.
Further, when a sample was taken out at a stage of 230 ° C. and subjected to accurate mass spectrometry, it was found that 2-tert-butyl-9,10-di ( The theoretical value of 2-naphthyl) anthracene: 486.2308 and the exact mass coincided with three decimal places.
From this, it was confirmed that HTL5 desorbs two molecules of n-butanoic acid from the molecule by heating, and quantitatively converts it into 2-tert-butyl-9,10-di (2-naphthyl) anthracene. It was.

[Example 13]
Example 13 was obtained by changing the compound used to HTL7 instead of HTL1 in the same manner as in Example 11.
The results are shown in Table 5 below.

[Example 14]
In the same manner as in Example 11, the compound used was changed to HTL14 instead of HTL1, and Example 14 was obtained.
The results are shown in Table 5 below.

[Example 15]
Example 15 was obtained by changing the compound used to HTL18 instead of HTL1 in the same manner as in Example 11.
The results are shown in Table 5 below.

[Example 16]
In the same manner as in Example 11, the compound used was changed to HTL19 instead of HTL1 as Example 16.
The results are shown in Table 5 below.

In the mass analysis of Table 5, “◯” indicates that the exact mass coincided with three decimal places.
From this, it was confirmed that HTL7, HTL14, HTL18, and HTL19 detach 1 to 6 molecules of n-butanoic acid from the molecule by heating, and quantitatively convert the ester structure site into a benzene ring.

  From Examples 11 to 16, it became clear that the anthracene derivative of the present invention can be quantitatively converted into a structure in which a dissolving group is eliminated by heating to form a double bond, that is, a benzene ring.

[Example 17: Making anthracene derivative into ink (evaluation of solubility)]
The HTL1 obtained in Example 1 was added to each of toluene, THF, chloroform, 1,2,3,4-tetrahydronaphthalene (trade name: tetralin), and ethyl benzoate (100 mg each) until the residue remained, and the solvent The mixture was stirred for 10 minutes under reflux, cooled to room temperature, further stirred for 1 hour, allowed to stand for 16 hours, and then the supernatant was filtered through a 0.2 μm PTFE filter to obtain a saturated solution. The solubility of the compound with respect to each solvent was computed by drying this under reduced pressure.

[Example 18]
In the same manner as in Example 17, the solubility was calculated using HTL2 synthesized in Example 2 instead of HTL1. This is Example 18, and the results are similarly shown in Table 6 below.

[Example 19]
In the same manner as in Example 17, the solubility was calculated using HTL3 synthesized in Example 3 instead of HTL1. This is Example 19, and the results are similarly shown in Table 6 below.

[Example 20]
In the same manner as in Example 17, the solubility was calculated using HTL4 synthesized in Example 4 instead of HTL1. This is Example 20, and the results are similarly shown in Table 6 below.

[Example 21]
In the same manner as in Example 17, the solubility was calculated using HTL5 synthesized in Example 5 instead of HTL1. This is Example 21, and the results are similarly shown in Table 6 below.

[Example 22]
In the same manner as in Example 17, the solubility was calculated using HTL6 synthesized in Example 6 instead of HTL1. This is Example 22, and the results are similarly shown in Table 6 below.

[Example 23]
In the same manner as in Example 17, the solubility was calculated using HTL7 synthesized in Example 7 instead of HTL1. This is Example 23 and the results are similarly shown in Table 6 below.

[Example 24]
In the same manner as in Example 17, the solubility was calculated using HTL14 synthesized in Example 8 instead of HTL1. This is Example 24 and the results are similarly shown in Table 6 below.

[Example 25]
In the same manner as in Example 17, the solubility was calculated using HTL18 synthesized in Example 9 instead of HTL1. This is Example 25 and the results are similarly shown in Table 6 below.

[Example 26]
In the same manner as in Example 17, the solubility was calculated using HTL19 synthesized in Example 10 instead of HTL1. This is Example 26 and the results are similarly shown in Table 6 below.

The evaluation criteria in Table 6 are as follows.
A: Solubility is 5 wt% or more,
○: 1 wt% or more and less than 5 wt% Δ: 0.1 wt% or more and less than 0.5 wt% ×: less than 0.1 wt%

Table 6 shows that all anthracene derivatives are used in various solvents such as toluene (boiling point 110 ° C.), THF (66 ° C.), chloroform (61 ° C.), tetralin (boiling point 207 ° C.), ethyl benzoate (boiling point 212 ° C.). On the other hand, a high solubility of approximately 1.0 wt% or more and a maximum of 5.0 wt% or more was confirmed.
This indicates that the contribution of the soluble group contained in the skeleton is large.
As for the solvent polarity, a solvent having a small polarity such as toluene and tetralin, a halogen-containing solvent such as chloroform, and a high polarity solvent such as ethyl benzoate can be selected. In addition, a solvent having a boiling point in the range of about 60 ° C. to 200 ° C. can be selected.
In order to obtain desired physical properties such as polarity and boiling point depending on the film forming method, it is considered effective to mix the above-mentioned solvent, for example.
Since the anthracene derivative of the present invention has high solubility in many solvents even in a skeleton in which film formation is difficult by a vapor deposition method having a molecular weight exceeding 1000, an ink having a concentration and viscosity suitable for various solution processes. Is easy to prepare.

Example 27: Thin film production example 1
HTL1 synthesized in Example 1 was dissolved in chloroform to a concentration of 1.0 wt%, and filtered through a 0.2 μm filter to prepare a solution. 100 μL of the prepared solution is dropped with a pipette onto an N-type silicon substrate having a thermal oxide film with a thickness of 300 nm that has been washed for 24 hours in concentrated sulfuric acid, and is left to stand until the solvent is dried. Then, a thin film was produced. Thin film observation was performed using a polarizing microscope and a scanning probe microscope [Contact Mode, Nanopics (trade name), Seiko Instruments Inc. It was found that a smooth continuous amorphous film was obtained.
Next, after the thin film was annealed at 150 ° C. for 5 minutes in an argon atmosphere, the film was observed in the same manner as described above. When confirmed with a modified microscopic image even after the annealing treatment, it was found that no crystallization occurred and an amorphous continuous smooth film was maintained. The annealed thin film was dissolved in chloroform and subjected to accurate mass spectrometry. As a result, m / z, measured value of the thin film extract after heating: 430.1752, 9,10-di (2-naphthyl) The theoretical value of anthracene: 430.1722 and the exact mass coincided with two decimal places. From this, the film formed from HTL1 was desorbed by heating to form a double bond, thereby quantitatively forming amorphous properties of 9,10-di (2-naphthyl) anthracene. It was found that it was converted into a film.

[Comparative Example 1]
In Example 27, except that HTL1 was changed to 9,10- (2-naphthyl) -anthracene, a thin film was prepared and observed, and it was partially crystallized in a polarization microscope image. Was confirmed. Further, it was confirmed in the scanning probe microscope image that a discontinuous film was formed by crystallization. Similarly, when the film was heated to 150 ° C. and the polarizing microscope image was confirmed again, it was confirmed that crystallization was further advanced.

  From Example 27 and Comparative Example 1, it was found that the anthracene derivative of the present invention has low crystallinity and can easily form an amorphous film suitable for an organic EL material. Further, when the corresponding compound (in this case, 9,10- (2-naphthyl) -anthracene) formed after heat conversion is simply formed as a solution, a crystalline discontinuous film is obtained. It has also been clarified that an amorphous continuous film can be obtained by heat-treating the anthracene derivative of the present invention after film formation.

[Application Example 1; Organic EL device creation example 1]
Examples of the application of the anthracene derivative of the present invention and its heat conversion film to an organic EL device will be described below, but the application of the anthracene derivative of the present invention is not limited thereto.
A substrate made of 40 × 40 mm square transparent glass was prepared, and the substrate surface was cleaned by a known cleaning process. Next, ITO was formed on one surface of the substrate by a known film forming method, and then patterned into a stripe shape to form an anode (electrode). Thereafter, the ITO surface was cleaned by O2 plasma treatment. Next, a mixed aqueous solution containing PEDOT and PSS is prepared, and this is applied to one surface of the substrate on which the anode is formed by a spin coating method, and then dried at 150 ° C. for 5 minutes to form a hole injection layer made of PEDOT: PSS. Formed.
Next, a 1.0 wt% THF solution prepared by mixing the anthracene derivative HTL1 synthesized in Example 1 and an arylamine derivative (the following formula D-1) as a luminescent dye at a weight ratio (20: 1) was prepared, and the substrate A light emitting layer (thickness: 30 nm) doped with a luminescent dye (D-1) in HTL1 was obtained by applying the film by spin coating and then drying. Next, the substrate was placed in a chamber of a vacuum apparatus, and an exciton element layer made of BPhen and an electron transport layer made of Alq3 were formed in this order by vacuum deposition. Next, a striped cathode (electrode) in which LiF (film thickness: 0.5 nm) and MgAg (film thickness: 100 nm) were stacked in this order was formed by a vacuum evaporation method using a metal mask.

(Element evaluation)
About the produced organic EL element, the voltage dependence of current density, the voltage dependence of luminance, and the emission spectrum were measured, and the absolute fluorescence quantum efficiency was calculated.

[Application Example 2]
In application example 1, except that HTL1 was changed to HTL4, the organic EL element was produced and evaluated, and this was designated as application example 2.

[Application Example 3]
In application example 1, except that HTL1 was replaced with HTL5, the organic EL element was manufactured and evaluated, and this was designated as application example 3.

[Application Example 4]
In Application Example 1, except that HTL1 was replaced with HTL7, an organic EL element was produced and evaluated, and this was designated as Application Example 4.

[Application Example 5]
In Application Example 1, except that HTL1 was changed to HTL14, an organic EL element was produced and evaluated, and this was designated as Application Example 5.

[Application Example 6]
In Application Example 1, except that HTL1 was replaced with HTL18, an organic EL element was produced and evaluated, and this was designated as Application Example 6.

[Application Example 7]
In Application Example 1, except that HTL1 was changed to HTL19, an organic EL element was produced and evaluated, and this was designated as Application Example 7.

[Application Example 8]
In Application Example 1, 9,10- (2-naphthyl) corresponding to the structure in which the detachable substituent is eliminated by forming a mixed film of HTL1 and D-1 and heating at 160 ° C. for 30 minutes. An organic EL device was prepared and evaluated in the same manner except that it was converted into a mixed film of anthracene (RHRH1 below) and D-1.

[Application Example 9]
In Application Example 5, except that HTL1 is replaced with HTL4 and the annealing temperature is set to 200 ° C. In the same manner, the organic EL device is converted into the corresponding compound from which the leaving group is eliminated (RHTL2 below) and the device Evaluation was performed and this was designated as Application Example 9.

[Application Example 10]
In Application Example 5, except that HTL1 was changed to HTL5, an organic EL device converted into a corresponding compound from which a leaving group was eliminated (RHTL3 below) was prepared and evaluated. Example 10 was taken.

[Application Example 11]
In Application Example 5, except that HTL1 was changed to HTL7, an organic EL device converted into a corresponding compound from which the leaving group was eliminated (RHTL4 below) was prepared and evaluated. Example 11 was used.

[Application Example 12]
In Application Example 5, except that HTL1 was replaced with HTL14 and the annealing temperature was changed to 200 ° C., and the production and device of an organic EL device converted into the corresponding compound from which the leaving group was eliminated (RHTL5 below) Evaluation was performed and this was designated as Application Example 12.

[Application Example 13]
In Application Example 5, except that HTL1 was replaced with HTL18 and the annealing temperature was changed to 230 ° C. In the same manner, an organic EL device converted into a corresponding compound from which a leaving group was eliminated (RHTL6 below) and an element Evaluation was performed and this was designated as Application Example 13.

[Application Example 14]
In Application Example 5, except that HTL1 was replaced with HTL19 and the annealing temperature was changed to 230 ° C., production of an organic EL device converted into a corresponding compound from which a leaving group was eliminated (RHTL7 below) and the device Evaluation was performed and this was designated as Application Example 14.

[Application Comparative Example 1]
In Application Example 1, an organic EL element was produced and evaluated in the same manner except that HTL1 was replaced with RHTL1 and the annealing process at 160 ° C. was omitted.

[Application Comparative Example 2]
Application Comparative Example 2 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL2.

[Application Comparative Example 3]
Application Comparative Example 3 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL3.

[Application Comparative Example 4]
Application Comparative Example 4 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL4.

[Application Comparative Example 5]
Application Comparative Example 5 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL5.

[Application Comparative Example 6]
Application Comparative Example 6 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL6.

[Application Comparative Example 7]
Application Comparative Example 7 was obtained by replacing RHTL1 in Application Comparative Example 1 with RHTL7.

The evaluation results of absolute fluorescence quantum efficiencies of Application Examples 1 to 14 and Application Comparative Examples 1 to 7 are shown in the table below.
FIG. 4 shows the results of evaluating the voltage dependence of the current density of the organic EL element (application example 7).
FIG. 5 shows the results of evaluating the voltage dependence of the luminance of the organic EL element (application example 7). FIG. 6 shows an emission spectrum when the current density of the organic EL element (application example 7) is 10 mA / cm ² .
From FIG. 4, the current density at an applied voltage of 7 V was about 80 mA / cm ² . From FIG. 5, the emission start voltage was 2.5V. The maximum external quantum efficiency was about 1.2%.
From FIG. 6, the peak considered to be due to light emission seen in the short wavelength region was hardly observed. This is a result showing that almost all excitons generated in the device are obtained as light emission of the luminescent dye (D-1). To the anthracene derivative film of the present invention formed by the printing process This is a result showing that 2-tert-butyl-9,10- (2-naphthyl) anthracene (RHTL3) obtained by applying external energy functions as a light emitting layer of the organic EL element.

Table 8 shows that the anthracene derivative of the present invention exhibits high absolute quantum efficiency as a host material (Application Example 1-7). Moreover, it turns out that the device using the anthracene derivative which heat-converted these films | membranes shows a higher characteristic (application example 8-14). It can be seen that these characteristics cannot be obtained by forming a film of the corresponding compound simply as a solution (Application Comparative Example 1-7).
In particular, when huge molecules are simply formed from a solution as in Application Comparative Examples 6 and 7, it can be seen that the deterioration of the characteristics is remarkable due to the mixing with the dopant and the nonuniformity of the film quality.

JP 2000-68057 A JP 2010-034484 A JP 2007-305783 A US Pat. No. 5,935,721 US Patent Application Publication No. 2006/0014046 WO2005 / 080527 pamphlet US Pat. No. 6,534,199 JP 2008-166629 A JP 2011-213705 A Japanese Patent Application No. 2011-086973

Appl. Phys. Lett. 86, 071104 (2005)

Claims (10)

Anthracene derivatives represented by the following general formula (1).

(In the general formula (1), Ar ₁ and Ar ₂ are each independently a group having a partial structure represented by the following general formula (1-1) or general formula (1-2), substituted or unsubstituted A group selected from the group formed by an aromatic ring or a heterocyclic ring having 1 to 30 nuclear carbon atoms].
R ¹ to R ⁸ are a hydrogen atom, a substituent having a partial structure represented by the following general formula (1-1) or general formula (1-2), a substituted or unsubstituted aryl group having 6 to 50 nuclear carbon atoms. Substituted or unsubstituted heteroaryl group having 5 to 50 nucleus atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, substituted or unsubstituted From an alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted nuclear number 5 It is selected from 50 arylthio groups, substituted or unsubstituted silyl groups, carboxyl groups, halogen atoms, cyano groups, nitro groups and hydroxy groups.
Further, adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.
However, at least one of Ar ₁ and Ar ₂ and R _{1 to} R ₈ is a substituent having a partial structure represented by the following general formula (1-1) or (1-2). )

(In the general formulas (1-1) and (1-2), X and Y, (X ₁ and X ₂ ) and (Y ₁ and Y ₂ ) represent a hydrogen atom or a leaving substituent, One of Y, (X ₁ and X ₂ ) and (Y ₁ and Y ₂ ) is a leaving substituent and the other is a hydrogen atom, Q _{1 to} Q ₆ are a hydrogen atom, a halogen atom Or an organic group other than the above-mentioned leaving substituent, which may be bonded to each other to form a ring.) In the general formulas (1-1) and (1-2), the leaving substituent X or Y, (X ₁ and X ₂ ) or (Y ₁ and Y ₂ ) may be substituted. The anthracene derivative according to claim 1, wherein the anthracene derivative is one or more [ether group or acyloxy group] and the other is a hydrogen atom. _3. The anthracene derivative according to claim 1, wherein each of R ₂ , R ₃ , R ₆ , and R ₇ is a hydrogen atom. The R ₁ , R _4, R _{5, or} R ₈ is a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted cycloalkyl group. Anthracene derivatives according to   The anthracene derivative according to any one of claims 1 to 4, which is a material for an organic electroluminescence element.   6. The anthracene derivative according to claim 5, wherein the material for an organic electroluminescence element is a light emitting material for an organic electroluminescence element.   An organic electroluminescent material ink comprising at least a solvent and the anthracene derivative according to any one of claims 1 to 4.   The organic electroluminescent luminescent material ink according to claim 7, comprising a solvent, the anthracene derivative according to claim 1, and a luminescent dye.   A step of applying an external stimulus to a film formed using the ink according to claim 7 or 8 to release a leaving component, and to remove the leaving substituent to form a double bond. A method for producing an anthracene derivative-containing film.   A method for producing an anthracene derivative, comprising the step of applying an external stimulus to the anthracene derivative according to claim 1 to remove the leaving substituent to form a double bond.

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