JP2016088927A - Anthracene derivative and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anthracene derivative desirably having controlled solubility, deposition property, wet coating property and orientation property (further desirably thermal stability) and an electroluminescent element excellent in at least one of efficacy, life and driving voltage by using the compound as a constituent of the electroluminescent element.SOLUTION: There is provided an anthracene derivative represented by the following formula (1). Ar-An-L-FG (1), where An is anthracene, Ar is aryl having 6 to 18 carbon atoms which may be substituted, L is arylene having 7 to 18 carbon atoms which may be substituted and 2 or more rings are condensed and FG is an oligophenylene structure bound at a meta position which may be substituted (functional group).SELECTED DRAWING: None

Description

  The present invention relates to an anthracene derivative and an organic electroluminescent device using the same. More specifically, an anthracene derivative having a functional functional group that can be formed by either a vacuum deposition method or a wet film formation method, and that provides excellent characteristics when used as a constituent component of an organic electroluminescence device. About.

  Organic electroluminescence devices are being actively studied as next-generation light-emitting display devices because they can produce thin and light flexible display devices and illumination with low power drive.

  An organic electroluminescent element has a structure which consists of a pair of electrode which consists of an anode and a cathode, and the one layer or several layer which is arrange | positioned between the said pair of electrodes and contains an organic compound. The layer containing an organic compound includes a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons. As a method for forming these organic layers, a vacuum deposition method or a wet film formation method is used.

  The vacuum deposition method has advantages such as being able to form a high-quality film uniformly on the substrate, easy to obtain a light-emitting element that is easy to stack and has excellent characteristics, and that there are very few impurities from the manufacturing process. Many of the organic electroluminescent devices currently in practical use are based on a vacuum deposition method using a low molecular weight material. On the other hand, the vacuum vapor deposition apparatus used in the vacuum vapor deposition method is generally expensive and difficult to continuously produce. If all steps are performed in a vacuum, there is a problem that the manufacturing cost is high.

  On the other hand, the wet film forming method does not require a vacuum process and does not require an expensive vacuum vapor deposition apparatus, so that a layer can be formed relatively inexpensively. Further, there is an advantage that a large area and continuous production are possible, and a plurality of materials having various functions can be put in one layer (coating liquid). On the other hand, in the wet film formation method, stacking is difficult, and it is difficult to obtain a high-quality and uniform coating film that does not contain impurities derived from the manufacturing process (for example, a solvent).

  Since the low molecular weight material assumes the production of an organic electroluminescent device by a vacuum deposition method, the solubility in a solvent is very low. Some low molecular weight materials that have been designed with a molecular design assuming a wet film formation method have alkyl chains and polar groups, but low molecular weight materials that have alkyl chains and polar groups are low molecular weight materials that do not have alkyl chains or polar groups. The light emitting device characteristics are inferior to

  Since high-molecular-weight materials are easier to obtain high-quality coatings than low-molecular-weight materials, high-molecular materials are used in wet film formation methods, but it is difficult to control the degree of polymerization and molecular weight distribution of high-molecular materials. There are problems such as deterioration due to terminal residues during continuous driving, high purity of the polymer material itself and difficulty in containing impurities, and it is difficult to obtain performance that can withstand practical use. .

  In addition, in order to further improve the characteristics of the organic electroluminescent device, various ideas have been incorporated into the development of the compound, and various ideas have been made on the compound. For example, one of them is orientation control. They have a rigid and linear structure, and the organic electroluminescence device containing an orientation compound as a constituent component effectively improves the characteristics.

International Publication No. 2001/072673 International Publication No. 2012/102333 JP 2006-0455503 A JP2013-168411A JP2013-247179A US Application Publication No. 2013/214259

  However, there has been no material that is a low-molecular material and has excellent solubility in a solvent and gives excellent characteristics when used as a constituent component of an organic electroluminescent element. The present invention relates to an anthracene derivative in which at least one of solubility, film forming property, wet coating property, thermal stability, and orientation property of a low-molecular compound is controlled by a functional functional group, Anthracene derivatives with controlled properties, film formability, wet coatability, and orientation (more desirably, thermal stability) are provided, and the compound is used as a component of an organic electroluminescent device, whereby efficiency, lifetime, and It is an object of the present invention to provide an organic electroluminescent device excellent in at least one of driving voltages.

  As shown below, the present inventors used an anthracene derivative (referred to as an “anthracene derivative having a functional functional group”) to which an oligophenylene skeleton linked at the meta position is bonded, so that the solubility of this derivative and film formation It has been found that at least one of property, wet coating property, thermal stability, and orientation can be controlled. In addition, it has been found that an organic electroluminescent device produced using an anthracene derivative having the functional functional group is excellent in at least one of efficiency, lifetime and driving voltage.

Ａｒは炭素数６〜１８のアリールであり、該アリールにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数３〜２４のシクロアルキルで置き換えられていてもよく、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられていてもよく、前記アルキルにおける前記アリールに直結している−ＣＨ_２−を除く任意の−ＣＨ_２−は炭素数６〜２４のアリーレンで置き換えられていてもよく、前記シクロアルキルにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく；
Ｌは２つ以上の環が縮合した炭素数７〜１８のアリーレンであってＡｎとＦＧとを連結し、前記アリーレンにおける少なくとも１つの水素は、炭素数１〜１２のアルキル、炭素数３〜２４のシクロアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく；
ＦＧは下記の構造式で表され、

Ｒは、それぞれ独立して、フッ素、トリメチルシリル、トリフルオロメチル、炭素数１〜２４のアルキルまたは炭素数３〜２４のシクロアルキルであり、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられていてもよく、前記アルキルにおけるフェニルまたはフェニレンに直結している−ＣＨ_２−を除く任意の−ＣＨ_２−は炭素数６〜２４のアリーレンで置き換えられていてもよく、前記シクロアルキルにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく、
ＦＧの隣り合う炭素に結合した２つのＲがアルキルまたはシクロアルキルであるとき、２つのＲ同士が結合して環を形成していてもよく、
ｍはそれぞれ独立して０〜４の整数であり、
ｎは０〜５の整数であり、
ｐは１〜５の整数であるが、上記式（１）が下記式（Ｘ−１）であるときｐは３〜５の整数であり、上記式（１）が下記式（Ｘ−２）であるときｐは２〜５の整数であり、下記式（Ｘ−１）または下記式（Ｘ−２）中のＡｒ、ＡｎおよびＦＧは上記式（１）における定義と同じである。

[1] An anthracene derivative represented by the following general formula (1).
Ar-An-L-FG (1)
(In the above formula (1),
An is represented by the following structural formula, Q is each independently hydrogen, alkyl having 1 to 24 carbons or alkoxy having 1 to 24 carbons, and bonded to Ar and L at the 9th and 10th positions, respectively. And

Ar is aryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl may be replaced with alkyl having 1 to 24 carbon atoms or cycloalkyl having 3 to 24 carbon atoms, and any — CH ₂ — may be replaced by —O—, and any —CH ₂ — except for —CH ₂ — directly bonded to the aryl in the alkyl is replaced by arylene having 6 to 24 carbon atoms. And at least one hydrogen in the cycloalkyl may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons;
L is an arylene having 7 to 18 carbon atoms in which two or more rings are condensed and connects An and FG, and at least one hydrogen in the arylene is an alkyl having 1 to 12 carbons and an alkyl having 3 to 24 carbon atoms. Optionally substituted with cycloalkyl or aryl having 6 to 12 carbon atoms;
FG is represented by the following structural formula:

R is each independently fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 24 carbons, and any —CH ₂ — in the alkyl is replaced by —O—. Any —CH ₂ — except for —CH ₂ — directly bonded to phenyl or phenylene in the alkyl may be substituted with arylene having 6 to 24 carbon atoms, and at least in the cycloalkyl One hydrogen may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons,
When two R bonded to adjacent carbons of FG are alkyl or cycloalkyl, the two Rs may be bonded to each other to form a ring,
m is each independently an integer of 0 to 4,
n is an integer of 0 to 5,
p is an integer of 1 to 5, but when the above formula (1) is the following formula (X-1), p is an integer of 3 to 5, and the above formula (1) is the following formula (X-2). P is an integer of 2 to 5, and Ar, An and FG in the following formula (X-1) or the following formula (X-2) are the same as defined in the above formula (1).

[2] The anthracene derivative according to the above [1], wherein p is 1 to 2.

上記式（１−１）〜（１−１０）中のＡｒ、ＡｎおよびＦＧは上記式（１）における定義と同じである。 [3] The anthracene derivative according to the above [1] or [2], wherein the formula (1) is represented by any of the following formulas (1-1) to (1-10).

Ar, An and FG in the above formulas (1-1) to (1-10) are the same as defined in the above formula (1).

[4] The anthracene derivative according to the above [3], wherein the formula (1) is represented by the formula (1-1) and Q is hydrogen.

上記式（１−１Ａ）中のＡｒ、ＡｎおよびＦＧは上記式（１）における定義と同じである。 [5] The anthracene derivative according to the above [4], wherein the formula (1-1) is represented by the following formula (1-1A).

Ar, An, and FG in the above formula (1-1A) are the same as defined in the above formula (1).

上記式（１−１Ｂ）中のＡｒ、ＡｎおよびＦＧは上記式（１）における定義と同じである。 [6] The anthracene derivative according to the above [4], wherein the formula (1-1) is represented by the following formula (1-1B).

Ar, An and FG in the above formula (1-1B) are the same as defined in the above formula (1).

[7] Ar is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5- Naphthacenyl, 1-pyrenyl, 2-pyrenyl, or 4-pyrenyl, in which at least one hydrogen may be replaced by alkyl having 1 to 12 carbons or cycloalkyl having 3 to 12 carbons, the above [ The anthracene derivative according to any one of [1] to [6].

[8] The anthracene derivative according to the above [7], wherein Ar is phenyl, 1-naphthyl, or 2-naphthyl, and at least one hydrogen thereof may be replaced by alkyl having 1 to 4 carbon atoms. .

[9] Each R is independently fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 12 carbons or cycloalkyl having 3 to 12 carbons,
m is each independently an integer of 0 to 2,
n is an integer from 0 to 2,
The anthracene derivative according to any one of the above [1] to [8], wherein p is 1 or 2.

[10] An ink composition comprising the anthracene derivative according to any one of [1] to [9].

（上記式（Ｓ−１）中、
ｈはｒ価のベンゼンまたはナフタレンであり、
ｊは、それぞれ独立して、単結合、エーテル結合、チオエーテル結合、カルボニル結合、エステル結合またはアミド結合であり、
ｋは、それぞれ独立して、アルキル、シクロアルキル、アリールまたはアルキルアリールであり、
ｒは１〜３の整数であり、
ｈにおいて隣接する炭素に結合する上記（ｊ−ｋ）同士が結合して環を形成していてもよい。） [11] The ink composition according to [10], further including a compound represented by the following general formula (S-1).

(In the above formula (S-1),
h is r-valent benzene or naphthalene;
each j is independently a single bond, an ether bond, a thioether bond, a carbonyl bond, an ester bond or an amide bond;
each k is independently alkyl, cycloalkyl, aryl or alkylaryl;
r is an integer of 1 to 3,
The above (jk) bonded to adjacent carbon in h may be bonded to form a ring. )

[12] j is a single bond or an ether bond,
The ink composition according to [11], wherein k is alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons, aryl having 6 to 12 carbons, or alkylaryl having 7 to 12 carbons.

[13] The ink composition according to the above [11] or [12], wherein r is 1.

[14] h is r-valent benzene,
The ink composition according to any one of [11] to [13], wherein k is alkyl having 6 to 12 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, methylphenyl, dimethylphenyl, or trimethylphenyl. .

[15] The ink composition according to any one of [11] to [14] above, comprising a compound having a boiling point of 200 ° C to 300 ° C.

[16] The ink composition according to any one of [10] to [15] above, which contains a condensed aromatic compound having an arylamino group bonded thereto, or a styryl derivative having an arylamino group bonded thereto.

[17] An organic electroluminescence device comprising an organic layer produced using the ink composition according to any one of [10] to [16].

  The anthracene derivative having a functional functional group according to the present invention can control solubility, film-forming property, wet coating property, thermal stability and orientation by the functional functional group. In addition, by forming each layer of the organic electroluminescent element with an anthracene derivative having a functional functional group, it is possible to extend the lifetime of the element, suppress an increase in voltage during driving, and decrease a driving voltage.

  When the number of functional functional groups phenyl or phenylene is increased, high solubility in organic solvents tends to be obtained. Since the functional functional group in the present invention has a structure in which phenylene is linked at the m-position, when a plurality of rotations between phenyl and phenyl in the functional functional group are combined, the functional functional group. Can draw a large rotational volume. In other words, the functional group is very flexible due to the m-position phenylene linkage structure. In addition, the biphenyl structure is known to take a planar structure when the angle between the phenyl rings is 0 ° in the crystal, and the functional group is expected to be the same. That is, the functional functional group has flexibility in a solution, but the flexibility of the functional functional group is suppressed after film formation, and it is considered that molecules are packed sufficiently densely in the film. This leads to an improvement in carrier mobility and a decrease in driving voltage because a carrier transport path is generated in the film. In addition, the molecular motion in the membrane is restricted, leading to improved stability against internal and external heat. Therefore, an anthracene derivative having a functional functional group used not only as a component of an organic electroluminescent device produced by using a vacuum deposition method but also an ink composition for a wet coating method and a wet coating method. It is also suitable for producing an organic electroluminescent element.

  Furthermore, the orientation of the functional functional group can be improved by controlling the size and substitution position of the functional functional group to improve the orientation, and the carrier mobility is controlled by the molecular orientation during vapor deposition and coating and drying. be able to.

It is a schematic sectional drawing which shows the organic electroluminescent element which concerns on this embodiment. It is a figure explaining the method to produce an organic electroluminescent element using the inkjet method on the board | substrate which has a bank.

Ａｒは炭素数６〜１８のアリールであり、該アリールにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数３〜２４のシクロアルキルで置き換えられていてもよく、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられていてもよく、前記アルキルにおける前記アリールに直結している−ＣＨ_２−を除く任意の−ＣＨ_２−は炭素数６〜２４のアリーレンで置き換えられていてもよく、前記シクロアルキルにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく；
Ｌは２つ以上の環が縮合した炭素数７〜１８のアリーレンであってＡｎとＦＧとを連結し、前記アリーレンにおける少なくとも１つの水素は、炭素数１〜１２のアルキル、炭素数３〜２４のシクロアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく；
ＦＧは下記の構造式で表され、

Ｒは、それぞれ独立して、フッ素、トリメチルシリル、トリフルオロメチル、炭素数１〜２４のアルキルまたは炭素数３〜２４のシクロアルキルであり、前記アルキルにおける任意の−ＣＨ_２−は−Ｏ−で置き換えられていてもよく、前記アルキルにおけるフェニルまたはフェニレンに直結している−ＣＨ_２−を除く任意の−ＣＨ_２−は炭素数６〜２４のアリーレンで置き換えられていてもよく、前記シクロアルキルにおける少なくとも１つの水素は炭素数１〜２４のアルキルまたは炭素数６〜１２のアリールで置き換えられていてもよく、
ＦＧの隣り合う炭素に結合した２つのＲがアルキルまたはシクロアルキルであるとき、２つのＲ同士が結合して環を形成していてもよく、
ｍはそれぞれ独立して０〜４の整数であり、
ｎは０〜５の整数であり、
ｐは１〜５の整数であるが、上記式（１）が下記式（Ｘ−１）であるときｐは３〜５の整数であり、上記式（１）が下記式（Ｘ−２）であるときｐは２〜５の整数である。

1. The anthracene derivative having a functional functional group represented by the general formula (1) The present invention is an anthracene derivative represented by the following general formula (1), and is useful as, for example, an organic semiconductor compound for an organic electroluminescence device It is.
Ar-An-L-FG (1)
(In the above formula (1),
An is represented by the following structural formula, Q is each independently hydrogen, alkyl having 1 to 24 carbons or alkoxy having 1 to 24 carbons, and bonded to Ar and L at the 9th and 10th positions, respectively. And

Ar is aryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl may be replaced with alkyl having 1 to 24 carbon atoms or cycloalkyl having 3 to 24 carbon atoms, and any — CH ₂ — may be replaced by —O—, and any —CH ₂ — except for —CH ₂ — directly bonded to the aryl in the alkyl is replaced by arylene having 6 to 24 carbon atoms. And at least one hydrogen in the cycloalkyl may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons;
L is an arylene having 7 to 18 carbon atoms in which two or more rings are condensed and connects An and FG, and at least one hydrogen in the arylene is an alkyl having 1 to 12 carbons and an alkyl having 3 to 24 carbon atoms. Optionally substituted with cycloalkyl or aryl having 6 to 12 carbon atoms;
FG is represented by the following structural formula:

R is each independently fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 24 carbons, and any —CH ₂ — in the alkyl is replaced by —O—. Any —CH ₂ — except for —CH ₂ — directly bonded to phenyl or phenylene in the alkyl may be substituted with arylene having 6 to 24 carbon atoms, and at least in the cycloalkyl One hydrogen may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons,
When two R bonded to adjacent carbons of FG are alkyl or cycloalkyl, the two Rs may be bonded to each other to form a ring,
m is each independently an integer of 0 to 4,
n is an integer of 0 to 5,
p is an integer of 1 to 5, but when the above formula (1) is the following formula (X-1), p is an integer of 3 to 5, and the above formula (1) is the following formula (X-2). P is an integer of 2-5.

1-1. The structure An represented by An is represented by the following structural formula, anthracene-9,10-diyl, and is bonded to Ar and L at positions 9 and 10 of An, respectively.

1-1-2. Substituent Q to An
Each Q is independently hydrogen, alkyl having 1 to 24 carbons or alkoxy having 1 to 24 carbons. Hydrogen is particularly preferable from the viewpoint of the emission characteristics and lifetime of the produced organic electroluminescence device.

  The “C1-C24 alkyl” may be either linear or branched, and examples thereof include straight-chain alkyl having 1 to 24 carbons and branched-chain alkyl having 3 to 24 carbons. From the viewpoint of the light emission characteristics and lifetime of the produced organic electroluminescent device, alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, and alkyl having 1 to 12 carbon atoms (3 to 3 carbon atoms). 12-branched alkyl) is more preferred, alkyl having 1 to 6 carbon atoms (branched alkyl having 3 to 6 carbon atoms) is further preferred, and alkyl having 1 to 4 carbon atoms (branched having 3 to 4 carbon atoms). Chain alkyl) is particularly preferred.

  Specific examples of the “alkyl having 1 to 24 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t -Pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1- Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-he Sadeshiru, n- heptadecyl, n- octadecyl, and n- eicosyl but like, but is not so limited.

  Examples of the “alkoxy having 1 to 24 carbon atoms” include alkoxy having 1 to 15 carbon atoms from the viewpoint of light emission characteristics and lifetime of the produced organic electroluminescent element. Furthermore, C1-C12 alkoxy is preferable and C1-C6 alkoxy is more preferable. Specific alkoxy includes methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy.

1-2. The structure Ar represented by Ar is a substituted or unsubstituted aryl having 6 to 18 carbon atoms. The “aryl having 6 to 18 carbon atoms” is preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms, and particularly preferably aryl having 6 to 10 carbon atoms.

  Specific examples of aryl from the viewpoint of light emission characteristics and lifetime of the produced organic electroluminescence device include 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, and 3-phenanthryl. 4-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-p-terphenyl, 3- p-terphenyl, 4-p-terphenyl, 2-m-terphenyl, 3-m-terphenyl, 4-m-terphenyl, 2-o-terphenyl, 3-o-terphenyl, 4-o -Terphenyl, 2'-p-terphenyl, 2'-m-terphenyl, 4'-m-terphenyl, 5'-m-terphenyl, 3 ' o- terphenyl, and 4'-o--terphenyl, etc. Although the like, but is not so limited. Among these, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-p-terphenyl, 3-p-terphenyl, 4-p-terphenyl, 2-m -Terphenyl, 3-m-terphenyl, 4-m-terphenyl, 2-o-terphenyl, 3-o-terphenyl, 4-o-terphenyl, 2'-p-terphenyl, 2'- Preferred are m-terphenyl, 4′-m-terphenyl, 5′-m-terphenyl, 3′-o-terphenyl, and 4′-o-terphenyl, phenyl, 1-naphthyl, and 2-naphthyl. Is more preferable.

1-2-1. Substituent to Ar At least one hydrogen in Ar may be substituted, and examples of the substituent include alkyl having 1 to 24 carbon atoms, cycloalkyl having 3 to 24 carbon atoms, and optional —CH ₂ —. -O- with replaced alkyl having 1 to 24 carbon atoms, -CH connected directly to Ar ₂ - arbitrary -CH ₂ except - from 1 to 24 carbon atoms which is replaced by an arylene having 6 to 24 carbon atoms Or an alkyl having 3 to 24 carbon atoms in which at least one hydrogen is replaced with an alkyl having 1 to 24 carbon atoms, or 3 to 24 carbon atoms in which at least one hydrogen is replaced with an aryl having 6 to 12 carbon atoms. Of cycloalkyl.

The “C1-C24 alkyl” may be either linear or branched, and examples thereof include straight-chain alkyl having 1 to 24 carbons and branched-chain alkyl having 3 to 24 carbons. C1-C18 alkyl (C3-C18 branched alkyl) is preferable, C1-C12 alkyl (C3-C12 branched alkyl) is more preferable, C1-C6 Of alkyl (C3-C6 branched alkyl) is more preferred, and C1-C4 alkyl (C3-C4 branched alkyl) is particularly preferred.
In these alkyls, any —CH ₂ — may be replaced by —O—, and any —CH ₂ — (except for —CH ₂ — directly connected to Ar) has 6 to 6 carbon atoms. It may be replaced with 24 arylenes. Examples of the arylene include, but are not limited to, the bivalent aryls described above as specific examples of Ar.

  Specific examples of the “alkyl having 1 to 24 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t -Pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1- Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-he Sadeshiru, n- heptadecyl, n- octadecyl, and n- eicosyl but like, but is not so limited.

Specific examples of “alkyl having 1 to 24 carbon atoms in which arbitrary —CH ₂ — is replaced by —O—” include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-propoxyethoxy, 2-butoxyethoxy, 2-ethoxy- (2-ethoxyethoxy), and 2- Examples include, but are not limited to, ethoxy- (2-ethoxy- (2-ethoxyethoxy)).

Examples of "- - arbitrary -CH ₂ except -CH ₂ connected directly to the Ar-alkyl of 1 to 24 carbon atoms is replaced by an arylene 6 to 24 carbon atoms" specifically includes methyl benzyl, Examples include, but are not limited to, ethyl benzyl and propyl benzyl.

  As the “cycloalkyl having 3 to 24 carbon atoms”, cycloalkyl having 3 to 12 carbon atoms is preferable, cycloalkyl having 3 to 10 carbon atoms is more preferable, cycloalkyl having 3 to 8 carbon atoms is further preferable, 3-6 cycloalkyl is particularly preferred.

  Specific examples of the cycloalkyl having 3 to 24 carbon atoms include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

  “C3-C24 cycloalkyl in which at least one hydrogen is replaced by alkyl having 1 to 24 carbons” or “C3-C24 in which at least one hydrogen is replaced by aryl having 6 to 12 carbons” Specific examples of “cycloalkyl” include, but are not limited to, methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, phenylcyclohexyl, naphthylcyclohexyl, and the like.

  From the viewpoint of the emission characteristics and lifetime of the produced organic electroluminescent device, the substituent for Ar preferably has a smaller number of carbon atoms, for example, those having 1 to 12 carbon atoms are preferred, and those having 1 to 8 carbon atoms are preferred. Are more preferable, and those having 1 to 4 carbon atoms are more preferable.

1-3. The structure L represented by L is an arylene having 7 to 18 carbon atoms in which two or more rings are condensed, and any two hydrogens in the arylene are replaced by FG and An (L is An and FG is connected). The “arylene having 7 to 18 carbon atoms” is preferably arylene having 7 to 16 carbon atoms, more preferably arylene having 7 to 14 carbon atoms, and further preferably arylene having 7 to 10 carbon atoms.
Specifically, the arylene shown in the structure represented by the following general formulas (1-1) to (1-10) can be given, for example. In the following formulas (1-1) to (1-10), An is replaced with any one hydrogen atom in L, and FG is replaced with any one hydrogen atom except for the hydrogen atom in which An is replaced in L. It is done.

  In the above formulas (1-1) to (1-10), arylene having no substituent other than An and FG is shown, but at least the hydrogen atom replaced with An and FG in the arylene in the above formula is excluded. One hydrogen may be replaced by alkyl having 1 to 12 carbons, cycloalkyl having 3 to 24 carbons or aryl having 6 to 12 carbons.

  L is preferably arylene in the formulas (1-1) to (1-10) having no substituent other than An and FG from the viewpoint of the light emission characteristics and lifetime of the produced organic electroluminescent device, and particularly An and FG. Arylene in formula (1-1) having no substituent other than is preferable.

1-3-1. At least one hydrogen other than the hydrogen atom replaced with An and FG in the substituent L to L may be substituted, and examples of the substituent include alkyl having 1 to 12 carbons, Examples thereof include cycloalkyl and aryl having 6 to 12 carbon atoms.

Specific examples of the “alkyl having 1 to 12 carbon atoms” include those having 1 to 12 carbon atoms among those mentioned in the description of the substituent for Ar.
Specific examples of the “cycloalkyl having 3 to 24 carbon atoms” include those exemplified in the description of the substituent for Ar.
Specific examples of the “aryl having 6 to 12 carbon atoms” include those having 6 to 12 carbon atoms among those mentioned in the description of the structure represented by Ar.

1-4. The structure FG represented by FG is an aryl represented by the following structural formula.

1-4-1. Number of phenylene linkages p
The number p of phenylene linkages is preferably 1 to 5, more preferably 1 to 3, from the viewpoints of solubility, film formability, wet coatability, thermal stability, and orientation of anthracene derivatives having a functional functional group. 1 or 2 is more preferable.

1-4-2. Number of substitutions R and m
Regarding the number of substitutions m and n of the substituent R, 0 to 4 is preferable, 0 to 2 is more preferable, 0 to 1 is more preferable, 0 is particularly preferable, and 0 is particularly preferable to 0. 0 to 3 are more preferable, 0 to 1 are more preferable, and 0 is particularly preferable.

1-4-3. Substituent R to FG
Regarding the substituent R to FG, from the viewpoint of the flexibility of the functional functional group and the filling property at the time of film formation, other than the o-position with respect to the phenyl-phenyl bond (based on the bond position between adjacent phenyl groups) It preferably has a substituent R, and more preferably has a substituent R at a position further away from the phenyl-phenyl bond.

R is fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 24 carbons, cycloalkyl having 3 to 24 carbons, or alkyl having 1 to 24 carbons in which any —CH ₂ — is replaced by —O—. Any of —CH ₂ — except for —CH ₂ — directly bonded to phenyl or phenylene, is substituted with aryl having 6 to 24 carbon atoms, and at least one hydrogen is substituted with 1 to Cycloalkyl having 3 to 24 carbon atoms substituted with 24 alkyl, or cycloalkyl having 3 to 24 carbon atoms in which at least one hydrogen is replaced with aryl having 6 to 12 carbon atoms.

As the “alkyl having 1 to 24 carbon atoms”, specifically, those mentioned in the description of the substituent for Ar can be cited.
Specific examples of the “cycloalkyl having 3 to 24 carbon atoms” include those exemplified in the description of the substituent for Ar.
As the “alkyl having 1 to 24 carbon atoms in which arbitrary —CH ₂ — is replaced by —O—”, specifically, those exemplified in the description of the substituent to Ar can be cited.
The "- - arbitrary -CH ₂ except -CH ₂ connected directly to the phenyl or phenylene alkyl of 1 to 24 carbon atoms which is replaced by an arylene of 6 to 24 carbon atoms", specifically, Ar Citation is made for the description of “alkyl having 1 to 24 carbon atoms in which any —CH ₂ — except for —CH ₂ — directly bonded to Ar” is substituted with arylene having 6 to 24 carbon atoms ”. can do.
“C3-C24 cycloalkyl in which at least one hydrogen is replaced by alkyl having 1 to 24 carbons” or “C3-C24 in which at least one hydrogen is replaced by aryl having 6 to 12 carbons” As the “cycloalkyl”, specifically, those exemplified in the description of the substituent for Ar can be cited.

1-5. Structure and expression characteristic of anthracene derivative having functional functional group An anthracene derivative having a functional functional group according to the present invention has a functional functional group having an appropriate length and structure at an appropriate position in the molecule. By disposing, it is possible to control the solubility of the derivative in a solvent, film formability, wet coatability, thermal stability, orientation, and the like.

1-5-1. Controlling solubility in solvents One of the molecular design guidelines for controlling solubility is to impart flexibility to molecules. It is believed that this can improve or control the solubility by reducing the cohesion between solid molecules and promoting rapid solvent infiltration during dissolution. In general, an alkyl chain is introduced into a molecule, but when used as an organic electroluminescent device, the alkyl chain may inhibit the accumulation of molecules and destroy the carrier path. In some cases, the drive voltage may increase or the mobility may decrease.

  In such a situation, the present inventor has found that by introducing a functional functional group having a structure in which phenylene is linked at the m-position, high solubility can be imparted without deteriorating the characteristics of the organic electroluminescent device. It was. When multiple rotations between phenyl and phenyl in the functional functional group are combined, the functional functional group can draw a large rotational volume and is very flexible. It is believed that the resulting derivatives can have high solubility. From the viewpoint of solubility, a longer functional functional group is preferable because it has higher flexibility and can impart solubility to molecules. Further, it is preferable to take a structure that does not disturb the flexibility of the functional functional group in the whole molecule because the flexibility of the functional functional group is maximized and sufficient solubility is imparted.

  In addition, it is known that the biphenyl structure takes a planar structure when the angle between the phenyl rings is 0 ° in the crystal, and the functional functional group can take a planar structure in the solid as well. Although the functional functional group has flexibility in the solution, it is considered that the flexibility of the functional functional group is suppressed after film formation, and molecules are packed sufficiently densely in the film. This leads to an improvement in carrier mobility and a decrease in driving voltage because a carrier transport path is generated in the film. From the viewpoint of the carrier transport path, a shorter functional functional group is preferable because the density of structures other than the functional functional group responsible for the path can be increased.

1-5-2. Control of film formability In this specification, “film formability” indicates a measure of the smoothness and uniformity of a film formed by vacuum deposition. If the compound has high crystallinity during film formation by the vacuum evaporation method, crystallization proceeds immediately after film formation, so that smoothness and uniformity of the film cannot be obtained.

  According to the functional group in the present invention, it is possible to give flexibility to a molecule and reduce crystallinity. Therefore, the film formability during vacuum deposition is improved by the addition of this functional functional group.

1-5-3. Control of wet coatability In this specification, “wet coatability” refers to a measure of smoothness and uniformity of a film formed by wet coatability. At the time of wet film formation, if the solubility is low, the film does not become a film and crystals are precipitated. On the other hand, if the solubility is high, film defects such as pinholes and flipping may occur. Strictly speaking, if there is too much difference from the solubility of other components, separation of components occurs, and further, compatibility with the solvent and composition, film formation / drying / firing processes affect the film quality, In order to obtain a high-quality film, it may be necessary to finely adjust each element. Therefore, it is considered that controlling the solubility without changing the HOMO and LUMO of the molecule leads to the control of the wet coatability.

  According to the functional functional group in the present invention, the solubility can be controlled without greatly affecting the structure other than the functional functional group responsible for HOMO and LUMO. Further, according to this functional functional group, it is possible to give a wide range of solubility, and it is possible to flexibly adjust the ink composition.

1-5-4. Controlling thermal stability The stability of organic electroluminescent devices during driving is estimated by the thermal stability (glass transition point). To increase the glass transition point, one is the cohesive force of molecules. I think that it is good to enlarge. That is, the better the solubility, the softer the molecule, the lower the glass transition point, and the lower the thermal stability.

  According to the functional functional group in the present invention, it is possible to give flexibility to the molecule, while expecting dense packing in the film, and as a result, the molecular motion can be restricted. Leads to improved stability against From the viewpoint of thermal stability, the longer the functional functional group, the larger the molecule, and the higher the Tg.

1-5-5. Controlling orientation With the aim of improving the properties of compounds used in organic electroluminescent devices, studies have been made to impart orientation by imparting a rigid structure in the molecule. In general, a compound having orientation has a rigid and highly linear structure such as p-terphenyl, and therefore has poor solubility.

  However, the present inventors have found that, contrary to conventional technical common sense, by replacing the functional functional group so that the molecule is long and the rod is in a rod shape, high orientation can be given even if it is not a rigid molecule. discovered. In this case, since the structure is not rigid and highly linear, the solubility does not decrease. From the viewpoint of orientation, it is preferable that the functional functional group is long and the molecule is rod-shaped. In addition, when the functional functional group is sufficiently long, high orientation can be expressed even if the molecule is bent.

1-6. Specific examples of anthracene derivatives having a functional functional group represented by the general structural formula (1) are shown below, but are not limited to the following derivatives. Among the following derivatives, the following formulas (1-1A-* # 1), (1-1B-* # 1), (1-1A-* # 2) and (1-1B-* # 2) (all * Is an alphabet, and # is a number. A derivative represented by the following formulas (1-1A-P # 1), (1-1B-P # 1), (1-1A-P # 2) and (1- 1B-P # 2) (where # is a number) is more preferable, and the following formulas (1-1B-P # 1) and (1-1B-P # 2) (both are numbers) The derivative represented by is more preferable.

2. Method for synthesizing anthracene derivative represented by general formula (1) An anthracene derivative having a functional functional group represented by general formula (1) is obtained by using a halogenated aryl derivative and an anthracene derivative boronic acid as starting materials by a known method. As a starting material, or using a halogenated arylboronic acid derivative and a halogenated anthracene as a starting material, a suitable combination of Suzuki-Miyaura coupling, Kumada-Tamao-Colleu coupling, Negishi coupling, halogenation reaction, or boration reaction Can be synthesized.

  The reactive functional group of the halide and boronic acid derivative in the Suzuki-Miyaura coupling may be replaced as appropriate, and the functional group involved in these reactions also in the Kumada / Tamao / Coryu coupling and Negishi coupling. May be replaced. Further, when converting to the Grignard reagent, the metal magnesium and the isopropyl grinder reagent may be appropriately replaced. The boronic acid ester may be used as it is, or may be hydrolyzed with an acid and used as a boronic acid. When used as a boronic ester, an alkyl group other than those exemplified above can be used as the alkyl group of the ester moiety.

Specific examples of the palladium catalyst used in the reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , Palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba) ₃ · CHCl _3, bis (dibenzylideneacetone) palladium _{(0): Pd (dba)} 2, bis (tri-t- butyl phosphino) palladium _{(0): Pd (t-} Bu 3 P) 2, [1,1 '-Bis (diphenylphosphino) ferrocene] dichloropalladium (II): Pd (d ppf) Cl ₂ , [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (1: 1): Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , PdCl ₂ {P (t _{-Bu) 2 - (p-NMe} 2 -Ph)} 2: (A- ta Phos) 2 PdCl 2, palladium bis (dibenzylideneacetone), [1,3-bis (diphenylphosphino) propane] nickel (II) _{dichloride, PdCl 2 [P (t-} Bu) 2 - (p-NMe 2 -Ph)] 2: (A- ta Phos) 2 PdCl 2 (Pd-132: trademark, manufactured by Johnson Matthey Inc.).

  In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphos Fino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, or An example is 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl.

  Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, potassium acetate. , Tripotassium phosphate, or potassium fluoride.

  Specific examples of the solvent used in the reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, anisole, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl. Examples include methyl ether, 1,4-dioxane, methanol, ethanol, t-butyl alcohol, cyclopentyl methyl ether, and isopropyl alcohol. These solvents can be appropriately selected and may be used alone or as a mixed solvent.

3. Ink Composition The anthracene derivative having a functional functional group of the present invention can be used as a component of an ink composition for coating and forming an organic electroluminescent element. The ink composition contains at least one anthracene derivative having a functional functional group represented by the general formula (1) as a first component and at least one organic solvent as a second component.

3-1. The organic solvent ink composition contains at least one organic solvent as the second component. The second component controls and improves the film formability, the presence or absence of defects in the coating film, the surface roughness and the smoothness by controlling the evaporation rate of the solvent during film formation. Also, during film formation using the ink jet method, the meniscus stability at the pinhole of the ink jet head is controlled to control and improve the ejection performance. In addition, by controlling the drying speed of the film and the orientation of the derivative molecules, it is possible to improve the electrical characteristics, light emitting characteristics, efficiency, and lifetime of the organic electroluminescent device having a light emitting layer obtained from the ink composition. .

  The boiling point of the organic solvent is preferably 130 ° C to 300 ° C, more preferably 140 ° C to 270 ° C or 150 ° C to 300 ° C, and further preferably 150 ° C to 250 ° C or 200 ° C to 300 ° C. When the boiling point is higher than 130 ° C., it is preferable from the viewpoint of ink jetting properties. Moreover, when a boiling point is lower than 300 degreeC, it is preferable from a viewpoint of the defect of a coating film, surface roughness, a residual solvent, and smoothness.

  After the film formation, the organic solvent is removed from the coating film by a drying process such as vacuum, reduced pressure, or heating. When heating, it is preferable to carry out below the glass transition temperature (Tg) of a 1st component. Even if the heating temperature is lower than the boiling point of the organic solvent, the organic solvent is sufficiently removed because the film is thin. A plurality of drying methods may be used in combination.

（上記式（Ｓ−１）中、
ｈはｒ価のベンゼンまたはナフタレンであり、
ｊは、それぞれ独立して、単結合、エーテル結合、チオエーテル結合、カルボニル結合、エステル結合またはアミド結合であり、
ｋは、それぞれ独立して、アルキル、シクロアルキル、アリールまたはアルキルアリールであり、
ｒは１〜３の整数であり、
ｈにおいて隣接する炭素に結合する上記（ｊ−ｋ）同士が結合して環を形成していてもよい。） As the organic solvent, for example, a compound represented by the following general formula (S-1) can be used.

(In the above formula (S-1),
h is r-valent benzene or naphthalene;
each j is independently a single bond, an ether bond, a thioether bond, a carbonyl bond, an ester bond or an amide bond;
each k is independently alkyl, cycloalkyl, aryl or alkylaryl;
r is an integer of 1 to 3,
The above (jk) bonded to adjacent carbon in h may be bonded to form a ring. )

  The alkyl in k may be either a straight chain or a branched chain, and examples thereof include a straight chain alkyl having 1 to 24 carbon atoms and a branched chain alkyl having 3 to 24 carbon atoms. Among these, alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms) is preferable, alkyl having 1 to 12 carbon atoms (branched alkyl having 3 to 12 carbon atoms) is more preferable, and carbon number 1 Alkyl having 6 to 6 (branched alkyl having 3 to 6 carbon atoms) is more preferable, and alkyl having 1 to 4 carbons (branched alkyl having 3 to 4 carbon atoms) is particularly preferable.

  Specific examples of the alkyl for k include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, and n-hexyl. 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl , 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n- Dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl n- heptadecyl, n- octadecyl, and n- eicosyl but like, but is not so limited.

  Examples of cycloalkyl at k include cycloalkyl having 3 to 24 carbon atoms. Among them, cycloalkyl having 3 to 12 carbon atoms is preferable, cycloalkyl having 3 to 10 carbon atoms is more preferable, cycloalkyl having 3 to 8 carbon atoms is further preferable, and cycloalkyl having 3 to 6 carbon atoms is particularly preferable.

  Specific examples of cycloalkyl at k include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

  Examples of the aryl at k include aryl having 6 to 18 carbon atoms. Among them, aryl having 6 to 16 carbon atoms is preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable.

Specific examples of the aryl for k include 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 1-naphthacenyl and 2-naphthacenyl. 5-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-p-terphenyl, 3-p-terphenyl, 4-p-terphenyl, 2-m-terphenyl, 3-m-terphenyl, 4-m-terphenyl, 2-o-terphenyl, 3-o-terphenyl, 4-o-terphenyl, 2′-p-terphenyl, 2'-m-terphenyl, 4'-m-terphenyl, 5'-m-terphenyl, 3'-o-terphenyl, 4'-o-terphenyl, etc. Including but but are not limited to.
Among these, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-p-terphenyl, 3-p-terphenyl, 4-p-terphenyl, 2-m -Terphenyl, 3-m-terphenyl, 4-m-terphenyl, 2-o-terphenyl, 3-o-terphenyl, 4-o-terphenyl, 2'-p-terphenyl, 2'- Preferred are m-terphenyl, 4′-m-terphenyl, 5′-m-terphenyl, 3′-o-terphenyl, and 4′-o-terphenyl, phenyl, 1-naphthyl, and 2-naphthyl. Is more preferable.

  Examples of the alkylaryl (alkyl-substituted aryl) in k include those in which the alkyl group described as k is substituted for the aryl group described as k. Specific examples include, but are not limited to, methylphenyl, dimethylphenyl, trimethylphenyl, methylnaphthyl, dimethylnaphthyl, and trimethylnaphthyl.

  r is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

  The above (jk) bonded to adjacent carbon in h may be bonded to form a ring. The ring thus formed may be an aliphatic ring or an aromatic ring, and examples thereof include the same ring structure as cycloalkyl and aryl described as k, and for h (benzene ring or naphthalene ring) The ring structure is condensed.

3-1-1. Specific examples of organic solvents Specific examples of organic solvents used in the ink composition include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexane-2-ol, heptane-2. -Ol, octan-2-ol, decan-2-ol, dodecan-2-ol, cyclohexanol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, terpineol (mixture), ethylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Diisopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, Diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, p-xylene, m-xylene, o-xylene, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro- o- Xylene, 2-chlorobenzotrifluoride, cumene, toluene, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, bromobenzene, 4-fluoroanisole, 3-fluoroanisole, 3 -Trifluoromethylanisole, mesitylene, 1,2,4-trimethylbenzene, t-butylbenzene, 2-methylanisole, phenetole, benzodioxole, 4-methylanisole, s-butylbenzene, 3-methylanisole, 4 -Fluoro-3-methylanisole, cymene, 1,2,3-trimethylbenzene, 1,2-dichlorobenzene, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, n-butylbenzene, 3-fluorobenzonitrile, Karin (decahydronaphthalene), neopentylbenzene, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethylanisole, 1-fluoro-3,5-dimethoxybenzene, methyl benzoate, Isopentylbenzene, 3,4-dimethylanisole, o-tolunitrile, n-amylbenzene, veratrol, 1,2,3,4-tetrahydronaphthalene, ethyl benzoate, n-hexylbenzene, n-heptylbenzene, n-octyl Benzene, n-nonylbenzene, n-decylbenzene, n-undecylbenzene, n-dodecylbenzene, propyl benzoate, cyclohexylbenzene, 1-methylnaphthalene, butyl benzoate, biphenyl, 2-methylbiphenyl, diphenyl ether, 3- Fe Kishitoruen, 2,2' bitolyl, and the like but, but is not so limited. Moreover, a solvent may be used alone or may be mixed.

3-1-2. The optional component ink composition may contain an optional component as long as its properties are not impaired. Examples of optional components include a binder and a surfactant.

3-1-2-1. The binder ink composition may contain a binder. The binder forms a film at the time of film formation and bonds the obtained film to the substrate. Also, it plays a role of dissolving, dispersing and binding other components in the ink composition. Further, a semiconductor polymer may be used as a binder. The semiconducting polymer serves to control the optical or electrical properties of the film obtained from the ink composition.

  Examples of the binder used in the ink composition include acrylic resin, polyethylene terephthalate, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, acrylonitrile-ethylene-styrene copolymer (AES) resin, ionomer, and chlorine. Polyether, diallyl phthalate resin, unsaturated polyester resin, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, Teflon, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer Polymer (AS) resin, phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, polyurethane, and copolymer of the above resin and polymer, but only But it is not limited.

  Examples of the semiconductor polymer that may be used as a binder include polyphenylene vinylene, polyphenylene, polyfluorene, polythiophene, polyvinyl carbazole, and the like. Furthermore, fluorene, triphenylamine, benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene. , Copolymers having structural units such as chrysene, triphenylene, pyrene, benzofuran, carbazole, acridine, and phenothiazine, but are not limited thereto.

  The binder used in the ink composition may be only one kind or a mixture of plural kinds.

3-1-2-2. The surfactant ink composition may contain, for example, a surfactant for controlling the film surface uniformity, the lyophilicity and the liquid repellency of the film surface of the ink composition. Surfactants are classified into ionic and nonionic based on the structure of the hydrophilic group, and further classified into alkyl, silicon, and fluorine based on the structure of the hydrophobic group. Further, the molecular structure is classified into a monomolecular system having a relatively small molecular weight and a simple structure, and a polymer system having a large molecular weight and having a side chain and a branch. Moreover, it classify | categorizes into the mixed system which mixed the single system and 2 or more types of surfactant and the base material from a composition. As the surfactant that can be used in the ink composition, all kinds of surfactants can be used.

  Examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by BYK Japan), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Footent 222F, Footage 251, FTX-218 (trade name, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, Mitsubishi Materials Corporation) ), Megafuck F-470, Megafuck F-471, Megafuck F-475, Megafuck R-08, Megafuck F-477, Megafuck F-479, Megafuck F-553, Megafuck F-554 (Trade name, manufactured by DIC Corporation), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (Fluo Alkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene laurate, polyoxyethylene oleate Ate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxy Ethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene Mention may be made of naphthyl ether, alkylbenzene sulfonates and alkyl diphenyl ether disulfonate salt.

  Moreover, surfactant may be used by 1 type and may use 2 or more types together.

4). Composition and Physical Properties of Ink Composition An ink composition for forming an organic electroluminescent element containing an anthracene derivative having a functional functional group of the present invention has an organic solvent in which a first component and an arbitrary component are uniformly dissolved ( A second component).

  The content of each component in the ink composition includes good solubility, storage stability and film formability of each component in the ink composition, and good film quality of the coating film obtained from the ink composition, From the viewpoint of good discharge characteristics when using an ink jet method, and good electrical characteristics, light emission characteristics, efficiency, and lifetime of an organic electroluminescent device having a light emitting layer produced using the composition, the first component is 0.01 wt% to 10.0 wt% with respect to the total weight of the ink composition, and the second component is preferably 90.0 wt% to 99.99 wt% with respect to the total weight of the ink composition, The first component is 0.05 wt% to 5.0 wt% based on the total weight of the ink composition, and the second component is 95.0 wt% to 99.95 wt% based on the total weight of the ink composition. % Is more preferable, and the first component is based on the total weight of the ink composition. .1% to 3.0 wt%, the second component relative to the total weight of the ink composition, more preferably 99.9 wt% ～97.0 wt%.

  The ink composition can be produced by appropriately selecting the above-described components by stirring, mixing, heating, cooling, dissolving, dispersing and the like by a known method. Further, after preparation, filtration, degassing (also referred to as degas), ion exchange treatment, inert gas replacement / encapsulation treatment, and the like may be selected as appropriate.

  As the viscosity of the ink composition, the higher the viscosity, the better the film formability and the better the ejection property when the ink jet method is used. On the other hand, it is easier to make a thin film with a low viscosity. From this, the viscosity of the ink composition is usually 0.3 mPa · s to 30 mPa · s at 25 ° C., 0.3 mPa · s to 3 mPa · s, or 1 mPa · s to 10 mPa · s. It is preferably 1 mPa · s to 3 mPa · s. In the present invention, the viscosity is a value measured using a conical plate type rotational viscometer (cone plate type).

  The lower the surface tension of the ink composition, the better the film formability and the coating film without defects. On the other hand, higher ink jetting properties can be obtained. Therefore, the viscosity of the ink composition is preferably 20 mN / m to 40 mN / m, more preferably 20 mN / m to 30 mN / m, at 25 ° C. In the present invention, the surface tension is a value measured using the hanging drop method.

5. Organic Electroluminescent Device The anthracene derivative represented by the above general formula (1) according to the present invention can be used as a material for an organic electroluminescent device, for example. Below, the organic EL element which concerns on this embodiment is demonstrated in detail based on drawing. FIG. 1 is a schematic cross-sectional view showing an organic EL element according to this embodiment.

5-1. Structure of Organic Electroluminescent Device The organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a positive electrode. A hole transport layer 104 provided on the hole injection layer 103; a light-emitting layer 105 provided on the hole transport layer 104; an electron transport layer 106 provided on the light-emitting layer 105; The electron injection layer 107 provided on the layer 106 and the cathode 108 provided on the electron injection layer 107 are included.

  The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. An electron transport layer 106 provided on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Each of the layers may be composed of a single layer or a plurality of layers.

  As an aspect of the layer constituting the organic electroluminescence device, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ”,“ substrate ” / Anode / light emitting layer / electron transport layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / hole transport layer / light emitting layer / “Electron transport layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport” Layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / cathode "may be configured aspect of the" substrate / anode / light emitting layer / electron injection layer / cathode ".

5-2. The substrate substrate 101 in the organic electroluminescent element serves as a support for the organic electroluminescent element 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

5-3. The anode 102 in the organic electroluminescent element plays a role of injecting holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

  Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide). Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances currently used as an anode of an organic electroluminescent element, and can use it.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 50 to 300 nm.

5-4. The hole injection layer, the hole transport layer, and the hole injection layer 103 in the organic electroluminescence device have a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. To fulfill. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

  As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, an anthracene derivative represented by the above general formula (1) can be used. In addition, among photoconductive materials, compounds conventionally used as hole charge transport materials, p-type semiconductors, and known materials used in hole injection layers and hole transport layers of organic electroluminescence devices Any one can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine, ^4, N ^{4 '-} diphenyl ^{-N 4,} N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] ^{-4,4'-diamine, N} 4, N ^4, N ^{4 ',} N ^4' - tetramethyl [1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -4,4'-diamine, 4,4 ', 4 "- tris (Triphenylamine derivatives such as (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives And thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7, 0,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the above monomers in the side chain are preferred, but light emission There is no particular limitation as long as it is a compound that can form a thin film necessary for manufacturing the device, inject holes from the anode, and further transport holes.

  It is also known that the conductivity of organic semiconductors is strongly influenced by the doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine ZnPc and the like). 2005-167175).

5-5. The light emitting layer 105 in the organic electroluminescent device emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. . The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency. In the present invention, an anthracene derivative represented by the general formula (1) can be used as a material for the light emitting layer.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is. The anthracene derivative represented by the general formula (1) can also be used as a host material.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented. The anthracene derivative represented by the general formula (1) can also be used as a dopant material.

  Host materials that can be used in combination with the anthracene derivative represented by the general formula (1) include condensed ring derivatives such as anthracene and pyrene, bisstyrylanthracene derivatives and distyrylbenzene derivatives that have been known as light emitters. And bisstyryl derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives, and the like.

  Moreover, it does not specifically limit as a dopant material which can be used together with the anthracene derivative represented by the said General formula (1), A well-known compound can be used and various according to desired luminescent color. You can choose from various materials. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazoles Derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, distyrylbenzene derivatives, etc. (Japanese Patent Laid-Open No. 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-247278), diazaine Isobenzofuran derivatives such as dacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, Dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives , Coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives, oxobes Zoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadiazo Lopylene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

  Illustrated for each color light, blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic complex such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazoles, thiazoles, thiadiazos Azole derivatives such as sulfazole, carbazole, oxazole, oxadiazole, triazole and metal complexes thereof and N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1 Examples include aromatic amine derivatives represented by '-diamine.

  Examples of green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene, and the above blue The compound which introduce | transduced the substituent which enables long wavelength, such as aryl, heteroaryl, aryl vinyl, amino, and cyano to the compound illustrated as a blue-green dopant material is also mentioned as a suitable example.

  Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazones Substituents that enable longer wavelengths such as aryl, heteroaryl, arylvinyl, amino, and cyano are added to the compounds exemplified as the above-mentioned blue to blue-green and green to yellow dopant materials. The introduced compound is also a suitable example.

  In addition, as a dopant, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

  Among the dopant materials described above, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferable.

当該式中、Ａｒ^１は炭素数６〜３０のアリールに由来するｍ価の基であり、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであるが、Ａｒ^１〜Ａｒ^３の少なくとも１つはスチルベン構造を有し、Ａｒ^１〜Ａｒ^３は置換されていてもよく、そして、ｍは１〜４の整数である。 The amine having a stilbene structure is represented by the following formula, for example.

In the formula, Ar ¹ is an m-valent group derived from aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, Ar ^{1 to} Ar ^At least one of ³ has a stilbene structure, Ar ^{1 to} Ar ³ may be substituted, and m is an integer of 1 to 4.

当該式中、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^２およびＡｒ^３は置換されていてもよい。 The amine having a stilbene structure is more preferably a diaminostilbene represented by the following formula.

In the formula, Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

  Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, naphthyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrycenyl, naphthacenyl, perylene, stilbenyl, distyrylphenyl, distyrylbiphenylyl. , Distyrylfluorenyl and the like.

Specific examples of amines having a stilbene structure include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl) ) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (2-naphthyl) -4,4′-diaminostilbene, N, N′-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethyl Fluorene, 4,4′-bis (9-ethyl-3-cal And bazovinylene) -biphenyl and 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl.
Moreover, you may use the amine which has a stilbene structure described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc.

Examples of perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene 3- (9′-anthryl) -8,11-di (t-butyl) perylene, 3,3′-bis (8,11-di (t-butyl) perylenyl), and the like.
Also, JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A No. 2000-34234, JP-A No. 2001-267075, JP-A No. 2001-217077 and the like may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9′-anthryl) dimesitylborylnaphthalene, 4- (10 ′). -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) -10- (Dimesitylboryl) anthracene and the like.
Moreover, you may use the borane derivative described in the international publication 2000/40586 pamphlet.

当該式中、Ａｒ^４は炭素数６〜３０のアリールに由来するｎ価の基であり、Ａｒ^５およびＡｒ^６はそれぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^４〜Ａｒ^６は置換されていてもよく、そして、ｎは１〜４の整数である。 The aromatic amine derivative is represented by the following formula, for example.

In the formula, Ar ⁴ is an n-valent group derived from aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are It may be substituted and n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ Are more preferably aromatic amine derivatives wherein n is 2 and n is 2.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and pentacene.

  Examples of the aromatic amine derivative include chrysene-based compounds such as N, N, N ′, N′-tetraphenylchrysene-6,12-diamine, N, N, N ′, N′-tetra (p-tolyl). Chrysene-6,12-diamine, N, N, N ′, N′-tetra (m-tolyl) chrysene-6,12-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) chrysene -6,12-diamine, N, N, N ', N'-tetra (naphthalen-2-yl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis ( 4-ethylphenyl) chrysene-6 2-diamine, N, N′-diphenyl-N, N′-bis (4-isopropylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-t-butyl) Phenyl) chrysene-6,12-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) chrysene-6,12-diamine, and the like.

  Examples of the pyrene-based compound include N, N, N ′, N′-tetraphenylpyrene-1,6-diamine, N, N, N ′, N′-tetra (p-tolyl) pyrene-1,6. -Diamine, N, N, N ', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) pyrene-1 , 6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'- Su (4-isopropylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-t-butylphenyl) pyrene-1,6-diamine, N, N′-bis (4-Isopropylphenyl) -N, N′-di (p-tolyl) pyrene-1,6-diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) -3,8- And diphenylpyrene-1,6-diamine.

  Examples of the anthracene system include N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N ′, N′-tetra (p-tolyl) anthracene-9,10-diamine. N, N, N ′, N′-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthrace -9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4- t-butylphenyl) anthracene-9,10-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-di -T-butyl-N, N, N ', N'-tetra (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-diphenyl-N, N' -Bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) Anthracene-9,10-diamy 2,6-dicyclohexyl-N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N′- Bis (4-isopropylphenyl) -N, N′-bis (4-t-butylphenyl) anthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, 9,10-bis (4-Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p- Tolylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino- And 9- (6-diphenylamino-2-naphthyl) anthracene.

Examples of pyrene-based compounds include N, N, N, N-tetraphenyl-1,8-pyrene-1,6-diamine and N-biphenyl-4-yl-N-biphenyl-1,8-pyrene-1. , ^6-diamine, N 1, ^{N 6} - diphenyl ^-N 1, ^{N 6} - bis - (4-trimethylsilanyl - phenyl)-1H, such 8H- 1,6-diamine.

Other examples include [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalen-2-yl] -diphenylamine, 4,4 ′. -Bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, and the like.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

Examples of the coumarin derivative include coumarin-6 and coumarin-334.
Moreover, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, and Unexamined-Japanese-Patent No. 6-298758.

また、特開2005-126399号公報、特開2005-097283号公報、特開2002-234892号公報、特開2001-220577号公報、特開2001-081090号公報、および特開2001-052869号公報などに記載されたピラン誘導体を用いてもよい。 Examples of the pyran derivative include the following DCM and DCJTB.

Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869. Alternatively, pyran derivatives described in the above may be used.

5-6. Electron injection layer and electron transport layer in the organic electroluminescence device The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

  The electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, an anthracene derivative represented by the general formula (1) can be used. In addition, it can be arbitrarily selected from compounds conventionally used as electron transport compounds in photoconductive materials and known compounds used in electron injection layers and electron transport layers of organic electroluminescent devices. .

  Materials used for the electron transport layer or the electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, and pyrrole derivatives. And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.

  Specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles. Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4- Triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phen Lene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2′-bis (benzo [h] quinolin-2-yl) -9,9′-spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzo Imidazole derivatives (such as tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 '-(2,2': 6'2 "-terpyridinyl)) benzene), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine Derivatives, carbazole derivatives, India Le derivatives, phosphorus oxide derivatives, such as bis-styryl derivatives.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give.

  Although the above-mentioned materials are used alone, they may be mixed with different materials.

  Among the materials described above, quinolinol-based metal complexes, bipyridine derivatives, phenanthroline derivatives, or borane derivatives are preferable.

式中、Ｒ^１〜Ｒ^６は水素または置換基であり、ＭはＬｉ、Ａｌ、Ｇａ、ＢｅまたはＺｎであり、ｎは１〜３の整数である。 The quinolinol-based metal complex is a compound represented by the following general formula (E-1).

In the formula, R ^{1 to} R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be, or Zn, and n is an integer of 1 to 3.

  Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4-me Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl) -8-quinolinolate) (3,5-di-tert-butyl) Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis ( 2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenol) Lat) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2 -Methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8) Quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano- 8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium and the like.

式中、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、ピリジン−ピリジンまたはピリジン−Ｇの結合に用いられない炭素は置換されていてもよい。 A bipyridine derivative is a compound represented by the following general formula (E-2).

In the formula, G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8. Further, carbon not used for bonding of pyridine-pyridine or pyridine-G may be substituted.

Examples of G in the general formula (E-2) include the following structural formulas. In addition, R in the following structural formula is each independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, or terphenylyl.

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-pyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Pyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-pyridine-6) -Yl) anthracene, 9,10-di (2,2'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) anthracene, 9,10-di (2 , 3′-Pyridin-5-yl) anthracene, 9,10-di (2,3′-pyridine) -Yl) -2-phenylanthracene, 9,10-di (2,3'-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,2'-pyridin-6-yl)- 2-phenylanthracene, 9,10-di (2,2′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,4′-pyridin-6-yl) -2-phenylanthracene 9,10-di (2,4′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (3,4′-pyridin-6-yl) -2-phenylanthracene, 9,10 -Di (3,4'-pyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'-pyridin-6-yl) thiophene, 3,4-diphenyl -2,5-di (2,3'-pyridine 5-yl) thiophene, 6'6 "- di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '- like quaterphenyl pyridine.

式中、Ｒ^１〜Ｒ^８は水素または置換基であり、隣接する基は互いに結合して縮合環を形成してもよく、Ｇは単なる結合手またはｎ価の連結基を表し、ｎは２〜８の整数である。また、一般式（Ｅ−３−２）のＧとしては、例えば、ビピリジン誘導体の欄で説明したものと同じものがあげられる。 A phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E-3-2).

In the formula, R ^{1 to} R ⁸ are hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent linking group, and n represents 2 It is an integer of ~ 8. Moreover, as G of general formula (E-3-2), the same thing as what was demonstrated in the column of the bipyridine derivative is mention | raise | lifted, for example.

  Specific examples of the phenanthroline derivative include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline- 2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9′-difluoro -Bi (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and the like.

  In particular, the case where a phenanthroline derivative is used for an electron transport layer and an electron injection layer will be described. In order to obtain stable light emission over a long period of time, a material excellent in thermal stability and thin film formation is desired, and among phenanthroline derivatives, the substituent itself has a three-dimensional structure, or a phenanthroline skeleton or Those having a three-dimensional structure by steric repulsion with an adjacent substituent or those having a plurality of phenanthroline skeletons linked to each other are preferred. Furthermore, when linking a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the linking unit is more preferable.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘは、置換されていてもよいアリーレンであり、Ｙは、置換されていてもよい炭素数１６以下のアリール、置換されているボリル、または置換されていてもよいカルバゾリルであり、そして、ｎはそれぞれ独立して０〜３の整数である。 The borane derivative is a compound represented by the following general formula (E-4), and is disclosed in detail in JP-A-2007-27587.

In the formula, each of R ¹¹ and R ¹² independently represents at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X is an optionally substituted arylene, and Y is Optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazolyl, and n is each independently an integer of 0 to 3.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｒ^２１およびＲ^２２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、ｎはそれぞれ独立して０〜３の整数であり、そして、ｍはそれぞれ独立して０〜４の整数である。 Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-1), and further the following general formulas (E-4-1-1) to (E-4) The compound represented by -1-4) is preferable. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.

In the formula, each of R ¹¹ and R ¹² independently represents at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen, alkyl, At least one of optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or cyano, and X ¹ is optionally substituted arylene having 20 or less carbon atoms. Each of n is independently an integer of 0 to 3, and each of m is independently an integer of 0 to 4.

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数２０以下のアリーレンであり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-2), and a compound represented by the following general formula (E-4-2-1) Is preferred.

In the formula, each of R ¹¹ and R ¹² independently represents at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and X ¹ is an optionally substituted arylene having 20 or less carbon atoms. And n is each independently an integer of 0 to 3.

式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In the formula, R ^{31 to} R ³⁴ are each independently any of methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently any of hydrogen, methyl, isopropyl or phenyl It is.

式中、Ｒ^１１およびＲ^１２は、それぞれ独立して、水素、アルキル、置換されていてもよいアリール、置換されているシリル、置換されていてもよい窒素含有複素環、またはシアノの少なくとも一つであり、Ｒ^１３〜Ｒ^１６は、それぞれ独立して、置換されていてもよいアルキル、または置換されていてもよいアリールであり、Ｘ^１は、置換されていてもよい炭素数１０以下のアリーレンであり、Ｙ^１は、置換されていてもよい炭素数１４以下のアリールであり、そして、ｎはそれぞれ独立して０〜３の整数である。 Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-3-3), and further, the following general formula (E-4-3-1) or (E-4) The compound represented by -3-2) is preferable.

In the formula, each of R ¹¹ and R ¹² independently represents at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano. R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, and X ¹ is an optionally substituted arylene having 10 or less carbon atoms. Y ¹ is optionally substituted aryl having 14 or less carbon atoms, and n is independently an integer of 0 to 3.

各式中、Ｒ^３１〜Ｒ^３４は、それぞれ独立して、メチル、イソプロピルまたはフェニルのいずれかであり、そして、Ｒ^３５およびＲ^３６は、それぞれ独立して、水素、メチル、イソプロピルまたはフェニルのいずれかである。

In each formula, R ^{31 to} R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl. It is.

式中、Ａｒ^１〜Ａｒ^３はそれぞれ独立に水素または置換されてもよい炭素数６〜３０のアリールである。特に、Ａｒ^１が置換されてもよいアントリルであるベンゾイミダゾール誘導体が好ましい。 The benzimidazole derivative is a compound represented by the following general formula (E-5).

In the formula, Ar ^{1 to} Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. In particular, a benzimidazole derivative which is anthryl optionally substituted with Ar ¹ is preferable.

  Specific examples of the aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, and fluorene-1- Yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, Triphenylene-1-yl, triphenylene-2-yl, pyreth -1-yl, pyren-2-yl, pyren-4-yl, chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, chrysene-6 -Yl, naphthacene-1-yl, naphthacene-2-yl, naphthacene-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, pentacene-1-yl, pentasen-2-yl , Pentacene-5-yl and pentacene-6-yl.

  Specific examples of the benzimidazole derivative include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene-2) -Yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1- Phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10 -(Naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (naphthalene) 2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl ) -2-phenyl-1H-benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracen-2-yl) -1,2-diphenyl-1H-benzo [d] imidazole is there.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more alkali metals is also preferable. Particularly, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

5-7. The cathode 108 in the organic electroluminescence device plays a role of injecting electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as that for forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium -Indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are often often unstable in the atmosphere. In order to improve this point, for example, a method is known in which an organic layer is doped with a small amount of lithium, cesium or magnesium and a highly stable electrode is used. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

  Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.

5-8. The material used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which is equal to or higher than the binder that may be used in each layer, can form each layer alone. Polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, Solvent-soluble resins such as vinyl acetate resin, ABS resin, polyurethane resin, and curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. Dispersed in It is also possible to have.

5-9. Manufacturing method of organic electroluminescent element Each layer constituting the organic electroluminescent element is made by vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method. It can be formed by forming a thin film by a method such as a coating method or a laser heating drawing method (LITI). The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm.

5-9-1. Vacuum deposition method In the vacuum deposition method, a material placed in a boat or a crucible in a vacuum is vaporized and scattered by heating and deposited on a substrate. The vacuum deposition method has advantages such as being able to form a high-quality film uniformly on the substrate, easy to obtain a light-emitting element that is easy to stack and has excellent characteristics, and that there is very little contamination from the manufacturing process. Many of the organic electroluminescent devices currently in practical use are based on a vacuum deposition method using a low molecular weight material. On the other hand, the vacuum deposition apparatus used in the vacuum deposition method is generally expensive, and the wet film forming method described later is superior in continuous productivity and manufacturing cost.

  In the case of thinning using a vacuum deposition method, the deposition conditions vary depending on the type of material, the intended crystal structure and association structure of the film, and the like. In general, the deposition conditions are appropriately set in the range of boat heating temperature +50 to + 400 ° C., vacuum degree 160 to 130 Pa, deposition rate 0.01 to 50 nm / second, substrate temperature −150 to + 300 ° C., film thickness 2 nm to 5 μm. It is preferable. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like.

5-9-2. Wet film-forming method In the case of forming a film using an anthracene derivative having a functional functional group of the present invention, a wet film-forming method can be used.

  In the wet film forming method, generally, a coating film is formed through an application step of applying an ink composition to a substrate and a drying step of removing a solvent from the applied ink composition. Depending on the coating process, a method using a spin coater is called a spin coating method, and a method using an ink jet printer is called an ink jet method. Examples of the drying process include air drying, heating, and drying under reduced pressure. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, for example, different methods may be used together, such as firing under reduced pressure.

  The wet film forming method is a film forming method using a solution, for example, a partial printing method (ink jet method), a spin coating method or a casting method, a coating method, or the like. Unlike the vacuum vapor deposition method, the wet film formation method does not require the use of an expensive vacuum vapor deposition apparatus and can form a film at atmospheric pressure. In addition, the wet film-forming method enables large area and continuous production, leading to reduction in manufacturing cost.

  On the other hand, when compared with the vacuum evaporation method, the wet film formation method is difficult to stack. When making a laminated film using the wet film formation method, it is necessary to prevent dissolution of the lower layer by the upper layer composition. The composition with controlled solubility, lower layer cross-linking and orthogonal solvent (Orthogonal solvent) Not a solvent). However, even if these techniques are used, it may be difficult to use a wet film formation method for coating all films.

  Therefore, in general, a method is employed in which only a few layers are formed using a wet film forming method, and the rest are formed using a vacuum vapor deposition method.

For example, a procedure for manufacturing an organic electroluminescent element by partially applying a wet film forming method is shown below.
(Procedure 1) Anode deposition by vacuum deposition (Procedure 2) Hole injection layer deposition by wet deposition (Procedure 3) Hole transport layer deposition by wet deposition (Procedure 4) Host material Film formation by wet film formation method (procedure 5) of electron transport layer by vacuum vapor deposition method (procedure 6) film formation of electron injection layer by vacuum vapor deposition method (procedure 7) Film Formation by Vacuum Deposition Method Through this procedure, an organic electroluminescence device comprising an anode / hole injection layer / hole transport layer / light emitting layer comprising a host material and a dopant material / electron transport layer / electron injection layer / cathode Is obtained.

5-9-3. Other Film Forming Method For forming the ink composition described in this specification into a film, a laser heating drawing method (LITI) can be used. LITI is a method in which a compound attached to a base material is heated and vapor-deposited with a laser, and an ink composition can be used as a material applied to the base material.

5-9-4. Before or after any of steps each step of the film formation, a suitable process step, a washing step and a drying step may be inserted as appropriate. Examples of the treatment process include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment. Furthermore, a series of steps for producing a bank is also included.

5-9-4-1. Bank (partition wall material)
Photolithographic technology can be used for manufacturing the bank. As a bank material that can be used for photolithography, a positive resist material and a negative resist material can be used. In addition, a patternable printing method such as an inkjet method, gravure offset printing, reverse offset printing, or screen printing can also be used. In this case, a permanent resist material can be used.

  Materials used for the bank include polysaccharides and derivatives thereof, homopolymers and copolymers of hydroxyl-containing ethylenic monomers, biopolymer compounds, polyacryloyl compounds, polyesters, polystyrenes, polyimides, polyamideimides, polyetherimides , Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane, epoxy (meth) acrylate, melamine (meth) acrylate, polyolefin, cyclic polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin, polyvinyl chloride, chlorine Polyethylene, chlorinated polypropylene, polyacetate, polynorbornene, synthetic rubber, polyfluorovinylidene, polytetrafluoroethylene, polyhexafluoro Fluorinated polymers Oro propylene, etc., fluoroolefins - hydrocarbonoxy olefin copolymer, fluorocarbon polymers, and the like, but is not so limited.

5-10. Example of Manufacturing Organic Electroluminescent Element Next, an example of a method of manufacturing an organic electroluminescent element by a vacuum deposition method and a wet film forming method using an ink jet will be described.

5-10-1. Example of Fabrication of Organic Electroluminescent Device by Vacuum Deposition Method An example of a method of fabricating an organic electroluminescent device by vacuum deposition method is as follows: anode / hole injection layer / hole transport layer / light emitting layer composed of host material and dopant material / electron A method for producing an organic electroluminescent device comprising a transport layer / electron injection layer / cathode will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained. In the preparation of the above-described organic electroluminescence device, the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.

5-10-2. Example of Fabrication of Organic Electroluminescent Device by Inkjet A method of fabricating an organic electroluminescent device using a inkjet method on a substrate having a bank will be described with reference to FIG. First, the bank (200) is provided on the electrode (120) on the substrate (110). In this case, an ink droplet (310) is dropped between the banks (200) from the inkjet head (300) and dried to produce the coating film (130). This process is repeated until the next coating film (140) and further the light emitting layer (150) are prepared, and the electron transport layer, the electron injection layer, and the electrode are formed using the vacuum deposition method. An organic electroluminescent device can be produced.

5-11. Confirmation of electric characteristics and light emission characteristics of organic electroluminescence device When applying a direct voltage to the organic electroluminescence device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When approximately -40 V is applied, light emission can be observed from the transparent or translucent electrode side (anode or cathode, and both). The organic electroluminescence device emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

5-12. Application Example of Organic Electroluminescent Device The present invention can also be applied to a display device provided with an organic electroluminescent device or a lighting device provided with an organic electroluminescent device.
A display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

  Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-13035066, JP-A-2003-321546, JP, 2004-281806, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  A matrix means a pixel in which pixels for display are two-dimensionally arranged such as a lattice or a mosaic, and displays a character or an image with a set of pixels. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

  In the segment system (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

<Synthesis of derivatives used in Examples>
Hereinafter, synthesis of derivatives used in Examples in Synthesis Examples 1 to 18 will be described.

<Synthesis Example 1: Synthesis of derivative (1-1B-P72)>

<Synthesis of P3Br>
42.44 g (150 mmol, 1.0 eq.) Of 1-bromo-3-iodobenzene, 29.70 g (1.0 eq.) Of biphenyl-3-ylboronic acid, 31.80 g (2.0 eq.) Of sodium carbonate, and Tetrakis (triphenylphosphine) palladium (0) 3.47 g (0.02 eq.) Was weighed into a 1 L three-necked round bottom flask, sufficiently degassed under reduced pressure and purged with nitrogen, and then 360 mL of toluene and ethanol under a nitrogen atmosphere. 90 mL and 90 mL of water were added, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “P3Br” was obtained as a clear oil (yield: 26.60 g, yield: 57.3%).

<Synthesis of P3Bpin>
P3Br 26.60 g (86.03 mmol, 1.0 eq.), Bispinacolate diboron 103.23 g (1.2 eq.), Potassium acetate 25.33 g (3 eq.) And bis (diphenylphosphino) ferrocene-palladium ( II) Dichloride Dichloromethane Complex 2.11 g (0.03 eq.) Was weighed into a 1 L three-necked round bottom flask, sufficiently degassed under reduced pressure and purged with nitrogen, and then 300 mL of cyclopentyl methyl ether was added under a nitrogen atmosphere, and 100 ° C. At reflux and stirring. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through activated carbon column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained yellow oil was dissolved in hot methanol, and allowed to stand at room temperature and then ice-cooled. The target product “P3Bpin” of the precipitated needle crystal was recovered (yield: 28.48 g, yield: 92.9%).

<Synthesis of P4Br>
1-bromo-3-iodobenzene 3.57 g (12.6 mmol, 1.0 eq.), P3Bpin 4.55 g (1.0 eq.), Sodium carbonate 4.01 g (3.0 eq.), And tetrakis (tri Phenylphosphine) palladium (0) 0.44 g (0.03 eq.) Was weighed into a 300 mL three-necked round bottom flask, sufficiently degassed under vacuum and purged with nitrogen, and then 40 mL of toluene, 10 mL of ethanol and water in a nitrogen atmosphere. 10 mL was added and refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was passed through silica gel column chromatography using heptane-toluene (9: 1 (volume ratio)) as an eluent, and the fraction containing the desired product was collected and concentrated under reduced pressure. The target product “P4Br” was obtained as a clear oil (yield: 3.97 g, yield: 80.8%).

<Synthesis of P4Bpin>
P4Br 3.97 g (10.20 mmol, 1.0 eq.), Bispinacolate diboron 3.11 g (1.2 eq.), Potassium acetate 3.00 g (3 eq.) And bis (diphenylphosphino) ferrocene-palladium ( II) Dichloromethane complex 0.25 g (0.03 eq.) Was weighed into a 200 mL three-necked round bottom flask, sufficiently degassed under reduced pressure and purged with nitrogen, and then added with 40 mL of cyclopentyl methyl ether under a nitrogen atmosphere, and 100 ° C. At reflux and stirring. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through activated carbon column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “P4Bpin” was obtained as a clear oil (yield: 4.30 g, yield: 95.1%).

<Synthesis of Derivative (1-1B-P72)>
P4Bpin 2.11 g (4.74 mmol, 1.0 eq.), 7- (10-phenylanthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate 2.51 g (1.0 eq), potassium phosphate 2.01 g (2.0 eq.) And 0.16 g (0.03 eq.) Of tetrakis (triphenylphosphine) palladium (0) were weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was passed through silica gel column chromatography using heptane-toluene (3: 1 (volume ratio)) as an eluent, and the fraction containing the desired product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 340 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P72) as a yellowish green glassy solid (yield: 1.20 g, yield). Rate: 37.0%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 2: Synthesis of a mixture of derivatives (1-1A-P32) and (1-1B-P42)>

<Synthesis of 14NpOTf2>
5.00 g (31.2 mmol, 1.0 eq.) Of 1,4-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 12.6 mL (74.9 mmol, 2.4 eq.) Of trifluoromethylsulfonic anhydride was added under ice cooling. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane (1: 4 (volume ratio)) as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “14NpOTf2” as a white solid (yield: 9.23 g, yield: 69.6%, purity: 99.8% (HPLC)). .

<Synthesis of PA3OTf and PB4OTf>
9-Phenylanthryl-10-boronic acid (9PA10BA) 1.40 g (4.7 mmol, 1.0 eq.), 14NpOTf2 2.00 g (4.7 mmol, 1 eq.), Potassium carbonate 1.30 g (9.4 mmol, 2.0 eq.) And 0.11 g (0.03 eq.) Of tetrakis (triphenylphosphine) palladium (0) were weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target products “PA3OTf” and “PB4OTf” (mixture) were obtained as white powder (yield: 0.80 g, yield: 32.2%, purity: 99.0% (HPLC)).

<Synthesis of Derivatives (1-1A-P32) and (1-1B-P42)>
1.73 g (4.00 mmol, 1.0 eq.) Of P4Bpin, 2.11 g (1.0 eq) of a mixture of PA3OTf and PB4OTf, 2.54 g (3.0 eq.) Of potassium phosphate and tetrakis (triphenylphosphine) palladium ( 0) 0.14 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing vacuum degassing and nitrogen substitution, 12 mL of toluene, 3 mL of ethanol and 3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder is subjected to sublimation purification at 340 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a mixture of derivatives (1-1A-P32) and (1-1B-P42) as a yellow-green glassy solid. It was. The contents of the derivatives (1-1A-P32) and (1-1B-P42) were 1: 4 (weight) (yield: 0.83 g, yield: 30.3%, purity: 99.9% or more) (HPLC)).

<Synthesis Example 3: Synthesis of Derivative (1-1A-P31)>

<Synthesis of 1Np3OTf and 3Np1OTf>
5.00 g (31.2 mmol, 1.0 eq.) Of 1,3-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 5.8 mL (34.3 mmol, 1.1 eq.) Of trifluoromethylsulfonic anhydride under ice cooling. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and subjected to silica gel column chromatography using toluene-ethyl acetate as an eluent. The fractions containing the target product were collected and concentrated to obtain the target products “1Np3OTf” and “3Np1OTf” as white solids.
1Np3OTf Yield: 2.56 g, Yield: 28.1%, Purity: 98.0% (HPLC)
3Np1OTf Yield: 2.10 g, Yield: 23.0%, Purity: 97.0% (HPLC)

<Synthesis of PA3OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 3Np1OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PA3OH” was obtained as a white powder (yield: 1.04 g, yield: 39.1%, purity: 98.0% (HPLC)).

<Synthesis of PA3OTf>
PA3OH 1.04 g (2.62 mmol, 1.0 eq.) Was dissolved in 30 mL of pyridine, and 0.5 mL (2.97 mmol, 1.1 eq.) Of trifluoromethylsulfonic anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “PA3OTf” as a white solid (yield: 0.95 g, yield: 68.6%, purity: 98.7% (HPLC)). .

<Synthesis of Derivative (1-1A-P31)>
PA3OTf 0.95 g (1.80 mmol, 1.0 eq.), P3Bpin 0.64 g (1.0 eq.), Potassium phosphate 1.15 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium (0) 0. 06 g (0.03 eq.) Was weighed into a 50 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient degassing under reduced pressure and nitrogen substitution, 5.3 mL of toluene, 1.3 mL of ethanol and 1.3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 300 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P31) as a yellowish green glassy solid (yield: 0.40 g, yield). Rate: 36.5%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 4: Synthesis of Derivative (1-1A-P32)>

PA3OTf 2.11 g (4.00 mmol, 1.0 eq.), P4Bpin 1.73 g (1.0 eq.), Potassium phosphate 2.54 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium (0) 0. 13 g (0.03 eq.) Was weighed into a 100 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 12 mL of toluene, 3 mL of ethanol and 3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 340 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P32) as a yellow-green glassy solid (yield: 0.95 g, yield). (Rate: 34.7%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 5: Synthesis of Derivative (1-1B-P41)>

<Synthesis of PB4OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 1Np3OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PB4OH” was obtained as a white powder (yield: 1.20 g, yield: 45.1%, purity: 98.0% (HPLC)).

<Synthesis of PB4OTf>
1.20 g (3.03 mmol, 1.0 eq.) Of PB4OH was dissolved in 30 mL of pyridine, and 0.6 mL (3.57 mmol, 1.2 eq.) Of trifluoromethylsulfonic acid anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “PB4OTf” as a white solid (yield: 1.22 g, yield: 76.3%, purity: 98.5% (HPLC)). .

<Synthesis of Derivative (1-1B-P41)>
PB4OTf 1.22 g (2.31 mmol, 1.0 eq.), P3Bpin 0.82 g (1.0 eq.), Potassium phosphate 1.47 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium (0) 0. 08 g (0.03 eq.) Was weighed into a 50 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient degassing under reduced pressure and nitrogen substitution, 5.3 mL of toluene, 1.3 mL of ethanol and 1.3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 300 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P41) as a yellowish green glassy solid (yield: 0.54 g, yield). Rate: 38.4%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 6: Synthesis of derivative (1-1B-P42)>

PB4OTf 2.11 g (4.00 mmol, 1.0 eq.), P4Bpin 1.73 g (1.0 eq.), Potassium phosphate 2.54 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium (0) 0. 13 g (0.03 eq.) Was weighed into a 100 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 12 mL of toluene, 3 mL of ethanol and 3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 340 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P42) as a yellow-green glassy solid (yield: 1.10 g, yield). Rate: 40.2%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 7: Synthesis of derivative (1-1B-P31)>

<Synthesis of 23NpOTf2>
5.00 g (31.2 mmol, 1.0 eq.) Of 2,3-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 12.6 mL (74.9 mmol, 2.4 eq.) Of trifluoromethylsulfonic anhydride was cooled with ice. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane (1: 4 (volume ratio)) as an eluent. The fraction containing the target product was collected and concentrated to obtain the target product “23NpOTf2” as a white solid (yield: 9.23 g, yield: 69.6%, purity: 99.8% (HPLC)). .

<Synthesis of PB3OTf>
9PA10BA 3.00 g (10.1 mmol, 1.0 eq.), 23NpOTf2 4.26 g (10.1 mmol, 1 eq.), Potassium carbonate 4.17 g (30.2 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.35 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 24 mL of toluene, 6 mL of ethanol and 6 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PB3OTf” was obtained as a white powder (yield: 1.60 g, yield: 30.1%, purity: 97.6% or more (HPLC)).

<Synthesis of Derivative (1-1B-P31)>
PB3OTf 1.48 g (2.80 mmol, 1.0 eq), P3Bpin 1.00 g (2.80 mmol, 1.0 eq.), Potassium phosphate 1.78 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.10 g (0.03 eq.) Was weighed into a 100 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen replacement, 8 mL of toluene, 2 mL of ethanol and 2 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P31) as a yellowish green glassy solid (yield: 0.58 g, yield). Rate: 34.0%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 8: Synthesis of Derivative (1-1B-P32)>

PB4OTf 1.74 g (3.29 mmol, 1.0 eq), P4Bpin 1.42 g (3.29 mmol, 1.0 eq.), Potassium phosphate 2.10 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.11 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar replacement was performed 5 times. After sufficient vacuum degassing and nitrogen replacement, 8 mL of toluene, 2 mL of ethanol and 2 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P32) as a yellowish green glassy solid (yield: 0.74 g, yield). Rate: 32.8%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 9: Synthesis of Derivative (1-1B-P51)>

<Synthesis of 1Np6OTf and 6Np1OTf>
5.00 g (31.2 mmol, 1.0 eq.) Of 1,6-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 5.8 mL (34.5 mmol, 1.1 eq.) Of trifluoromethylsulfonic anhydride under ice cooling. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and subjected to silica gel column chromatography using toluene-ethyl acetate as an eluent. The fractions containing the target product were collected and concentrated to obtain the target products “1Np6OTf” and “6Np1OTf” as white solids.
1Np6OTf Yield: 2.67 g, Yield: 29.3%, Purity: 98.4% (HPLC)
6Np1OTf Yield: 2.58 g, Yield: 28.3%, Purity: 99.0% (HPLC)

<Synthesis of PB5OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 1Np6OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PB5OH” was obtained as a white powder (yield: 0.93 g, yield: 35.0%, purity: 98.0% (HPLC)).

<Synthesis of PB5OTf>
0.93 g (2.35 mmol, 1.0 eq.) Of PB5OH was dissolved in 30 mL of pyridine, and 0.5 mL (2.97 mmol, 1.3 eq.) Of trifluoromethylsulfonic acid anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “PB5OTf” as a white solid (yield: 0.91 g, yield: 73.5%, purity: 98.9% (HPLC)). .

<Synthesis of Derivative (1-1B-P51)>
PB5OTf 0.91 g (1.72 mmol, 1.0 eq), P3Bpin 0.61 g (1.72 mmol, 1.0 eq.), Potassium phosphate 1.10 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.06 g (0.03 eq.) Was weighed into a 50 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 4 mL of toluene, 1 mL of ethanol and 1 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P51) as a yellowish green glassy solid. Yield: 0.36 g Yield: 34.3% Purity: 99.9% or higher (HPLC)

<Synthesis Example 10: Synthesis of Derivative (1-1B-P52)>

<Synthesis of Derivative (1-1B-P52)>
PB5OTf 2.00 g (3.79 mmol, 1.0 eq), P4Bpin 1.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 10 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 310 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P52) as a yellow-green glassy solid (yield: 1.05 g, yield). Rate: 40.5%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 11: Synthesis of Derivative (1-1A-P61)>

<Synthesis of PA6OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 6Np1OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PA6OH” was obtained as a white powder (yield: 1.11 g, yield: 41.7%, purity: 98.6% (HPLC)).

<Synthesis of PA6OTf>
1.11 g (2.80 mmol, 1.0 eq.) Of PA6OH was dissolved in 30 mL of pyridine, and 0.6 mL (35.7 mmol, 1.3 eq.) Of trifluoromethylsulfonic acid anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “PA6OTf” as a white solid (yield: 0.99 g, yield: 67.0%, purity: 99.0% (HPLC)). .

<Synthesis of Derivative (1-1A-P61)>
PA6OTf 0.99 g (1.87 mmol, 1.0 eq), P3Bpin 0.67 g (1.87 mmol, 1.0 eq.), Potassium phosphate 1.19 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.06 g (0.03 eq.) Was weighed into a 50 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 4 mL of toluene, 1 mL of ethanol and 1 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P61) as a yellowish green glassy solid (yield: 0.36 g, yield). Rate: 31.5%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 12: Synthesis of Derivative (1-1A-P62)>

PA6OTf 2.00 g (3.79 mmol, 1.0 eq), P4Bpin 1.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 10 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 340 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P62) as a yellow-green glassy solid (yield: 0.96 g, yield). Rate: 37.0%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 13: Synthesis of Derivative (1-1B-P11)>

<Synthesis of 1Np2OTf and 2Np1OTf>
5.00 g (31.2 mmol, 1.0 eq.) Of 1,2-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 5.8 mL (34.5 mmol, 1.1 eq.) Of trifluoromethylsulfonic anhydride under ice cooling. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and subjected to silica gel column chromatography using toluene-ethyl acetate as an eluent. The fractions containing the target product were collected and concentrated to obtain the target products “1Np2OTf” and “2Np1OTf” as white solids.
1Np2OTf Yield: 2.74 g, Yield: 30.0%, Purity: 97.7% (HPLC)
2Np1OTf Yield: 2.60 g, Yield: 28.5%, Purity: 97.6% (HPLC)

<Synthesis of PB1OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 1Np2OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PB1OH” was obtained as a white powder (yield: 1.17 g, yield: 44.0%, purity: 98.8% (HPLC)).

<Synthesis of PB1OTf>
1.17 g (2.95 mmol, 1.0 eq.) Of PB1OH was dissolved in 30 mL of pyridine, and 0.6 mL (35.7 mmol, 1.2 eq.) Of trifluoromethylsulfonic anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the target product was collected and concentrated to obtain the target product “PB1OTf” as a white solid (yield: 0.83 g, yield: 53.3%, purity: 99.2% (HPLC)). .

<Synthesis of Derivative (1-1B-P11)>
PB1OTf 0.83 g (1.57 mmol, 1.0 eq), P3Bpin 0.56 g (1.57 mmol, 1.0 eq.), Potassium phosphate 1.00 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.05 g (0.03 eq.) Was weighed into a 50 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 4 mL of toluene, 1 mL of ethanol and 1 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P11) as a yellowish green glassy solid (yield: 0.39 g, yield). Rate: 40.8%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 14: Synthesis of Derivative (1-1B-P12)>

PB1OTf 2.00 g (3.79 mmol, 1.0 eq), P4Bpin 1.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 10 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1B-P12) as a yellowish green glassy solid (yield: 0.88 g, yield). Rate: 33.9%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 15: Synthesis of Derivative (1-1A-P21)>

<Synthesis of PA2OH>
9PA10BA 2.00 g (6.7 mmol, 1.0 eq.), 2Np1OTf 1.96 g (6.7 mmol, 1 eq.), Potassium carbonate 2.78 g (20.1 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.23 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PA2OH” was obtained as a white powder (yield: 1.10 g, yield: 41.4%, purity: 98.8% (HPLC)).

<Synthesis of PA2OTf>
PA2OH 1.10 g (2.77 mmol, 1.0 eq.) Was dissolved in 30 mL of pyridine, and 0.6 mL (35.7 mmol, 1.3 eq.) Of trifluoromethylsulfonic anhydride was slowly added dropwise under ice cooling. . After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “PA2OTf” as a white solid (yield: 0.83 g, yield: 56.6%, purity: 99.0% (HPLC)). .

<Synthesis of Derivative (1-1A-P21)>
PA2OTf 0.83 g (1.57 mmol, 1.0 eq), P3Bpin 0.56 g (1.57 mmol, 1.0 eq.), Potassium phosphate 1.00 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.06 g (0.03 eq.) Was weighed into a 50 mL three-neck round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 4 mL of toluene, 1 mL of ethanol and 1 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P21) as a yellowish green glassy solid (yield: 0.33 g, yield). Rate: 34.5%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 16: Synthesis of Derivative (1-1A-P22)>

PA2OTf 2.00 g (3.79 mmol, 1.0 eq), P4Bpin 1.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 15 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 340 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P22) as a yellowish green glassy solid (yield: 0.80 g, yield) Rate: 30.9%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 17: Synthesis of Derivative (1-1A-P41)>

<Synthesis of 14NpOTf2>
5.00 g (31.2 mmol, 1.0 eq.) Of 1,4-dihydroxynaphthalene was dissolved in 80 mL of pyridine, and 12.6 mL (74.9 mmol, 2.4 eq.) Of trifluoromethylsulfonic anhydride was added under ice cooling. Was slowly added dropwise. After stirring for 1 hour under ice cooling, the mixture was stirred for 1 hour at room temperature. Water was added and extracted three times with toluene, and the combined toluene layer was dehydrated with anhydrous sodium sulfate. After sodium sulfate was removed, the filtrate was concentrated and passed through silica gel column chromatography using toluene-heptane (1: 4 (volume ratio)) as an eluent. The fraction containing the desired product was collected and concentrated to obtain the desired product “14NpOTf2” as a white solid (yield: 9.61 g, yield: 72.6% (HPLC), purity: 99.5%). .

<Synthesis of PB4OTf>
9PA10BA 3.00 g (10.1 mmol, 1.0 eq.), 14NpOTf2 4.26 g (10.1 mmol, 1 eq.), Potassium carbonate 4.17 g (30.2 mmol, 3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.35 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 24 mL of toluene, 6 mL of ethanol and 6 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The target product “PB4OTf” was obtained as a white powder (yield: 2.67 g, yield: 50.2%, purity: 98.8% (HPLC)).

<Synthesis of Derivative (1-1A-P41)>
PA4OTf 2.67 g (5.06 mmol, 1.0 eq), P3Bpin 1.80 g (5.06 mmol, 1.0 eq.), Potassium phosphate 3.22 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.18 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar replacement was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 310 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P41) as a yellowish green glassy solid (yield: 1.09 g, yield). Rate: 35.4%, purity: 99.9% or higher (HPLC)).

<Synthesis Example 18: Synthesis of derivative (1-1A-P42)>

PA4OTf 2.00 g (3.79 mmol, 1.0 eq), P4Bpin 1.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) palladium ( 0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing vacuum degassing and nitrogen substitution, 12 mL of toluene, 3 mL of ethanol and 3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 330 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a derivative (1-1A-P42) as a yellowish green glassy solid (yield: 0.87 g, yield). Rate: 33.6%, purity: 99.9% or higher (HPLC)).

<Synthesis of compounds used in Reference Examples and Comparative Examples>
Hereinafter, the synthesis of the compounds used in Reference Examples and Comparative Examples in Synthesis Examples 19 to 28 will be described.

<Synthesis Example 19: Synthesis of Compound (RC-1A)>

9PA10BA 2.00 g (6.71 mmol, 1.0 eq), 1-bromonaphthalene 1.39 g (6.71 mmol, 1.0 eq.), Potassium phosphate 3.22 g (3.0 eq.) And tetrakis (triphenylphosphine) ) 0.18 g (0.03 eq.) Of palladium (0) was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 310 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a compound (RC-1A) as a yellow-green glassy solid (yield: 0.97 g, yield: 38.0%, purity: 99.9% or more (HPLC)).

<Synthesis Example 20: Synthesis of Compound (RC-1B)>

9PA10BA 2.00 g (6.71 mmol, 1.0 eq), 2-bromonaphthalene 1.39 g (6.71 mmol, 1.0 eq.), Potassium phosphate 3.22 g (3.0 eq.) And tetrakis (triphenylphosphine) ) 0.18 g (0.03 eq.) Of palladium (0) was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficient vacuum degassing and nitrogen substitution, 16 mL of toluene, 4 mL of ethanol and 4 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was subjected to sublimation purification at 310 ° C. under reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a compound (RC-1B) as a yellowish green glassy solid (yield: 1.02 g, yield: 40.0%, purity: 99.9% or more (HPLC)).

<Synthesis Example 21: Synthesis of Compound (CH-BP72)>
The composition was synthesized with reference to Japanese Patent No. 4788202.

<Synthesis Example 22: Synthesis of Compound (CH-BP41)>
This was synthesized with reference to Korean published patent publication KR2014-058290.

<Synthesis Example 23: Synthesis of Compound (CH-BP42)>
This was synthesized with reference to Korean published patent publication KR2014-058290.

<Synthesis Example 24: Synthesis of Compound (CH-AP31)>
The synthesis was performed with reference to International Publication No. 2013/109030.

<Synthesis Example 25: Synthesis of Compound (CH-AP32)>
The synthesis was performed with reference to International Publication No. 2013/109030.

<Synthesis Example 26: Synthesis of Compound (CH-BP32)>
This was synthesized with reference to Korean published patent publication KR2014-095727.

<Synthesis Example 27: Synthesis of Compound (CH-BP12)>
This was synthesized with reference to Korean published patent publication KR2014-095727.

<Synthesis Example 28: Synthesis of Compound (CH-AP22)>

PA2OTf 2.00 g (3.79 mmol, 1.0 eq), biphenyl-3-ylboronic acid 0.75 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (tri Phenylphosphine) palladium (0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing degassing under reduced pressure and nitrogen substitution, 15 mL of toluene, 2.5 mL of ethanol and 2.5 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined, anhydrous sodium sulfate was added, and the mixture was allowed to stand for a while. Sodium sulfate was removed by filtration, and the solution was concentrated under reduced pressure. The obtained oil was passed through silica gel short column chromatography using toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography using heptane-toluene as an eluent, and a fraction containing the target product was collected and concentrated under reduced pressure. The obtained transparent oil was recrystallized using toluene as a good solvent, methanol or heptane as a poor solvent, and a white powder was recovered. The obtained powder was purified by sublimation at 300 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a compound (CH-AP22) as a yellow-green glassy solid (yield: 0.65 g, yield: 32.2%, purity: 99.9% or higher (HPLC)).

  Hereinafter, the synthesis of the compounds used in Comparative Examples in Synthesis Examples 29 and 30 will be described.

<Synthesis Example 29: Synthesis of Compound (CH-BP62)>
The composition was synthesized with reference to Japanese Patent No. 4788202.

<Synthesis Example 30: Synthesis of Compound (CH-AP41)>

PA4OTf 2.00 g (3.79 mmol, 1.0 eq), phenylboronic acid 0.64 g (3.79 mmol, 1.0 eq.), Potassium phosphate 2.41 g (3.0 eq.) And tetrakis (triphenylphosphine) Palladium (0) 0.13 g (0.03 eq.) Was weighed into a 100 mL three-necked round bottom flask, and vacuum degassing / Ar substitution was performed 5 times. After sufficiently performing vacuum degassing and nitrogen substitution, 12 mL of toluene, 3 mL of ethanol and 3 mL of water were added under a nitrogen atmosphere, and the mixture was refluxed and stirred at 74 ° C. After 3 hours, the heating was stopped and the reaction solution was returned to room temperature. After performing extraction three times with toluene, the organic solvent layers were combined and concentrated under reduced pressure. The fraction containing the target product was recovered and concentrated under reduced pressure by passing through silica gel column chromatography using heptane-toluene as an eluent. Further, the mixture was subjected to activated carbon column chromatography using heptane-toluene as an eluent, and the fraction containing the target product was collected and concentrated under reduced pressure to collect a white powder. The obtained powder was purified by sublimation at 300 ° C. under a reduced pressure of 2 × 10 ⁻⁴ Pa or less to obtain a compound (CH-AP41) as a yellow-green glassy solid (yield: 0.70 g, yield: 40.6%, purity: 99.9% or more (HPLC)).

<Physical property evaluation of derivatives>
The solubility, glass transition temperature, and ionization potential of the derivatives of Synthesis Examples 1 to 18 described above were evaluated. Further, the following compounds (RC-1A) and (RC-1B) having no functional functional group were used as comparative compounds (Reference Example 1 and Reference Example 2, respectively).

(1) Solubility test 10 mg of the derivative and the compound were weighed, a solvent (toluene, anisole, methyl benzoate) was added while stirring at room temperature, and the solubility was determined by weighing the dissolved liquid.

(2) Glass transition temperature 2.5 to 3.5 mg of the derivative and the compound were weighed into an aluminum pan and sealed to prepare a sample. The sample was set in a differential scanning calorimeter (Diamond DSC, manufactured by PerkinElmer), once the temperature was raised to the melting point, rapidly cooled, and then heated again at a heating rate of 10 K / min. The peak that appeared during reheating was taken as the glass transition temperature.
For the derivative (1-1A-P ##) (## is a predetermined number) series, the difference in glass transition temperature from the compound of Reference Example 1 (RC-1A) is shown in Table 1. For the derivative (1-1B-P ##) (## is a predetermined number) series, the difference in glass transition temperature from the compound of Reference Example 2 (RC-1B) is shown in Table 2.

(3) Ionization potential The ionization potential of the single layer film produced from the vacuum deposition method and the ink composition was measured using a photoelectron spectrometer (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).
For the derivative (1-1A-P ##) (## is a predetermined number) series, the difference in ionization potential with respect to the compound of Reference Example 1 (RC-1A) is shown in Table 1. For the derivative (1-1B-P ##) (## is a predetermined number) series, the difference in ionization potential with respect to the compound of Reference Example 2 (RC-1B) is shown in Table 2.

  Compared with the compounds of Reference Examples 1 and 2, the derivatives of Synthesis Examples 1 to 18 have good solubility and a high glass transition temperature. Moreover, the ionization potential was comparable as compared with Reference Examples 1 and 2, and the ionization potential did not change greatly by having a functional functional group.

<Evaluation of organic electroluminescence device (vacuum deposition method)>
The organic electroluminescent elements according to Examples 1 to 5 and Comparative Examples 1 to 3 were manufactured, and after measuring the drive voltage (V) and external quantum efficiency (%) at 1000 cd / m ² emission, respectively, the current density 37. The luminance retention time (LT80: time for maintaining luminance of 80% or more of the initial luminance) when the device was driven at constant current with the luminance obtained at 5 mA / cm ² as the initial luminance was measured.

  Note that the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency. The ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element. The external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.

The external quantum efficiency is measured as follows. A voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m ² to cause the element to emit light. Using a spectral radiance meter SR-3AR manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons in the entire wavelength region observed was integrated to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

Table 3 below shows the material structure of each layer in the produced organic electroluminescent elements according to Examples 1 to 5 and Comparative Examples 1 to 3.

The structures of HI1, IL, HT1, GPL1, ET1, and Liq in Table 3 are shown below.

<Comparative Example 1>
A glass substrate (manufactured by Optoscience Co., Ltd.) of 26 mm × 28 mm × 0.7 mm obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI1, a molybdenum vapor deposition boat containing IL, and a molybdenum vapor vessel containing HT1. Vapor deposition boat, molybdenum vapor deposition boat with CH-BP72, molybdenum vapor deposition boat with GPL1, molybdenum vapor deposition boat with ET1, molybdenum vapor deposition boat with Liq, magnesium A molybdenum deposition boat and a molybdenum deposition boat containing silver were installed.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI1 is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. The evaporation boat containing was heated and evaporated to a film thickness of 5 nm to form a second hole injection layer. Subsequently, the vapor deposition boat containing HT1 was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing CH-BP72 and the vapor deposition boat containing GPL1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of CH-BP72 to GPL1 was approximately 95: 5. The deposition rate of each layer was 0.01 to 1 nm / second. Next, the evaporation boat containing ET1 and the evaporation boat containing Liq were heated and evaporated to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of ET1 to Liq was approximately 1: 1. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic electroluminescence device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

About the produced organic electroluminescent element, the drive voltage and external quantum efficiency at the time of 1000 cd / m < ² > light emission were measured by making an ITO electrode into an anode and a Liq / magnesium + silver electrode as a cathode. In addition, the luminance holding time (LT80) was measured. Table 4 shows the measurement results.

<Example 1>
An organic electroluminescent element was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the derivative (1-1B-P72). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Comparative Example 2>
An organic electroluminescent element was obtained by a method according to Comparative Example 1 except that the compound (CH-BP72) was replaced with the compound (CH-BP41). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Example 2>
An organic electroluminescent element was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the derivative (1-1B-P41). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Example 3>
An organic electroluminescent element was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the derivative (1-1B-P42). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Comparative Example 3>
An organic electroluminescent device was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the compound (CH-AP31). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Example 4>
An organic electroluminescent element was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the derivative (1-1A-P31). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Example 5>
An organic electroluminescent element was obtained by the method according to Comparative Example 1 except that the compound (CH-BP72) was changed to the derivative (1-1A-P32). In the same manner as in Comparative Example 1, the driving voltage, the external quantum efficiency, and the luminance retention time (LT80) were measured.

<Evaluation of solubility of light emitting layer forming ink composition>
The ink composition for light emitting layer formation which concerns on Examples 6-21 and Comparative Examples 4-11 was prepared, and solubility was evaluated by confirming the turbidity and precipitation. The sample without turbidity and precipitation was designated as “OK”, and the sample with turbidity or precipitation as “NG”.

<Comparative example 4>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP72) 0.95 wt%
Toluene 99.00 wt%

<Example 6>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Toluene 99.00 wt%

<Example 7>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Anisole 99.00 wt%

<Example 8>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Methyl benzoate 99.00 wt%

<Example 9>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.5% by weight
Derivative (1-1B-P72) 9.5% by weight
Toluene 90.0 wt%

<Example 10>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 11>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Anisole 50.00% by weight
Decalin 49.00 wt%

<Example 12>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P72) 0.95 wt%
Mesitylene 69.00 wt%
Terpineol 30.00 wt%

<Comparative Example 5>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP41) 0.95 wt%
Toluene 99.00 wt%

<Comparative Example 6>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP42) 0.95 wt%
Toluene 99.00 wt%

<Example 13>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P41) 0.95 wt%
Toluene 99.00 wt%

<Example 14>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P42) 0.95 wt%
Toluene 99.00 wt%

<Example 15>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P42) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 16>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P42) 0.95 wt%
Mesitylene 69.00 wt%
Terpineol 30.00 wt%

<Comparative Example 7>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP31) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Comparative Example 8>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP32) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 17>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1A-P31) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 18>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1A-P32) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Comparative Example 9>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP32) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 19>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P32) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Comparative Example 10>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP12) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 20>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1B-P12) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Comparative Example 11>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP22) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

<Example 21>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Derivative (1-1A-P22) 0.95 wt%
Toluene 69.00 wt%
Decalin 30.00 wt%

Table 7 shows the results of evaluating the solubility of the prepared ink composition for forming a light emitting layer together with its concentration and composition.

<Evaluation of organic electroluminescence device (wet film-forming method)>
An organic electroluminescence device according to Examples 22 to 31 and Comparative Examples 12 to 14 was manufactured, and after measuring the drive voltage (V) and external quantum efficiency (%) at the time of 1000 cd / m ² emission, respectively, the current density 37. The luminance retention time (LT80: time for maintaining luminance of 80% or more of the initial luminance) when the device was driven at constant current with the luminance obtained at 5 mA / cm ² as the initial luminance was measured.

Table 8 shows the material configuration of each layer in the produced organic electroluminescent elements according to Examples 22 to 31 and Comparative Examples 12 to 14.

The structures of HI2, HT2 and HT3 in Table 8 are shown below.

<HI2 solution>
A commercially available HI2 solution (Clevios (TM) PVP AI4083, PEDOT: PSS aqueous dispersion, Heraeus Holdings) was used.

<Preparation of HT2 solution>
HT2 (LT-N159, OTPD, manufactured by Luminescence Technology Corp) and IK-2 (photocation polymerization initiator, manufactured by San Apro) were dissolved in toluene, and the HT2 concentration was 0.7 wt% and the IK-2 concentration was 0.007 wt%. An HT2 solution was made.

<Preparation of HT3 solution>
HT3 (polyvinylcarbazole) was dissolved in dichlorobenzene to prepare a 0.7 wt% HT3 solution.

<Comparative Example 12>
A HI2 solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 150 nm and baked on a hot plate at 200 ° C. for 1 hour to form a HI2 film having a thickness of 40 nm (hole injection layer). . Next, the HT2 solution was spin-coated and dried on a hot plate at 80 ° C. for 10 minutes. By exposing with an exposure machine at an exposure intensity of 100 mJ / cm ² and baking on a hot plate at 100 ° C. for 1 hour, an HT 2 film insoluble in a solution with a thickness of 20 nm was formed (hole transport layer). Subsequently, the light emitting layer forming ink composition prepared in Comparative Example 4 was spin coated.

  Since the compound (CH-BP72) was insoluble in the solution, a light emitting layer could not be formed on the HT2 film.

<Example 22>
A HI2 solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 150 nm and baked on a hot plate at 200 ° C. for 1 hour to form a HI2 film having a thickness of 40 nm (hole injection layer). . Next, the HT2 solution was spin-coated and dried on a hot plate at 80 ° C. for 10 minutes. By exposing with an exposure machine at an exposure intensity of 100 mJ / cm ² and baking on a hot plate at 100 ° C. for 1 hour, an HT 2 film insoluble in a solution with a thickness of 20 nm was formed (hole transport layer). Subsequently, the ink composition for light emitting layer formation prepared in Example 6 was spin-coated, and baked on a 120 degreeC hotplate for 1 hour, and the light emitting layer with a film thickness of 20 nm was formed into a film.

  The produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing Liq, and a molybdenum vapor containing magnesium. A vapor deposition boat and a molybdenum vapor deposition boat containing silver were mounted.

After depressurizing the vacuum tank to 5 × 10 ⁻⁴ Pa, the evaporation boat containing ET1 and the evaporation boat containing Liq were heated and evaporated to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of ET1 to Liq was approximately 1: 1. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic electroluminescence device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

About the produced organic electroluminescent element, the drive voltage and external quantum efficiency at the time of 1000 cd / m < ² > light emission were measured by making an ITO electrode into an anode and a Liq / magnesium + silver electrode as a cathode. In addition, the luminance holding time (LT80) was measured.

<Comparative Example 13>
An organic electroluminescent element was produced by the method according to Comparative Example 12 except that the light emitting layer forming ink composition prepared in Comparative Example 4 was replaced with the light emitting layer forming ink composition prepared in Comparative Example 5. Since the compound (CH-BP41) was insoluble in the solution, a light emitting layer could not be formed on the HT2 film.

<Comparative example 14>
An organic electroluminescent element was produced by the method according to Comparative Example 12 except that the light emitting layer forming ink composition prepared in Comparative Example 4 was replaced with the light emitting layer forming ink composition prepared in Comparative Example 6. Since the compound (CH-BP42) was insoluble in the solution, a light emitting layer could not be formed on the HT2 film.

<Example 23>
An organic electroluminescent element was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 13. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 24>
An organic electroluminescent element was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 14. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 25>
An organic electroluminescent element was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 17. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 26>
An organic electroluminescent element was obtained by a method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 18. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 27>
An organic electroluminescent element was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 19. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 28>
An organic electroluminescent element was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 20. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 29>
An organic electroluminescence device was obtained by the method according to Example 22 except that the light emitting layer forming ink composition prepared in Example 6 was replaced with the light emitting layer forming ink composition prepared in Example 21. In the same manner as in Example 22, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Example 30>
A HI2 solution was spin-coated on a glass substrate on which ITO was deposited to a thickness of 150 nm and baked on a hot plate at 200 ° C. for 1 hour to form a HI2 film having a thickness of 40 nm (hole injection layer). . Subsequently, the HT3 solution was spin-coated and baked on a hot plate at 180 ° C. for 1 hour to form a 20 nm-thick HT3 film (hole transport layer). Subsequently, the ink composition for light emitting layer formation prepared in Example 12 was spin-coated, and it baked on the 120 degreeC hotplate for 1 hour, and formed the light emitting layer with a film thickness of 20 nm.

  The produced multilayer film is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing ET1, a molybdenum vapor deposition boat containing Liq, and a molybdenum vapor containing magnesium. A vapor deposition boat and a molybdenum vapor deposition boat containing silver were mounted.

After depressurizing the vacuum tank to 5 × 10 ⁻⁴ Pa, the evaporation boat containing ET1 and the evaporation boat containing Liq were heated and evaporated to a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of ET1 to Liq was approximately 1: 1. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic electroluminescence device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

About the produced organic electroluminescent element, the drive voltage and external quantum efficiency at the time of 1000 cd / m < ² > light emission were measured by making an ITO electrode into an anode and a Liq / magnesium + silver electrode as a cathode. In addition, the luminance holding time (LT80) was measured.

<Example 31>
An organic electroluminescent element was obtained by the method according to Example 30 except that the light emitting layer forming ink composition prepared in Example 12 was replaced with the light emitting layer forming ink composition prepared in Example 16. In the same manner as in Example 30, the driving voltage, the external quantum efficiency, and the luminance holding time (LT80) were measured.

<Evaluation of solubility of ink composition>
The ink composition for light emitting layer formation which concerns on Examples 32-44 and Comparative Examples 15-24 was prepared, and solubility was evaluated by confirming the turbidity and precipitation. The sample without turbidity and precipitation was designated as “OK”, and the sample with turbidity or precipitation as “NG”.

<Evaluation of film formability>
With respect to the ink compositions (Examples 6 and 11, Examples 32-44, and Comparative Examples 15 and 22) that were “OK” in the evaluation of the solubility of the prepared ink composition, the following spin coat film formation or inkjet formation was performed. The film formability of the film obtained from the film was evaluated. After film formation, the film has “×” for pinholes or compound precipitation or unevenness, “No” for pinholes, compound precipitation or unevenness, and no pinholes, compound precipitation or unevenness, Those having high smoothness (Ra <5 nm) are indicated by “◎”.

<Spin coating film formation>
UV-O ₃ treatment was performed by irradiating a clean glass substrate having a thickness of 0.5 mm and a size of 28 × 26 mm with an irradiation energy of 1000 mJ / cm ² (low pressure mercury lamp (254 nm)). Next, 0.3 to 0.6 mL of the ink composition was dropped on the glass, and spin coating (slope for 5 seconds, 500 to 5000 rpm for 10 seconds, then slope for 5 seconds) was performed. Further, it was dried on a hot plate at 120 ° C. for 10 minutes.

<Inkjet film formation>
UV-O ₃ treatment was performed by irradiating a glass substrate on which a bank of 200 μm × 30 μm was formed with irradiation energy of 1000 mJ / cm ² (low pressure mercury lamp (254 nm)). Subsequently, it was dripped in the bank using the inkjet apparatus. Further, it was dried on a hot plate at 120 ° C. for 10 minutes.

<Evaluation of inkjet discharge stability>
Evaluation of inkjet discharge stability was performed on the ink compositions (Examples 6 and 11 and Examples 32-44) that were “」 ”or“ 」” in the evaluation of the ink-jet film forming property of the prepared ink composition. went. In the initial stage and after standing for 24 hours, the ink droplets that were ejected from the ink jet flew straight and the ink droplets that were ejected from the ink jet ejected straight. However, “○” indicates that splashes remain in the vicinity of the discharge hole, and “X” indicates that discharge is difficult.

<Comparative Example 15>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Toluene 99.00 wt%

<Comparative Example 16>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Xylene 99.00 wt%

<Comparative Example 17>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Xylene 49.00 wt%
Cyclohexylbenzene 50.00 wt%

<Comparative Example 18>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Xylene 49.00 wt%
Octylbenzene 50.00 wt%

<Comparative Example 19>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Xylene 49.00 wt%
Diphenyl ether 50.00% by weight

<Comparative Example 20>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Xylene 49.00 wt%
1-methylnaphthalene 50.00% by weight

<Comparative Example 21>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-BP62) 0.95 wt%
Cyclohexylbenzene 49.00 wt%
3-phenoxytoluene 50.00 wt%

<Comparative Example 22>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP41) 0.95 wt%
Toluene 99.00 wt%

<Comparative Example 23>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP41) 0.95 wt%
Xylene 99.00 wt%

<Comparative Example 24>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (CH-AP42) 0.95 wt%
Xylene 49.00 wt%
Cyclohexylbenzene 50.00 wt%

<Example 32>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Xylene 99.00 wt%

<Example 33>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Xylene 49.00 wt%
Cyclohexylbenzene 50.00 wt%

<Example 34>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Xylene 49.00 wt%
Octylbenzene 50.00 wt%

<Example 35>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Xylene 49.00 wt%
Diphenyl ether 50.00% by weight

<Example 36>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Xylene 49.00 wt%
1-methylnaphthalene 50.00% by weight

<Example 37>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Cyclohexylbenzene 49.00 wt%
3-phenoxytoluene 50.00 wt%

<Example 38>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Cyclohexylbenzene 29.70 wt%
3-phenoxytoluene 69.30 wt%

<Example 39>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.15% by weight
Compound (1-1B-P72) 2.85% by weight
Cyclohexylbenzene 29.10 wt%
3-phenoxytoluene 67.90 wt%

<Example 40>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.025 wt%
Compound (1-1B-P72) 0.475 wt%
Cyclohexylbenzene 29.850% by weight
3-phenoxytoluene 69.650% by weight

<Example 41>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Octylbenzene 29.70 wt%
3-phenoxytoluene 69.30 wt%

<Example 42>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Cyclohexylbenzene 29.70 wt%
Diphenyl ether 69.30 wt%

<Example 43>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.05 wt%
Compound (1-1B-P72) 0.95 wt%
Octylbenzene 29.70 wt%
Diphenyl ether 69.30 wt%

<Example 44>
An ink composition was prepared by stirring the following components until a uniform solution was obtained.
Compound (GPL1) 0.025 wt%
Compound (1-1B-P72) 0.475 wt%
Cyclohexylbenzene 29.554 wt%
3-phenoxytoluene 68.961 wt%
4-fluoroanisole 0.985 wt%

  Table 11 shows the results of evaluating the solubility of the prepared ink composition. In addition, the thing which has not measured is shown by "-". In Table 11, “concentration” is solid content concentration (wt%), “SC” is spin coating film formation, “IJ” is ink jet film formation, and “ejection stability” is ink jet ejection stability.

<Evaluation of organic electroluminescence device (inkjet film forming method)>
A bank material is applied and baked on a glass substrate on which ITO is deposited to a thickness of 150 nm. Next, a bank is formed by dissolving and removing the element portion using photolithography, and a glass substrate with a bank is manufactured.

A UV-O ₃ treatment is performed by irradiating a glass substrate with a bank with an irradiation energy of 1000 mJ / cm ² (low pressure mercury lamp (254 nm)). First, HI2 is applied inside the bank by inkjet and baked on a hot plate at 200 ° C. for 1 hour to form a HI2 film having a thickness of 40 nm (hole injection layer). Next, the HT3 solution is applied to the inside of the bank by inkjet and baked on a hot plate at 180 ° C. for 1 hour to form an HT3 film having a thickness of 20 nm (hole transport layer). Further, the light emitting layer forming ink composition prepared in Example 33 was applied inside the bank by inkjet and baked on a hot plate at 120 ° C. for 1 hour to form a light emitting layer having a thickness of 20 nm.

The produced multilayer film was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), the vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and then a vapor deposition boat containing ET1 and Liq entered. An evaporation boat is heated to deposit a film with a thickness of 30 nm to form an electron transport layer.

  Thereafter, the evaporation boat containing Liq is heated and evaporated to a thickness of 1 nm. Next, the magnesium-containing boat and the silver-containing boat are heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. Finally, a glass sealing can is sealed so as to cover the element to obtain an organic electroluminescent element.

  According to a preferred embodiment of the present invention, an anthracene derivative with controlled solubility, film-forming property, wet coating property and orientation (more desirably, thermal stability) is provided, and the derivative is used as a structure of an organic electroluminescent device. By using it as a component, an organic electroluminescent element excellent in at least one of efficiency, life and driving voltage can be provided.

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode 110 Substrate 120 Electrode 130 Coating film 140 Coating film 150 Light emitting layer 200 Bank 300 Inkjet head 310 Ink droplet

Claims (17)

Anthracene derivatives represented by the following general formula (1).
Ar-An-L-FG (1)
(In the above formula (1),
An is represented by the following structural formula, Q is each independently hydrogen, alkyl having 1 to 24 carbons or alkoxy having 1 to 24 carbons, and bonded to Ar and L at the 9th and 10th positions, respectively. And

Ar is aryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl may be replaced with alkyl having 1 to 24 carbon atoms or cycloalkyl having 3 to 24 carbon atoms, and any — CH ₂ — may be replaced by —O—, and any —CH ₂ — except for —CH ₂ — directly bonded to the aryl in the alkyl is replaced by arylene having 6 to 24 carbon atoms. And at least one hydrogen in the cycloalkyl may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons;
L is an arylene having 7 to 18 carbon atoms in which two or more rings are condensed and connects An and FG, and at least one hydrogen in the arylene is an alkyl having 1 to 12 carbons and an alkyl having 3 to 24 carbon atoms. Optionally substituted with cycloalkyl or aryl having 6 to 12 carbon atoms;
FG is represented by the following structural formula:

R is each independently fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 24 carbons or cycloalkyl having 3 to 24 carbons, and any —CH ₂ — in the alkyl is replaced by —O—. Any —CH ₂ — except for —CH ₂ — directly bonded to phenyl or phenylene in the alkyl may be substituted with arylene having 6 to 24 carbon atoms, and at least in the cycloalkyl One hydrogen may be replaced by alkyl having 1 to 24 carbons or aryl having 6 to 12 carbons,
When two R bonded to adjacent carbons of FG are alkyl or cycloalkyl, the two Rs may be bonded to each other to form a ring,
m is each independently an integer of 0 to 4,
n is an integer of 0 to 5,
p is an integer of 1 to 5, but when the above formula (1) is the following formula (X-1), p is an integer of 3 to 5, and the above formula (1) is the following formula (X-2). P is an integer of 2 to 5, and Ar, An and FG in the following formula (X-1) or the following formula (X-2) are the same as defined in the above formula (1).

  The anthracene derivative according to claim 1, wherein p is 1 to 2. The anthracene derivative according to claim 1 or 2, wherein the formula (1) is represented by any of the following formulas (1-1) to (1-10).

Ar, An and FG in the above formulas (1-1) to (1-10) are the same as defined in the above formula (1).   The anthracene derivative according to claim 3, wherein the formula (1) is represented by the formula (1-1) and Q is hydrogen. The anthracene derivative according to claim 4, wherein the formula (1-1) is represented by the following formula (1-1A).

Ar, An, and FG in the above formula (1-1A) are the same as defined in the above formula (1). The anthracene derivative according to claim 4, wherein the formula (1-1) is represented by the following formula (1-1B).

Ar, An and FG in the above formula (1-1B) are the same as defined in the above formula (1).   Ar is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5-naphthacenyl, 1 -Pyrenyl, 2-pyrenyl, or 4-pyrenyl, in which at least one hydrogen may be replaced by alkyl having 1 to 12 carbons or cycloalkyl having 3 to 12 carbons. The anthracene derivative according to any one of the above.   The anthracene derivative according to claim 7, wherein Ar is phenyl, 1-naphthyl, or 2-naphthyl, and at least one hydrogen thereof may be replaced by alkyl having 1 to 4 carbon atoms. Each R is independently fluorine, trimethylsilyl, trifluoromethyl, alkyl having 1 to 12 carbons or cycloalkyl having 3 to 12 carbons;
m is each independently an integer of 0 to 2,
n is an integer from 0 to 2,
The anthracene derivative according to any one of claims 1 to 8, wherein p is 1 or 2.   An ink composition comprising the anthracene derivative according to any one of claims 1 to 9. Furthermore, the ink composition of Claim 10 containing the compound represented by the following general formula (S-1).

(In the above formula (S-1),
h is r-valent benzene or naphthalene;
each j is independently a single bond, an ether bond, a thioether bond, a carbonyl bond, an ester bond or an amide bond;
each k is independently alkyl, cycloalkyl, aryl or alkylaryl;
r is an integer of 1 to 3,
The above (jk) bonded to adjacent carbon in h may be bonded to form a ring. ) j is a single bond or an ether bond,
The ink composition according to claim 11, wherein k is alkyl having 1 to 12 carbons, cycloalkyl having 3 to 12 carbons, aryl having 6 to 12 carbons, or alkylaryl having 7 to 12 carbons.   The ink composition according to claim 11, wherein r is 1. h is r-valent benzene,
The ink composition according to any one of claims 11 to 13, wherein k is alkyl having 6 to 12 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, methylphenyl, dimethylphenyl or trimethylphenyl.   The ink composition according to any one of claims 11 to 14, comprising a compound having a boiling point of 200 ° C to 300 ° C.   The ink composition according to any one of claims 10 to 15, comprising a condensed aromatic compound having an arylamino group bonded thereto, or a styryl derivative having an arylamino group bonded thereto.   The organic electroluminescent element containing the organic layer produced using the ink composition as described in any one of Claims 10-16.

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