JP5458516B2 - Anthracene compound, charge transport material for wet film formation, charge transport material composition for wet film formation, organic electroluminescence device, and organic EL display - Google Patents

Description

  The present invention relates to an anthracene compound, a charge transport material for wet film formation, a composition for an organic electroluminescent element, and an organic electroluminescent element. Specifically, the solubility in a solvent is excellent, and the film formability and wet process suitability are improved. An excellent anthracene compound, a composition for an organic electroluminescence device using the same, a high-efficiency, long-life organic electroluminescence device using the same, and an organic EL display having the organic electroluminescence device It is.

  In recent years, as a thin film type electroluminescent element, an organic electroluminescent element using an organic thin film has been developed instead of using an inorganic material. The organic electroluminescent device usually has a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, etc. between the anode and the cathode, and suitable for each layer such as red, green, blue, etc. Development of light emitting devices is progressing. However, blue light-emitting elements are not satisfactory in terms of efficiency, life, and heat resistance, and there is a problem that application to full-color displays is limited.

  In addition, as a method for forming each layer of the organic electroluminescent element, there are a vapor deposition method and a wet film formation method. The vapor deposition method has a problem in terms of yield when manufacturing a medium or large full color panel for a television or a monitor. Therefore, the wet film-forming method is suitable for these large area applications.

  However, in order to form each layer of the organic electroluminescent element by the wet film forming method, it has been desired that the material for forming each layer is dissolved in a solvent and has high performance as an element even after the wet film formation. However, many materials that have been used in the conventionally developed vapor deposition method have not been suitable for the wet film formation method.

For example, Patent Document 1 discloses an element manufactured by a wet film formation method using a material represented by the following formula.

Patent Document 2 discloses an element manufactured by a wet film forming method using a material represented by the following formula.

However, these materials do not satisfy the required physical properties of the wet film formation process such as solubility in solvents and heat resistance, and the host hole injection / transport properties are poor, so they are practical for wet film formation applications. It wasn't.
International Publication No. 2006/070712 Pamphlet JP 2004-224766 A

  The present invention has been made in view of the above problems. That is, it is a compound useful for an organic layer formed by a wet film-forming method of an organic electroluminescent element, has excellent solubility, and has a high efficiency and a long life even when formed by a wet film-forming method. It is providing the compound which can provide.

  As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by using a compound represented by the following formula (I), and the present invention has been achieved.

（式（Ｉ）中、Ａｒ^１は、炭素数６以上２６以下の芳香族炭化水素基を置換基として有してもよい、フェニル基、１−ナフチル基、または２−ナフチル基を表わし、Ａｒ^２は、炭素数６以上１６以下の芳香族炭化水素基を置換基として有してもよい、フェニル基、１−ナフチル基、２−ナフチル基、１０−アリール−９−アントリル基、または１−ピレニル基を表わし、Ａｒ^３、Ａｒ^４は、それぞれ独立に、炭素数６以上１６以下の芳香族炭化水素基を置換基として有していてもよい、フェニル基、１−ナフチル基、または２−ナフチル基を表わす。Ｇ^１は、直接結合を表わす。） That is, the gist of the present invention resides in an anthracene compound represented by the following formula (I) (claim 1).

(In formula (I), Ar ¹ represents a phenyl group, 1-naphthyl group, or 2-naphthyl group, which may have an aromatic hydrocarbon group having 6 to 26 carbon atoms as a substituent, and Ar ² is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 10-aryl-9-anthryl group, or 1-, which may have an aromatic hydrocarbon group having 6 to 16 carbon atoms as a substituent. represents a pyrenyl group, Ar ^3, Ar ⁴ are each independently, an aromatic hydrocarbon group having 6 to 16 carbon atoms which may have a substituent, a phenyl group, a 1-naphthyl group or a 2- Represents a naphthyl group, G ¹ represents a direct bond .)

Also, amino groups in the ^molecule, -G 1 ^{N (Ar} 3) is preferably (Ar ⁴⁾ only (claim 2).

Another subject matter of the present invention lies in a charge transport material for wet film formation, characterized by comprising the above-mentioned anthracene compound (claim 3 ).

At this time, the glass transition point is preferably 120 ° C. or higher, and the solubility in toluene is preferably 5% by weight or higher (claim 4 ).

Another subject matter of the present invention lies in a charge transport material composition for wet film formation, which contains the anthracene compound described above (claim 5 ).

At this time, a wet film forming charge transporting material composition preferably contains less than 50 parts by weight or more and 1 part by weight of the luminescent material (claim 6).

At this time, a wet film forming charge transporting material composition preferably contains a solvent (claim 7).

Another gist of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic light emitting layer provided between the two electrodes, and has a layer containing the charge transport material for wet film formation. It is an organic electroluminescent device characterized in that (claim 8 ).

Another gist of the present invention is an organic electroluminescent device having an anode, a cathode, and an organic light emitting layer provided between the two electrodes, and has a layer containing the above-described charge transport material composition for wet film formation. It exists in the organic electroluminescent element characterized by the above-mentioned (Claim 9 ).

Another subject matter of the present invention lies in an organic EL display comprising the organic electroluminescent device described above (claim 10 ).

  According to the present invention, a novel compound can be provided. The compound has high solubility in a solvent and is suitable for an organic layer of an organic electroluminescent element formed by a wet film forming method. When an organic layer formed by a wet film-forming method manufactured using the compound is used, an organic electroluminescent element having a high efficiency and a long lifetime can be obtained.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following description, and various modifications can be made without departing from the gist of the present invention.

The present invention relates to an anthracene compound represented by the following formula (I), a charge transport material for wet film formation and a charge transport material composition for wet film formation using the anthracene compound, and an organic electroluminescent device containing them. .
Hereinafter, the description will be made in the order described above.

（式（Ｉ）中、Ａｒ^１〜Ａｒ^４は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基を表わす。Ｇ^１は、直接結合または連結基を表わす。Ａｒ^１が結合するアントラセン環は、更に置換基を有していてもよい。） [1. Anthracene compound]
<1-1. Structure of anthracene compound>
The anthracene compound of the present invention is not limited as long as it has a structure represented by the following formula (I). The structure will be described below.

(In formula (I), Ar ^{1 to} Ar ⁴ each independently represents an aromatic hydrocarbon group which may have a substituent. G ¹ represents a direct bond or a linking group. Ar ¹ represents (The anthracene ring to be bonded may further have a substituent.)

(About Ar ^{1 to} Ar ⁴ )
In formula (I), Ar ^{1 to} Ar ⁴ each independently represents an aromatic hydrocarbon group which may have a substituent.

The aromatic hydrocarbon group is a cyclic hydrocarbon group having aromaticity. The number of skeleton elements constituting one ring is usually 6 or more, preferably 10 or more, more preferably 12 or more, and usually 36 or less, preferably 30 or less, more preferably 24 or less. Moreover, the ring (For example, naphthalene ring etc.) which 2 or more normally and 5 or less rings were condensed may be sufficient. Among these aromatic hydrocarbon groups, an aromatic hydrocarbon group derived from a 6-membered monocyclic ring or a 2-5 condensed ring is preferable.
Examples thereof include groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, and the like.

  In addition, a group formed by connecting a plurality of the above-described single rings or 2 to 5 condensed rings is also preferable. For example, a biphenyl group, a terphenyl group, etc. are mentioned.

Ar ¹ is preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. These further have 6 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group, 10-aryl-9-anthryl group, 1-pyrenyl group, p-biphenyl group, m-biphenyl group, o-biphenyl group and the like. It may have an aromatic hydrocarbon group of 26 or less as a substituent.

Ar ² is preferably a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 10-aryl-9-anthryl group, or a 1-pyrenyl group. These are further substituted with aromatic hydrocarbon groups having 6 to 16 carbon atoms, such as phenyl group, 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, o-biphenyl group and the like. You may have.

Ar ³ and Ar ⁴ are preferably each independently a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. These further include an aromatic hydrocarbon group having 6 to 16 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-phenanthryl group, a 1-pyrenyl group, a p-biphenyl group, and an m-biphenyl group. As a substituent.

  Examples of the substituent that the aromatic hydrocarbon group may have include the substituents described in the following substituent group Q. As for these substituents, one type of substituent may be substituted independently per aromatic hydrocarbon group, or two or more types of substituents may be substituted in any combination and ratio. .

<Substituent group Q>
As the substituent group Q,
An alkyl group which may have a substituent (preferably a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, such as a methyl group, an ethyl group, n- Propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group and the like));
An alkenyl group that may have a substituent (preferably an alkenyl group having 2 to 8 carbon atoms that may have a substituent, such as a vinyl group, an allyl group, and a 1-butenyl group). ;);
An alkynyl group which may have a substituent (preferably an alkynyl group having 2 to 8 carbon atoms which may have a substituent, such as an ethynyl group and a propargyl group);
An aralkyl group which may have a substituent (preferably an aralkyl group having 7 to 15 carbon atoms which may have a substituent, such as a benzyl group);
An amino group which may have a substituent (preferably an amino group which has one or more alkyl groups having 1 to 8 carbon atoms and may have another substituent; For example, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, etc.);
An arylamino group which may have a substituent (for example, a phenylamino group, a diphenylamino group, a ditolylamino group, etc.);
A heteroarylamino group which may have a substituent (for example, pyridylamino group, thienylamino group, dithienylamino group and the like);
An acylamino group which may have a substituent (for example, acetylamino group, benzoylamino group and the like);
An alkoxy group which may have a substituent (preferably an alkoxy group having 1 to 8 carbon atoms which may have a substituent, and examples thereof include a methoxy group, an ethoxy group and a butoxy group. .);
An aryloxy group which may have a substituent (preferably an aryloxy group having an aromatic hydrocarbon group or a heterocyclic group, for example, a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group , Pyridyloxy group, thienyloxy group, etc.);
An acyl group which may have a substituent (preferably an acyl group having 1 to 8 carbon atoms which may have a substituent, and examples thereof include a formyl group, an acetyl group and a benzoyl group. .);
An alkoxycarbonyl group which may have a substituent (preferably an alkoxycarbonyl group having 2 to 13 carbon atoms which may have a substituent, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. .);
An aryloxycarbonyl group which may have a substituent (preferably an aryloxycarbonyl group having 2 to 13 carbon atoms which may have a substituent, such as an acetoxy group);
A cycloalkyl group which may have a substituent (preferably a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group. .);
A carboxy group;
A cyano group;
Hydroxyl group;
A thiol group;
An alkylthio group which may have a substituent (preferably an alkylthio group having 1 to 8 carbon atoms which may have a substituent, such as a methylthio group and an ethylthio group). ;
An arylthio group which may have a substituent (preferably an arylthio group having 1 to 8 carbon atoms which may have a substituent, such as a phenylthio group and a 1-naphthylthio group. .);
A sulfonyl group which may have a substituent (for example, mesyl group, tosyl group and the like);
A silyl group which may have a substituent (for example, a trimethylsilyl group, a triphenylsilyl group, etc.);
An optionally substituted boryl group (for example, a dimesitylboryl group);
A phosphino group which may have a substituent (for example, a diphenylphosphino group and the like);
An aromatic hydrocarbon group which may have a substituent (for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, etc. A group derived from);
An aromatic heterocyclic group which may have a substituent (for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring And an aromatic hydrocarbon group derived from a pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Raised It is.

  In addition, as a substituent which said substituent group Q may have, an alkyl group, a diarylamino group, an aromatic hydrocarbon group, an aromatic heterocyclic group, etc. are mentioned. Specific examples are the same as those listed in the substituent group Q above.

Moreover, the substituents each Ar ^{1 to} Ar ⁴ may combine with each other to form a ring. For example, an aliphatic ring such as a cyclohexane ring can be formed.

Here, from the viewpoint of electrical durability and charge transportability, any one of Ar ³ , Ar ⁴ , and G ¹ described later is an aromatic hydrocarbon derived from a condensed ring having 10 or more carbon atoms, or para A group derived from a benzene ring having a substituent at the position (phenyl group) is preferred.

However, in the anthracene compound of the present invention, the amino group in the molecule is preferably only -G ¹ N (Ar ³ ) (Ar ⁴ ), and it is preferable that none of Ar ^{1 to} Ar ⁴ is an amino group. In addition, it is preferably not substituted with an amino group. This is because it does not impair the resistance to electrical reduction, or prevents the development of more than necessary hole transportability.

(For further substituents on the anthracene ring)
The anthracene ring to which Ar ¹ is bonded may further have a substituent. Examples of the substituent include the groups described in the above substituent group Q.

  Among the substituent group Q, an aromatic hydrocarbon group which may have a substituent is preferable. In particular, a group derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, or a combination of these groups in any combination (usually) 2 or more, and usually 8 or less, preferably 4 or less) are preferably formed by linking.

In the group further substituted on the anthracene ring to which Ar ¹ is bonded, one type of substituent may be substituted alone, or two or more types of substituents may be substituted in any combination and ratio.

  The substitution positions of the above substituents are preferably 2, 3, 6, and 7 positions. This is in order to avoid a decrease in electrical durability that accompanies a significant loss of molecular planarity.

However, in the anthracene compound of the present invention, the amino group in the molecule is preferably only -G ¹ N (Ar ³ ) (Ar ⁴ ) for the same reason as described above. Therefore, it is preferable that the further substituent which anthracene ring has is not an amino group.

(For ^{G 1)}
G ¹ represents a direct bond or a linking group. That is, the N atom and the benzene ring may be directly bonded, or may be bonded via a linking group.

As the linking group, an aromatic hydrocarbon group which may have a substituent is preferable, and among them, an aromatic hydrocarbon group derived from a 6-membered monocyclic ring or a 2-5 condensed ring is preferable.
Examples thereof include groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, and the like.

  In addition, a divalent group formed by connecting a plurality of the above-described single rings or 2 to 5 condensed rings is also preferable. Examples thereof include a biphenylene group and a terphenylene group.

G ¹ is more preferably a group derived from a benzene ring or a naphthalene ring, or a group formed by linking a plurality of these groups (for example, a biphenylene group or a terphenylene group).

G ¹ may have a substituent.
The substituent is preferably, for example, an alkyl group, an aromatic hydrocarbon group, an acyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, an arylamino group. , Alkylamino group, aromatic heterocyclic group and the like.
An aromatic hydrocarbon group is preferable, and among them, a benzene ring, a naphthalene ring, or a group formed by connecting a plurality of these (for example, a biphenyl group, a terphenyl group, or the like) is preferable.

The number of substituents of G ¹ is not limited as long as the effect of the present invention is not significantly impaired, but is usually 2 or less, preferably 1, and may not be substituted. If it exceeds this range, the charge transportability may decrease.
In G ¹ , any one type of substituent may be substituted alone, or two or more types of substituents may be substituted in any combination and ratio.

Moreover, as described above, from the viewpoint of electrical durability and charge transportability, any one of Ar ³ , Ar ⁴ , and G ¹ is an aromatic hydrocarbon derived from a condensed ring having 10 or more carbon atoms, Or the group (phenyl group) derived from the benzene ring which has a substituent in para position is preferable.

<1-2. Physical properties of anthracene compounds>
(Molecular weight)
The molecular weight of the anthracene compound of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but is preferably 300 or more, more preferably 500 or more, particularly preferably 600 or more, and preferably 3000 or less, more preferably 2000 or less, particularly preferably 1500 or less. Below this range, crystallization is likely to occur during wet film formation, vaporization may occur during heat treatment, and heat resistance may decrease. On the other hand, if it exceeds this range, the solubility in organic solvents tends to be reduced, and the removal of impurities tends to be difficult.

(Crystallization temperature)
The crystallization temperature of the anthracene compound of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and particularly preferably not observed. This is because it is particularly preferable that the anthracene compound of the present invention does not cause crystallization during wet film formation or subsequent heat treatment.

(Vaporization temperature)
The vaporization temperature of the anthracene compound of the present invention is preferably 500 ° C. or less, more preferably 450 ° C. or less under the condition of 0.001 Pa. This is because sublimation purification under high vacuum can promote high purity of the compound.

(Glass transition point)
The glass transition point of the anthracene compound of the present invention is usually 120 ° C. or higher, preferably 125 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 300 ° C. or lower, more preferably 250 ° C. or lower. . If the glass transition point is below this range, the thin film produced using the charge transport material for wet film formation may be crystallized by heat treatment or energization. Moreover, when a glass transition point exceeds this range, there exists a tendency for the solubility with respect to a solvent to fall.

The glass transition point can be measured by differential scanning calorimetry.
As a reaction apparatus, DSC6220 manufactured by SII Nanotechnology Inc. is used. A sample amount of 2 to 6 mg is put in an aluminum liquid sample container, and the temperature is raised from the room temperature to 400 ° C. to the melting point or more at a heating rate of 10 ° C./min in a nitrogen flow (50 mL / min) atmosphere. In addition, when melting | fusing point is not detected, it heats up to 300 degreeC.
Next, after the sample that has been heated once is rapidly cooled to room temperature or lower at a rate of −100 ° C./min or higher, the glass transition point detected when the temperature is increased again at a temperature rising rate of 10 ° C./min, It is defined as the glass transition point of the present invention.

(Solubility in solvent)
When the anthracene compound of the present invention is dissolved in toluene, the solubility is preferably 5% by weight or more, more preferably 6% by weight or more, and particularly preferably 7% by weight or more. If the solubility is below this range, the film quality of the thin film formed when wet film formation is reduced tends to be non-uniform. In addition, the selection of various solvents may be limited.

For the measurement of solubility, a glass sample bottle having an internal volume of 2 mL or more and 10 mL or less was charged with solute Xg (usually in a range of 3 mg or more and 10 mg or less) and a solvent (for example, toluene) Yg, and the sample bottle was closed. Stirring, ultrasonic irradiation or heat treatment to promote dissolution as much as possible.
Thereafter, when the precipitate, suspension or layer separation is not confirmed by visual observation or microscopic observation when allowed to stand at room temperature (usually 10 ° C. or more and 30 ° C. or less) for 10 hours or more, the solubility is (X / ( X + Y) × 100)% or more, and when precipitates are confirmed, the solubility is determined to be less than (X / (X + Y) × 100)%.

<1-3. Method for producing anthracene compound>
The anthracene compound of the present invention can be produced by arbitrarily combining known synthesis methods.
Hereinafter, although an example is demonstrated, the manufacturing method of the anthracene compound of this invention is not limited to the following examples.

The anthracene compound of the present invention is preferably produced, for example, by the following synthesis route. Among the substituents of the compound represented by the following synthesis route, the same types of substituents, are denoted by the same symbols ^{(e.g., X 1, X 2, G} A , etc.). Further, the same substituents as those described in formula (I) and the like are indicated by the same symbols as in formula (I) (for example, Ar ¹ , G ^1, etc.). Hereafter, each reaction of the following synthetic pathway is explained in detail.

<Reaction 1>
Reaction 1 is a reaction in which compound a is reacted with intermediate A or intermediate B to synthesize compound b.
In the compound a, X ^{1 to} X ³ represent a halogen atom such as chlorine, bromine or iodine, a leaving group such as a CF ₃ SO ₃ — group, or the like.
In compound b, X ^{1 to} X ² are the same as compound a. Ar ^{3 to} Ar ⁴ are aromatic hydrocarbon groups which may have a substituent, and <1-1. This is the same as Ar ^{3 to} Ar ⁴ described in detail in Structure of Anthracene Compound>.

(When reacting with intermediate A)
Hereinafter, a case where compound a is reacted with intermediate A to obtain compound b will be described. Intermediate A is a compound obtained by <Reaction 6> described later.
G ^{1 of} compound b obtained by the reaction is a direct bond.
In the reaction with the intermediate A, there are a case where a copper catalyst is used and a case where a palladium complex catalyst is used. Each will be described below.

-When using a copper catalyst When making the compound a and the intermediate body A react using a copper catalyst, it is preferable to make the compound a and the intermediate body A react in presence of a copper catalyst and a basic substance. The reaction may be performed in an inert gas atmosphere, in a solvent, or in the absence of a solvent. Further, the reaction may be performed in the presence of a ligand.

  The amount of the intermediate A used is usually 0.1 equivalents or more and usually 2 equivalents or less with respect to 1 equivalent of the compound a.

Examples of the copper catalyst include copper powder; copper wire; copper halide such as CuCl, CuBr, and CuI; copper oxide such as CuO and Cu ₂ O; Cu (CH ₃ COO), Cu (CH ₃ COO) _{2, and the} like. Copper acetate; and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity using a copper catalyst is 0.01 equivalent or more normally with respect to 1 equivalent of compound a, and is 10 equivalent or less normally.

  Examples of the basic substance include triethylamine, triethanolamine, potassium carbonate, calcium carbonate, potassium phosphate, cesium carbonate, tert-butoxy sodium and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the basic substance used is usually 1 equivalent or more and usually 100 equivalents or less with respect to 1 equivalent of compound a.

  Examples of the inert gas include nitrogen; rare gases such as He, Ne, Ar, and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  Examples of the solvent include aromatic solvents such as nitrobenzene; alcohol solvents such as tetraglyme and polyethylene glycol; solvents such as acetonitrile, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethoxyethane. . One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.1 L (liter) or more normally with respect to 1 mol of compound a, and is 100 L or less normally.

  In addition to the above, the reaction may be performed in the presence of a ligand. Examples of the ligand include trans-1,2-cyclohexanediamine, N, N′-dimethyl-1,2-ethylenediamine, 1,2-ethylenediamine, N, N′-dimethyl-1,2-cyclohexanediamine, Salicylaldoxime, dimethylglyoxime, 2-pyridinealdoxime, 1,10-phenanthroline and the like can be mentioned. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity which uses a ligand is 1 mol or more normally with respect to 1 mol of copper catalysts, and is 10 mol or less normally.

  The reaction is preferably carried out by stirring and mixing. The reaction temperature at this time is usually 20 ° C. or higher and usually 300 ° C. or lower.

  The reaction time is usually 0.5 hours or longer and usually 60 hours or shorter.

When using a palladium complex catalyst When reacting compound a and intermediate A using a palladium complex catalyst, reacting compound a and intermediate A in the presence of a palladium complex catalyst and a basic substance Is preferred. The reaction is preferably performed in a solvent.

  The amount of the intermediate A used is the same as that using the copper catalyst.

As the palladium complex catalyst, it is preferable to use a zero-valent palladium complex and / or a palladium chloride complex.
Examples of the zero-valent palladium complex include Pd ₂ (dba) ₃ (where dba is “dibenzylideneacetone”), Pd (dba) ₂ , and divalent palladium such as palladium acetate. Catalyst, BINAP (IUPAC name: 2,2′-bis (diphenylphosphino-1,1′-binaphthyl)), tri (tert-butyl) phosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ) Ligands such as ethane, 1,3-bis (diphenylphosphino) propane, 1,3-bis (diphenylphosphino) butane, dppf (IUPAC name: 1,1′-bis (diphenylphosphino) ferrocene) The complex which combined these is mentioned.
Examples of the palladium chloride complex include PdCl ₂ (dppf) _{2 and the} like.
One of these palladium complex catalysts may be used alone, or two or more thereof may be used in any combination and ratio.

  Moreover, the quantity which uses a palladium complex catalyst is 0.001 equivalent or more normally with respect to 1 equivalent of compound a, and is 1 equivalent or less normally.

  Examples of the basic substance include tert-butoxy potassium, tert-butoxy sodium, potassium carbonate, cesium carbonate, triethylamine and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity which uses a basic substance is 2 equivalent or more normally with respect to 1 equivalent of compound a, and is 100 equivalent or less normally.

  Examples of the solvent include solvents such as tetrahydrofuran, dioxane, dimethoxyethane, N, N-dimethylformamide, dimethyl sulfoxide, xylene, toluene, triethylamine, and pyridine. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.1 L or more normally with respect to 1 mol of compound a, and is 100 L or less normally.

  The reaction is preferably carried out by stirring and mixing. The reaction temperature at this time is usually 20 ° C. or higher and usually 300 ° C. or lower.

  The reaction time is usually 0.5 hours or longer and usually 60 hours or shorter.

(When reacting with intermediate B)
Hereinafter, a case where compound a is reacted with intermediate B to obtain compound b will be described. In addition, the intermediate body B is a compound obtained by <reaction 10> mentioned later.
G ¹ in the compound b obtained by the reaction is a linking group, and <1-1. G ¹ described in detail in Structure of Anthracene Compound>.

  When the compound a and the intermediate B are reacted, it is preferable to react the compound a and the intermediate A in the presence of a palladium catalyst and a basic substance. The reaction is preferably performed in a solvent under an inert gas atmosphere. Further, the reaction may be performed in the presence of a ligand.

  The amount of intermediate B used is usually 0.1 equivalents or more and usually 2 equivalents or less with respect to 1 equivalent of compound a.

  Examples of the palladium catalyst include zero-valent palladium catalysts such as tetrakis (triphenylphosphine) palladium. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the palladium catalyst used is usually 0.0001 equivalent or more and usually 0.2 equivalent or less with respect to 1 equivalent of the compound a.

  Examples of the basic substance include tert-butoxy sodium, tert-butoxy potassium, cesium carbonate, sodium carbonate, potassium carbonate, tripotassium phosphate, triethylamine, potassium hydroxide, sodium hydroxide, potassium fluoride and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the basic substance used is usually 2 equivalents or more and usually 10 equivalents or less with respect to 1 equivalent of compound a.

  Examples of the solvent include water, methanol, ethanol, normal hexanol, ethylene glycol, ethylene glycol monoethyl ether, diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and dichloromethane. , N, N-dimethylformamide, cyclohexane, cyclohexanone, ethyl benzoate, ethyl acetate and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.01 L or more normally with respect to 1 mol of compound a, and is 100 L or less normally.

  As the inert gas, the inert gas exemplified in <Reaction 1> (when reacted with intermediate A) can be used.

  The reaction is preferably carried out by stirring and mixing. The reaction temperature at this time is usually −40 ° C. or higher and usually 150 ° C. or lower.

  The reaction time is usually 1 hour or longer and usually 60 hours or shorter.

<Reaction 2>
Reaction 2 is a reaction in which compound c is reacted with Ar ² -X ¹² to synthesize compound c.
In Ar ² -X ¹² , X ¹² represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue. Ar ² is an aromatic hydrocarbon group which may have a substituent, and <1-1. Ar ² described in detail in Structure of Anthracene Compound>.
In the compound c, X ^{2 to} X ³ are the same as the compound a. Ar ² is the same as Ar ² -X ¹² .

The reaction between compound a and Ar ² -X ¹² can be performed by using Ar ² -X ¹² instead of intermediate B in <Reaction 1> (when reacted with intermediate B).

Other conditions (for example, the type of catalyst, basic substance, solvent and the amount of them used; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, compound c can be obtained as a product.

<Reaction 3>
Reaction 3 is a reaction for synthesizing intermediate C by reacting compound b with Ar ² -X ¹² .
Ar ² -X ¹² is the same as Ar ² -X ¹² used in <Reaction 2>.
In intermediate C, Ar ² is the same as Ar ² -X ¹² . X ² and Ar ^{3 to} Ar ⁴ are the same as the compound b.

The reaction of compound b and Ar ² -X ¹² can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate B).
Specifically, the reaction of <Reaction 1> (when reacted with Intermediate B) is performed using Ar ² —X ¹² instead of Intermediate B.

Other conditions (for example, the type of catalyst, basic substance, solvent and the amount of them used; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, intermediate C can be obtained as a product.

<Reaction 4>
Reaction 4 is a reaction for synthesizing intermediate C by reacting compound c with intermediate A or intermediate B.
Intermediate A and Intermediate B are the same as Intermediate A and Intermediate B used in <Reaction 1>.
Intermediate C is the same as Intermediate C synthesized in <Reaction 3>.

The reaction of compound c and intermediate A or intermediate B can be carried out in the same manner as in <Reaction 1>.
Specifically, <Reaction 1> is performed using compound c instead of compound a. Accordingly, the amounts used of intermediate A, intermediate B, solvent, copper catalyst, palladium complex catalyst and the like are defined based on compound c.

Other conditions (for example, types of catalyst, basic substance, solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 1>.
As a result of this reaction, intermediate C can be obtained as a product.

As in <Reaction 1>, G ^{1 of} Intermediate C is a direct bond when the reaction is carried out using Intermediate A, and a linking group when the reaction is carried out using Intermediate B. It is. The type of linking group is <1-1. This is the same as G ¹ described in detail in Structure of Anthracene Compound>.

<Reaction 5>
Reaction 5 is a reaction for synthesizing intermediate D from intermediate C.
In the intermediate D, X ¹³ represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue. Ar ^{2 to} Ar ⁴ and G ¹ are the same as Intermediate C.
As reaction 5, three types of reactions will be described below.

(First method of reaction 5)
A first method for synthesizing intermediate D from intermediate C will be described.
First, intermediate C and a lithiating agent are mixed in the presence of a solvent under an inert gas atmosphere under anhydrous conditions to convert the leaving group X ² of intermediate C into Li. Next, a boronating agent, a metal halide, or the like is allowed to act to obtain intermediate D.

  As the lithiating agent, for example, n-butyllithium, tert-butyllithium and the like are preferable. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the lithiating agent used is usually 0.1 equivalents or more and usually 10 equivalents or less with respect to 1 equivalent of Intermediate C.

  Examples of the solvent include tetrahydrofuran, diethyl ether, n-hexane, toluene and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the solvent used is usually 0.1 L or more and usually 100 L or less with respect to 1 mol of the intermediate C.

The reaction of converting the leaving group X ² of the intermediate C in Li is preferably performed by stirring and mixing. The reaction temperature at this time is usually −90 ° C. or higher and usually 20 ° C. or lower.

The reaction time is usually 0.1 hour or longer and usually 24 hours or shorter.
These reactions, the leaving group X ² of the intermediate C is converted to Li.

  As the inert gas, the inert gas exemplified in <Reaction 1> (when reacted with intermediate A) can be used.

Next, a boronating agent and / or a metal halide is allowed to act on the intermediate C in which the leaving group X ² has been converted to Li to obtain an intermediate D.

  Examples of the iodinating agent include trimethoxyborane, tris (i-propyloxy) borane, methoxypinacolatoborane, and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

The amount of the iodinating agent is usually 1 equivalent or more and usually 10 equivalents or less with respect to 1 equivalent of the intermediate C in which the leaving group X ² is converted to Li.

  Examples of the metal halide include tin halide, zinc halide, magnesium halide and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

The amount of the metal halide used is usually 1 equivalent or more and usually 10 equivalents or less with respect to 1 equivalent of the intermediate C in which the leaving group X ² is converted to Li.

  In addition, when an iodinating agent is used, it is preferable to process with an acidic aqueous solution.

(Second method of reaction 5)
A second method for synthesizing intermediate D from intermediate C will be described.
First converts the intermediate C and magnesium metal, under anhydrous conditions, were mixed in the presence of a solvent under an inert gas atmosphere, the leaving group X ² of the intermediate C in the magnesium halide residue. Next, a boronating agent is allowed to act to obtain intermediate D.

  The amount of metal magnesium used is usually 1 equivalent or more and usually 5 equivalents or less with respect to 1 equivalent of Intermediate C.

  Examples of the solvent include tetrahydrofuran, diethyl ether and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of the solvent used is usually 0.1 L or more and usually 10 L or less with respect to 1 mol of the intermediate C.

  As the inert gas, the inert gas exemplified in <Reaction 1> (when reacted with intermediate A) can be used.

The reaction of converting the leaving group X ² of the intermediate C in the magnesium halide residue is preferably carried out in a stirred mixed. The reaction temperature at this time is usually −90 ° C. or higher and usually 100 ° C. or lower.

The reaction time is usually 0.1 hour or longer and usually 24 hours or shorter.
These reactions, the leaving group X ² of the intermediate C is converted to magnesium halide residue.

Next, an intermediate in which a boronic acid residue is introduced is obtained by allowing a boronating agent to act on intermediate C in which the leaving group X ² has been converted to a magnesium halide residue, followed by treatment with an acidic aqueous solution. D is obtained.
In addition, the method of making a boron agent act and the method of processing with acidic aqueous solution are the same as the method demonstrated by the above-mentioned (1st method of reaction 5).

(Third method of reaction 5)
A third method for synthesizing intermediate D from intermediate C will be described.
First, intermediate C, diborane, Pd catalyst, and basic substance are mixed under anhydrous conditions in the presence of a solvent under an inert gas atmosphere, and the leaving group X ² of intermediate C is converted into a boronic ester residue. The converted intermediate D is obtained.

  Examples of diborane include bis (pinacolato) diborane. One type of diborane may be used alone, or two or more types may be used in any combination and ratio.

  The amount of diborane used is usually 1 equivalent or more and usually 10 equivalents or less with respect to 1 equivalent of Intermediate C.

  Examples of the Pd catalyst include [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II), dichloromethane complex (1: 1), and the like.

  The amount of the Pd catalyst used is usually 0.001 equivalent or more and usually 0.5 equivalent or less with respect to 1 equivalent of the intermediate C.

  As a basic substance, potassium chloride etc. are mentioned, for example. One basic substance may be used alone, or two or more basic substances may be used in any combination and ratio.

  Examples of the solvent include dimethyl sulfoxide, 1,4-dioxane and the like. One type of solvent may be used alone, or two or more types may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.1 L or more normally with respect to 1 mol of compound a, and is 100 L or less normally.

As the inert gas, the inert gas exemplified in <Reaction 1> (when reacted with intermediate A) can be used.
In addition, when an inert gas is used, there is no limitation as long as the reaction can be performed in an inert gas atmosphere, but it is preferably used under a constant air flow.

The reaction of converting the leaving group X ² of the intermediate C boronic acid ester residue, it is preferably carried out by stirring and mixing. The reaction temperature at this time is usually 20 ° C. or higher and usually 120 ° C. or lower.

The reaction time is usually 1 hour or longer and usually 60 hours or shorter.
These reactions, intermediate D which leaving group X ² of the intermediate C was converted to boronic ester residue.

<Reaction 6>
Reaction 6 is a reaction for synthesizing intermediate A by reacting compound d with Ar ³ -X ¹⁵ .
In the compound d, Ar ⁴ is an aromatic hydrocarbon group which may have a substituent, and <1-1. Ar ⁴ described in detail in Structure of Anthracene Compound>.
In Ar ³ -X ¹⁵ , Ar ³ is an aromatic hydrocarbon group which may have a substituent, and <1-1. Ar ³ described in detail in Structure of Anthracene Compound>.
X ¹⁵ represents a halogen atom such as chlorine, bromine or iodine, a leaving group such as a CF ₃ SO ₃ — group or an —OH group.
In the intermediate A, Ar ³ is the same as Ar ³ -X ¹⁵ . Ar ⁴ is the same as compound d.

The reaction between compound d and intermediate A can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate A).
Specifically, the reaction of <reaction 1> (when reacted with intermediate A) is performed using Ar ³ -X ¹⁵ in place of compound a and compound d in place of intermediate A. However, the amount of Ar ³ —X ¹⁵ used is usually 0.1 equivalent or more and usually 1.25 equivalent or less with respect to 1 equivalent of compound d.

Other conditions (catalyst, basic substance, type of solvent and amount used thereof; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, intermediate A can be obtained as a product.

<Reaction 7>
Reaction 7 is a reaction for synthesizing compound e by reacting intermediate A with X ⁴ -G ^A -X ⁵ .
In X ⁴ -G ^A -X ⁵ , X ⁴ and X ⁵ each independently represent a halogen atom such as chlorine, bromine or iodine, a leaving group such as a CF ₃ SO ₃ — group, or the like. G ^A represents a divalent aromatic hydrocarbon group. G ^A may be the same as the G ^1, in combination with G ^B which will be described later, may be G ¹ precursor capable of forming a G ^1.
In compound e, Ar ^{3 to} Ar ⁴ are the same as intermediate A. G ^A and X ⁴ are the same as X ⁴ -G ^A -X ⁵ .

The reaction of intermediate A and X ⁴ -G ^A -X ⁵ can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate A).
Specifically, X ⁴ -G ^A -X ⁵ is used instead of compound a to perform <Reaction 1> (when reacted with intermediate A). Accordingly, the amounts of the intermediate A, the solvent, the copper catalyst, the palladium complex catalyst, and the like used are defined based on X ⁴ -G ^A -X ⁵ .

Other conditions (for example, types of catalyst, basic substance, solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 1> (when reacted with intermediate A).
As a result of this reaction, compound e can be obtained as a product.

<Reaction 8>
Reaction 8 is a reaction for synthesizing compound f from compound e.
In the compound f, G ^A and Ar ^{3 to} Ar ⁴ are the same as the chemical substance e. X ⁶ represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue.

The reaction of compound e can be carried out in the same manner as in <Reaction 5>.
Specifically, <Reaction 5> is performed using Compound e instead of Intermediate C. Accordingly, the amount of lithiating agent, magnesium halide, diborane, solvent, catalyst, etc. used is defined based on compound e.

Other conditions (for example, type of solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 5>.
As a result of this reaction, compound f can be obtained as a product.

<Reaction 9>
The reaction 9, the compound ^f, by reacting X 7 ^-G B -X ^8, is a reaction to synthesize the compound g.
In X ⁷ -G ^B -X ⁸ , X ⁷ and X ⁸ each independently represent a halogen atom such as chlorine, bromine or iodine, a leaving group such as a CF ₃ SO ₃ — group, or the like. G ^B represents a divalent aromatic hydrocarbon radical. G ^B may be the same as the G ^1, in combination with G ^A described above, it may be G ¹ precursor capable of forming a G ^1.
In compound g, Ar ^{3 to} Ar ⁴ are the same as compound f. X ^{7 is} the same as the X 7 ^-G B -X ^8. G ¹ is a direct bond or a linking group. The type of linking group is <1-1. This is the same as G ¹ described in detail in Structure of Anthracene Compound>.

And compounds ^f, reaction with X 7 ^-G B -X ⁸ may be carried out in the same manner as in <Reaction 1> (when reacted with Intermediate A).
Specifically, the X ⁷ -G ^B -X ⁸ in place of Compound a, using Compound f in place of Intermediate A, performs the <Reaction 1> (when reacted with Intermediate A). Along with it, the compound f, solvent, copper catalyst, the amount used of the palladium complex catalysts ^are defined to X 7 ^-G B -X ⁸ as a reference.

Other conditions (for example, types of catalyst, basic substance, solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 1> (when reacted with intermediate A).
As a result of this reaction, compound g can be obtained as a product.

<Reaction 10>
Reaction 10 is a reaction for synthesizing intermediate B from compound g.
In the intermediate B, G ¹ and Ar ^{3 to} Ar ⁴ are each the same as the chemical g.
X ⁹ represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue.

The reaction of compound g can be carried out in the same manner as in <Reaction 5>.
Specifically, <Reaction 5> is performed using Compound g instead of Intermediate C. Accordingly, the amount of lithiating agent, magnesium halide, diborane, solvent, catalyst, etc. used is defined based on compound g.

Other conditions (for example, type of solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 5>.
As a result of this reaction, intermediate B can be obtained as a product.

<Reaction 11>
Reaction 11 is a reaction for synthesizing compound i from compound h.
In the compound h, X ¹⁰ represents a halogen atom such as chlorine, bromine or iodine; a leaving group such as a CF ₃ SO ₃ — group or an —OH group;
In the compounds ^{i, X 10} and ^{X 11} are each independently chlorine, bromine, halogen atom such as iodine; -; represent like _CF 3 SO ₃ group, the leaving group such as -OH group.
As reaction 11, two types of reactions will be described below.

(First method of reaction 11)
A first method for synthesizing compound i from compound h will be described.
When obtaining a compound i in which X ¹¹ is a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), the compound h and a halogen molecule are mixed in the presence of a Lewis acid catalyst in the presence of a solvent.

Examples of the halogen molecule include chlorine, bromine, iodine and the like.
The amount of the halogen molecule used is usually 0.1 equivalent or more and usually 100 equivalent or less with respect to 1 equivalent of compound a.

  Examples of the Lewis acid catalyst include iron (III) chloride. A Lewis acid catalyst may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and a ratio.

  The amount of the Lewis acid catalyst used is usually 0.001 equivalents or more and usually 100 equivalents or less with respect to 1 equivalent of the compound h.

  Examples of the solvent include dichloromethane and the like. One type of solvent may be used alone, or two or more types may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.1 L or more normally with respect to 1 mol of compound h, and is 100 L or less normally.

  The reaction is preferably carried out by stirring and mixing. The reaction temperature at this time is usually −50 ° C. or higher and usually 100 ° C. or lower.

The reaction time is usually 0.1 hour or longer and usually 60 hours or shorter.
As a result of this reaction, compound i can be obtained as a product.

(Second method of reaction 11)
A second method for synthesizing compound i from compound h will be described.
As the second method, compound h and N-halogenated succinimide are preferably mixed in the presence of a solvent.

  Examples of the N-halogenated succinimide include N-bromosuccinimide, N-iodosuccinimide, and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  The amount of N-halogenated succinimide used is usually 0.1 equivalents or more and usually 100 equivalents or less with respect to 1 equivalent of compound h.

  Examples of the solvent include N, N-dimethylformamide, dichloromethane and the like. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the quantity using a solvent is 0.1 L or more normally with respect to 1 mol of compound h, and is 100 L or less normally.

  The reaction is preferably carried out by stirring and mixing. The reaction temperature at this time is usually −50 ° C. or higher and usually 200 ° C. or lower.

The reaction time is usually 0.1 hour or longer and usually 60 hours or shorter.
As a result of this reaction, compound i can be obtained as a product.

<Reaction 12>
Reaction 12 is a reaction in which compound h is reacted with Ar ¹ -X ¹² to synthesize compound j.
In Ar ¹ -X ¹² , X ¹² represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue. Ar ¹ is an aromatic hydrocarbon group which may have a substituent, and <1-1. Ar ¹ described in detail in Structure of Anthracene Compound>.
In compound j, Ar ¹ is the same as Ar ¹ -X ¹² .

The reaction of compound h and Ar ¹ -X ¹² can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate B).
Specifically, instead of the intermediate B, Ar ¹ -X ¹² is used to perform the reaction of <Reaction 1> (when reacted with the intermediate B).

Other conditions (for example, the type of catalyst, basic substance, solvent and the amount of them used; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, compound j can be obtained as a product.

<Reaction 13>
Reaction 13 is a reaction for synthesizing compound k from compound j.
In compound k, Ar ¹ is the same as chemical j. X ¹⁰ represents a halogen atom such as chlorine, bromine or iodine; a leaving group such as a CF ₃ SO ₃ — group or an —OH group;

The reaction of compound j can be carried out in the same manner as in <Reaction 11>.
Specifically, <reaction 11> is performed using compound j instead of compound h. Accordingly, the amount of halogen molecule, Lewis acid catalyst, N-halogenated succinic acid, solvent and the like is defined based on the compound h.

Other conditions (for example, types of halogen molecule, Lewis acid catalyst, solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 11>.
As a result of this reaction, compound k can be obtained as a product.

<Reaction 14>
Reaction 14 is a reaction in which compound i is reacted with Ar ¹ -X ¹² to synthesize compound k.
Ar ¹ -X ¹² is the same as Ar ¹ -X ¹² used in <Reaction 12>.
Compound k is the same as compound k synthesized in <Reaction 13>.

The reaction of compound c and Ar ¹ -X ¹² can be carried out in the same manner as in <Reaction 1>.
Specifically, <Reaction 1> is performed using Compound i in place of Compound a and Ar ¹ -X ^{12 in} place of Intermediate A or Intermediate B. Accordingly, the amounts used of Ar ¹ -X ¹² , solvent, copper catalyst, palladium complex catalyst, etc. are defined based on compound i.
However, compound i is as in example ^{9-bromo-10-iodo-anthracene,} it is preferable that the reactivity of ^{X 10} and ^{X 11} are different. For example, when the reactivity of X ¹⁰ and X ¹¹ is the same as 9,10-dibromoanthracene, the equivalent of Ar ¹ -X ¹² is usually 0.1 equivalent or more with respect to 1 equivalent of compound i, In addition, the amount is usually 1.5 or less.

Other conditions (for example, types of catalyst, basic substance, solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 1>.
As a result of this reaction, compound k can be obtained as a product.

<Reaction 15>
Reaction 15 is a reaction for synthesizing compound 1 from compound k.
In compound l, Ar ¹ is the same as chemical k. X ¹⁴ represents a leaving group such as a boronic acid residue, a boronic acid ester residue, a tin halide residue, a zinc halide residue, or a magnesium halide residue.

The reaction of compound l can be carried out in the same manner as in <Reaction 5>.
Specifically, <Reaction 5> is performed using Compound k instead of Intermediate C. Accordingly, the amount of lithiating agent, magnesium halide, diborane, solvent, catalyst, etc. used is defined based on compound k.

Other conditions (for example, type of solvent, etc .; reaction temperature, reaction time, etc.) are the same as in <Reaction 5>.
As a result of this reaction, compound l can be obtained as a product.

<Reaction 16>
Reaction 16 is a reaction in which compound l and intermediate C are reacted to synthesize the final product (anthracene compound of the present invention represented by formula (I)).
Intermediate C is the same as Intermediate C synthesized in <Reaction 3> or <Reaction 4>.

The reaction of compound 1 and intermediate C can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate B).
Specifically, using Intermediate C instead of Compound a and Compound 1 instead of Intermediate B, the same method as in <Reaction 1> (when reacted with Intermediate B) is performed. Accordingly, the amounts of palladium catalyst, basic substance, solvent, ligand, etc. used are defined based on Intermediate C.

Other conditions (for example, the type of catalyst, basic substance, solvent and the amount of them used; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, the anthracene compound of the present invention can be obtained as a product.

<Reaction 17>
Reaction 17 is a reaction in which compound k is reacted with intermediate D to synthesize a final product (anthracene compound of the present invention represented by formula (I)).
Intermediate D is the same as Intermediate D synthesized in <Reaction 5>.

The reaction of compound k and intermediate D can be carried out in the same manner as in <Reaction 1> (when reacted with intermediate B).
Specifically, using the compound k instead of the compound a and the intermediate D instead of the intermediate B, the same method as in <Reaction 1> (when reacted with the intermediate B) is performed. Accordingly, the amounts of palladium catalyst, basic substance, solvent, ligand, etc. used are defined based on compound k.

Other conditions (for example, the type of catalyst, basic substance, solvent and the amount of them used; reaction temperature, reaction time, etc.) are the same.
As a result of this reaction, the anthracene compound of the present invention can be obtained as a product.

<Methods for producing other anthracene compounds>
The manufacturing method of the anthracene compound according to the present invention is not limited to the above-described example, and may be manufactured by any other known method as long as the effects of the present invention are not significantly impaired. In addition, any other known raw material other than the examples described above may be used for the synthesis of the anthracene compound.

  As a specific example, “Palladium in Heterocyclic Chemistry: A guide for the Synthetic Chemist” (2nd edition, 2002, Jie Jack Li and Gordon W. Gribble, Takumi Organic, “Takumi” And the latest achievements "(1997, Junjiro, Kagaku Doujinsha)," Under Borhard Shore Modern Organic Chemistry "(2004, K.P.C. In addition, a ring-to-ring coupling (coupling) reaction (for example, a coupling reaction between an aryl halide and an aryl borate) can be used.

<Purification method of anthracene compound>
As a method for purifying the anthracene compound obtained by synthesis, any known method can be used as long as the effects of the present invention are not significantly impaired.

Specific examples include "Separation and Purification Technology Handbook" (1993, edited by The Chemical Society of Japan), "Advanced separation of trace components and difficult-to-purify substances by chemical conversion method" (1988, published by ICC Corporation). Or the method described in the section “Separation and purification” of “Experimental Chemistry Course (4th edition) 1” (1990, edited by The Chemical Society of Japan).

  More specifically, extraction (including suspension washing, boiling washing, ultrasonic washing, acid-base washing), adsorption, occlusion, melting, crystallization (including recrystallization from solvent, reprecipitation), distillation (ordinary) Pressure distillation, vacuum distillation), evaporation, sublimation (atmospheric pressure sublimation, vacuum sublimation), ion exchange, dialysis, filtration, ultrafiltration, reverse osmosis, pressure osmosis, zone dissolution, electrophoresis, centrifugation, flotation separation, sedimentation separation , Magnetic separation, various chromatography (shape classification: column, paper, thin layer, capillary. Mobile phase classification: gas, liquid, micelle, supercritical fluid. Separation mechanism: adsorption, distribution, ion exchange, molecular sieve, chelate, gel Filtration, exclusion, affinity) and the like.

The product confirmation and purity analysis methods include gas chromatograph (GC), high performance liquid chromatograph (HPLC), high speed amino acid analyzer (AAA), capillary electrophoresis measurement (CE), size exclusion chromatograph (SEC), Gel permeation chromatograph (GPC), cross-fractionation chromatograph (CFC) mass spectrometry (MS, LC / MS, GC / MS, MS / MS), nuclear magnetic resonance apparatus (NMR ( ¹ H-NMR, ¹³ C-NMR) ), Fourier transform infrared spectrophotometer (FT-IR), ultraviolet visible near infrared spectrophotometer (UV.VIS, NIR), electron spin resonance apparatus (ESR), transmission electron microscope (TEM-EDX), electron beam microanalyzer (EPMA), metal element analysis (ion chromatograph, inductively coupled plasma-emission spectroscopy (ICP-AES) atomic absorption Analysis (AAS) X-ray fluorescence analyzer (XRF)), non-metallic element analysis, trace component analysis (ICP-MS, GF-AAS, GD-MS) and the like can be applied as necessary.

<1-4. Preferred examples of anthracene compounds>
Hereinafter, preferred examples of the anthracene compound of the present invention will be illustrated. The following is an example, and the anthracene compound of the present invention is not limited as long as it satisfies the formula (I).

<1-5. Applications of anthracene compounds>
Since the anthracene compound of the present invention has high heat resistance, excellent solubility in an organic solvent, or high charge transportability, an electrophotographic photoreceptor, an organic electroluminescent element, a photoelectric conversion element can be used as a charge transporting material or a light emitting material. It can be suitably used for organic solar cells, organic rectifying elements and the like.
In addition, since it has a high singlet excitation level, an excellent fluorescence quantum yield, an excellent electrical durability, or an excellent amorphous property, by using a charge transport material comprising the anthracene compound of the present invention, An organic electroluminescent element that has excellent heat resistance and can be stably driven (emitted) for a long period of time can be obtained. Therefore, the anthracene compound and the charge transport material of the present invention are particularly suitable as an organic electroluminescent element material.

[2. Charge transport material for wet film formation]
The present invention also relates to a charge transport material for wet film formation comprising an anthracene compound represented by the above formula (I).
Here, the charge transport material for wet film formation refers to forming a film having charge transport properties by forming a film in a state of being dispersed or dissolved in a solvent and then removing part or all of the solvent. A material intended for

  The charge transport material for wet film formation has a glass transition point of 120 ° C. or higher and a solubility in toluene of 5% by weight or more in view of the use of the organic electroluminescence device utilizing the wet film formation method. preferable. Hereinafter, the glass transition point and the solubility in a solvent will be described in detail.

(Glass transition point)
The glass transition point of the charge transport material for wet film formation is usually 120 ° C. or higher, preferably 125 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 300 ° C. or lower, more preferably 250 ° C. or lower. It is. If the glass transition point is below this range, the thin film produced using the charge transport material for wet film formation may be crystallized by heat treatment or energization. Moreover, when a glass transition point exceeds this range, there exists a tendency for the solubility with respect to a solvent to fall.
In addition, the measurement of a glass transition point is <1-2. It can be measured in the same manner as the method described in “Physical Properties of Anthracene Compound>.

(Solubility in solvent)
When the charge transport material for wet film formation is dissolved in toluene, the solubility is preferably 5% by weight or more, more preferably 6% by weight or more, and particularly preferably 7% by weight or more. If the solubility is below this range, the film quality of the thin film formed when wet film formation is reduced tends to be non-uniform. In addition, the selection of various solvents may be limited.
In addition, the measurement of the solubility in a solvent is <1-2. It can be measured in the same manner as the method described in “Physical Properties of Anthracene Compound>.

[3. Charge transport material composition for wet film formation]
The present invention also relates to a charge transport material composition for wet film formation containing an anthracene compound represented by the above formula (I).
Here, the charge transport material composition for wet film formation refers to a mixture of a charge transport material for wet film formation and a compound or solvent other than the charge transport material for wet film formation. As a compound other than the anthracene compound of the present invention, for example, a charge transporting compound is preferably contained.

（式（ＩＩ）中、Ａｒ^３１は、置換基を有していてもよい炭素数６以上３０以下の芳香族炭化水素基を表わす。また、Ａｒ^３２およびＡｒ^３３は、それぞれ独立に、水素原子または置換基を有していてもよい芳香族炭化水素基を表わす。但し、Ａｒ^３２およびＡｒ^３３の少なくとも一方は、置換基を有していてもよい芳香族炭化水素基である。Ａｒ^３１が結合するアントラセン環は、更に置換基を有していてもよい。） <Charge transporting compound>
As the charge transporting compound, a compound represented by the following formula (II) is preferable.

(In formula (II), Ar ³¹ represents an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms. Ar ³² and Ar ³³ are each independently a hydrogen atom. or it represents an aromatic hydrocarbon group which may have a substituent. However, .Ar ³¹ at least one is an optionally substituted aromatic hydrocarbon group Ar ³² and Ar ³³ are (The anthracene ring to be bonded may further have a substituent.)

(About Ar ³¹ )
In the formula (II), Ar ³¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent.
Examples of the aromatic hydrocarbon group include <1-1. Described in the structure of the anthracene compound> include groups exemplified as Ar ¹ in compounds of formula (I). Of these, a group derived from a benzene ring or a naphthalene ring, or a group formed by linking a plurality of these groups (for example, a biphenyl group, a terphenyl group, etc.) is preferable.

  Examples of the substituent that the aromatic hydrocarbon group may have include the substituents described in the above substituent group Q. As for these substituents, one type of substituent may be substituted independently per aromatic hydrocarbon group, or two or more types of substituents may be substituted in any combination and ratio. .

(About Ar ³² and Ar ³³ )
In the formula (II), Ar ³² and Ar ³³ each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent. However, at least one of Ar ³² and Ar ³³ is an aromatic hydrocarbon group which may have a substituent.
Preferred types of aromatic hydrocarbon groups are the same as those for Ar ³¹ .

(Additional substituent of anthracene ring)
The anthracene ring to which Ar ³¹ is bonded may further have a substituent. Examples of the substituent include the groups described in the substituent group Q.

  Among the substituent group Q, an aromatic hydrocarbon group which may have a substituent is preferable. In particular, a group derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, or a combination of these groups in any combination (usually) 2 or more, and usually 8 or less, preferably 4 or less) are preferably formed by linking.

In the group further substituted on the anthracene ring to which Ar ³¹ is bonded, one type of substituent may be substituted alone, or two or more types of substituents may be substituted in any combination and ratio.

  The preferred substitution positions of the above substituents are preferably 2, 3, 6, and 7 positions. This is in order to avoid a decrease in electrical durability that accompanies a significant loss of molecular planarity.

(Molecular weight)
The molecular weight of the compound represented by the formula (II) is preferably 300 or more, more preferably 500 or more, particularly preferably 600 or more, preferably 3000 or less, more preferably 2000 or less, particularly preferably 1500 or less. If the molecular weight is less than this range, crystallization is likely to occur during wet film formation, vaporization may occur during heat treatment, and heat resistance may be reduced. On the other hand, if it exceeds this range, the solubility in organic solvents tends to be reduced, and the removal of impurities tends to be difficult.

(Crystallization temperature)
The crystallization temperature of the compound represented by the formula (II) is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and particularly preferably not observed.
This is because it is particularly preferable that the compound represented by the formula (II) does not cause crystallization during wet film formation or subsequent heat treatment.

(Vaporization temperature)
The vaporization temperature of the compound represented by the formula (II) is preferably 500 ° C. or less, more preferably 450 ° C. or less under the condition of 0.001 Pa. This is because sublimation purification under high vacuum can promote high purity of the compound.

(Mixing ratio)
In the charge transport material composition for wet film formation, when the anthracene compound of the present invention and the charge transport compound represented by the formula (II) are mixed, the mixing ratio is not limited.
However, when the charge transport material composition for wet film formation is 100 parts by weight, the anthracene compound of the present invention is usually 10 parts by weight or more, preferably 20 parts by weight or more, and usually 90 parts by weight or less, preferably 80 parts by weight. It is usually 10 parts by weight or more, preferably 20 parts by weight or more, and usually 90 parts by weight or less, preferably 80 parts by weight or less of the charge transporting compound represented by the formula (II). desirable.

<Light emitting material>
The charge transport material composition for wet film formation preferably further contains a light emitting material.
Here, the light emitting material is a material having a fluorescence quantum yield of 30% or more in a dilute solution at room temperature in an inert gas atmosphere, and it is determined based on the comparison with the fluorescence spectrum in the dilute solution. A part or all of an EL spectrum obtained when an organic electroluminescent element manufactured by using an electric current is energized is defined as a material attributed to light emission of the material.

Any known material can be applied as the light emitting material. For example, a fluorescent material or a phosphorescent material may be used, but a phosphorescent material is preferable from the viewpoint of internal quantum efficiency. Alternatively, blue may be used in combination, such as using a fluorescent material, and green and red using a phosphorescent material.
In order to improve the solubility in a solvent, it is preferable to reduce the symmetry and rigidity of the molecules of the luminescent material or introduce a lipophilic substituent such as an alkyl group.

Hereinafter, although the example of a fluorescent dye is mentioned among light emitting materials, a fluorescent dye is not limited to the following illustrations.
Examples of fluorescent dyes that give blue light emission (blue fluorescent dyes) include naphthalene, perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
Examples of fluorescent dyes that give green light emission (green fluorescent dyes) include quinacridone derivatives, coumarin derivatives, and aluminum complexes such as Al (C ₉ H ₆ NO) ₃ .
Examples of fluorescent dyes that give yellow light (yellow fluorescent dyes) include rubrene and perimidone derivatives.
Examples of fluorescent dyes that give red luminescence (red fluorescent dyes) include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzoates. Examples thereof include thioxanthene derivatives and azabenzothioxanthene.

As the phosphorescent material, for example, a long-period type periodic table (hereinafter referred to as a long-period type periodic table when referred to as “periodic table” unless otherwise specified) is selected from the seventh to eleventh groups. And an organometallic complex containing a metal.
Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
As the ligand of the complex, a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or a (hetero) arylpyrazole ligand and a pyridine, pyrazole, phenanthroline, or the like is connected is preferable. A pyridine ligand and a phenylpyrazole ligand are preferable. Here, (hetero) aryl represents an aryl group or a heteroaryl group.

  Specific examples of the phosphorescent material include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, and the like.

  The molecular weight of the compound used as the light emitting material is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10,000 or less, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and usually 100 or more, Preferably it is 200 or more, More preferably, it is 300 or more, More preferably, it is the range of 400 or more. If the molecular weight of the luminescent material is too small, the heat resistance will be significantly reduced, gas will be generated, the film quality will deteriorate when the film is formed, or the morphology of the organic electroluminescent element will change due to migration, etc. Sometimes come. On the other hand, if the molecular weight of the luminescent material is too large, it tends to be difficult to purify the organic compound, or it may take time to dissolve in the solvent.

  In addition, only 1 type may be used for the luminescent material mentioned above, and 2 or more types may be used together by arbitrary combinations and a ratio.

  The ratio of the light emitting material in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.05 wt% or more and usually 35 wt% or less. If the amount of the light emitting material is too small, uneven light emission may occur. If the amount is too large, the light emission efficiency may be reduced. In addition, when using together 2 or more types of luminescent material, it is made for the total content of these to be contained in the said range.

  Other specific examples of the light emitting material include a condensed aromatic ring compound substituted with an arylamino group, a styryl derivative substituted with an arylamino group, a condensed aromatic ring compound represented by the formula (III) described later, and the like Can be given.

  As the condensed aromatic ring compound substituted with an arylamino group, compounds represented by the formulas (6) to (11) in International Publication No. 2006/070712 are preferable. In addition, as an aryl group having 5 to 40 nuclear carbon atoms in the formula (11), benzophenanthryl is also preferable in addition to the examples described in International Publication No. 2006/070712 pamphlet.

  As the styryl derivative substituted with an arylamino group, a compound represented by the formula (12) is preferable in the pamphlet of International Publication No. 2006/070712.

式（ＩＩＩ）中、Ａｒ^１０は置換もしくは無置換の核炭素数５以上４０以下のアリール基である。該アリール基は、好ましくは３以上、更に好ましくは４以上、また、好ましくは７以下、さらに好ましくは６以下の芳香環核が縮合した構造を有する。 As the luminescent material, a condensed aromatic ring compound represented by the following formula (III) is also preferable.

In formula (III), Ar ¹⁰ is a substituted or unsubstituted aryl group having 5 to 40 nuclear carbon atoms. The aryl group preferably has a structure in which 3 or more, more preferably 4 or more, and preferably 7 or less, more preferably 6 or less aromatic ring nuclei are condensed.

In the formula (III), Ar ¹⁰ includes a chrycenyl group, a naphthacenyl group, an anthranyl group, a phenanthryl group, a pyrenyl group, a coronyl group, a fluoranthenyl group, a benzophenanthryl group, an acenaphthofluoranthenyl group, a fluorenyl group, and the like. Can be given.

  In the formula (III), R is selected from a hydrogen atom, an alicyclic hydrocarbon group, or a group exemplified as a substituent for the aryl group of the formula (11) in WO 2006/070712 pamphlet.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 5 or more and 8 or less carbon atoms, and specific examples thereof include a cyclohexyl group and a cyclopentyl group.
Of the groups exemplified as the substituent of the aryl group of the formula (11) in the pamphlet of International Publication No. 2006/070712, an alkyl group is preferable, and an alkyl having a tertiary carbon atom or a quaternary carbon atom is particularly preferable. Group is preferable, and an alkyl group having 4 to 15 carbon atoms is particularly preferable.

In addition, the following compounds can also be used as a blue light-emitting material.

  A preferable compound as a light emitting material for blue is an aryl group in which a central skeleton is preferably 3 or more, more preferably 4 or more, and preferably 7 or less, more preferably 6 or less, condensed with an aromatic ring nucleus. is there. Examples of the central skeleton include a chrycenyl group, a naphthacenyl group, an anthranyl group, a phenanthryl group, a pyrenyl group, a coronyl group, a fluoranthenyl group, a benzophenanthryl group, an acenaphthofluoranthenyl group, and a fluorenyl group.

As the light-emitting material of the charge transport material composition for wet film formation, one type may be used alone, or two or more types may be used in any combination and ratio.
The light emitting material for the charge transport material composition for wet film formation is usually 1 part by weight or more, usually 50 parts by weight or less, preferably 30 parts by weight or less, assuming that the composition is 100 parts by weight. If it exceeds this range, there is a possibility that the light emission efficiency, the drive life, the emission spectrum becomes broad, and the like. On the other hand, if it falls below this range, there is a possibility that the light emission life, drive life, and drive voltage increase.

<Solvent>
The charge transport material composition for wet film formation preferably further contains a solvent.
Here, the solvent is a volatile liquid component used for forming a layer containing the anthracene compound of the present invention by wet film formation.

The solvent is not particularly limited as long as the solute dissolves well, but the following examples are preferable.
For example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, and tetralin; halogenated fragrances such as chlorobenzene, dichlorobenzene, and trichlorobenzene Group hydrocarbons: 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethyl Aromatic ethers such as anisole and diphenyl ether; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate; Alicyclic ketones such as Sanone, Cyclooctanone and Fencon; Alicyclic alcohols such as cyclohexanol and cyclooctanol; Aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; Aliphatic alcohols such as butanol and hexanol; Ethylene And aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA).
Of these, alkanes and aromatic hydrocarbons are preferable. One of these solvents may be used alone, or two or more thereof may be used in any combination and ratio.

(boiling point)
The boiling point of the solvent is usually 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher. Below this range, during wet film formation, film formation stability may decrease due to solvent evaporation from the wet film formation charge transport material composition.
In order to obtain a more uniform film, it is preferable that the solvent evaporates from the liquid film immediately after the film formation at an appropriate rate. For this reason, the boiling point of the solvent is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and usually 270 ° C. or lower, preferably 250 ° C. or lower, more preferably 230 ° C. or lower.

(amount to use)
The amount of the solvent used is preferably 10 parts by weight or more, more preferably 50 parts by weight or more, particularly preferably 80 parts by weight or more, and preferably 99 parts by weight with respect to 100 parts by weight of the charge transport material composition for wet film formation. .95 parts by weight or less, more preferably 99.9 parts by weight or less, and particularly preferably 99.8 parts by weight or less. When the content is less than 10 parts by weight, the viscosity becomes too high, and the film forming workability may be lowered. On the other hand, if the amount exceeds 99.95 parts by weight, the thickness of the film obtained by removing the solvent after film formation cannot be obtained, so that film formation tends to be difficult.

<Others that may be included in the charge transport material composition for wet film formation>
The charge transport material composition for wet film formation may further contain other compounds in addition to the above-described compounds as necessary.

  For example, in addition to the above solvent, another solvent may be contained. Examples of such a solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, you may contain various additives, such as a leveling agent and an antifoamer, for the purpose of the improvement of film formability.

[4. Organic electroluminescent device]
The present invention also provides an organic electroluminescent device having an anode, a cathode, and an organic light emitting layer provided between the two electrodes on a substrate, the above-described wet film forming charge transport material or wet film forming charge transport. The present invention relates to an organic electroluminescence device having a layer containing a material composition.

<Configuration>
FIG. 1 is a schematic cross-sectional view showing an example of the organic electroluminescent element of the present invention.
In FIG. 1, an organic electroluminescent device 10 includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer (organic light emitting layer) 5, a hole blocking layer 6, an electron transport layer 7 on a substrate 1. A cathode buffer layer 8 and a cathode 9 are laminated in this order. Among these layers, the layers from the hole injection layer 3 to the cathode buffer layer 8 (excluding the light emitting layer 5) are laminated as required even if all the layers are laminated. It does not have to be.

  Moreover, the organic electroluminescent element of this invention is not limited to the structure of FIG. 1 unless the effect of this invention is impaired remarkably, Arbitrary shapes, arrangement | positioning, etc. can be taken. For example, the organic light emitting element 10 may be stacked on the substrate in the reverse order (that is, stacked from the cathode side).

The layer containing the wet film forming charge transport material or the wet film forming charge transport material composition is preferably the light emitting layer 5.
Hereinafter, the above layers will be described in detail with reference to FIG.

<Substrate 1>
The substrate 1 serves as a support for the organic electroluminescent element 10.
The material of the substrate 1 is not limited so as not to significantly impair the effects of the present invention, but is preferably a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. One of these may be used alone, or two or more may be used in any combination and ratio.

  In addition, when using a synthetic resin board | substrate as the board | substrate 1, it is desirable to pay attention to gas barrier property. If the gas barrier property of the substrate 1 is too low, the organic electroluminescent element 10 may be deteriorated by the outside air that has passed through the substrate 1. For this reason, it is preferable to take a method for providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate.

  The thickness of the substrate 1 is not limited, but is usually 0.01 mm or more, preferably 0.1 mm or more, more preferably 0.2 mm or more, and usually 5 cm or less, preferably 2 cm or less, more preferably 1 cm or less.

  In addition, the board | substrate 1 may be the structure which consists of a single layer, and may have the structure by which the several layer was laminated | stacked. In the latter case, the plurality of layers may be layers made of the same material or layers made of different materials.

<Anode 2>
An anode 2 is formed on the substrate 1.
The anode 2 serves to inject holes into an adjacent layer in the direction opposite to the substrate 1.

  The material of the anode 2 is not limited as long as it has conductivity. For example, a metal such as aluminum, gold, silver, nickel, palladium, or platinum, a metal oxide such as indium and / or tin oxide, Metal halides such as copper iodide, carbon black, or conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline are preferable. One of these may be used alone, or two or more may be used in any combination and ratio.

  Although the method for forming the anode 2 is not limited, a sputtering method, a vacuum deposition method, or the like is usually used. When the anode 2 is formed using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., these are used as an appropriate binder. The anode 2 can also be formed by dispersing it in a resin solution and applying it onto the substrate 1.

  Furthermore, when a conductive polymer is used as a material, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 ( Appl.Phys.Lett., 60, 2711, 1992).

In FIG. 1, the anode 2 has a single-layer structure, but may have a stacked structure in which a plurality of layers are stacked as desired. In the latter case, the plurality of layers may be layers made of the same material or layers made of different materials.
Furthermore, the anode 2 may be formed integrally with the substrate 1 described above, and the anode 2 may also serve as the substrate 1.

The thickness of the anode 2 is appropriately selected depending on the transparency required for the anode 2.
When the anode 2 is required to be transparent, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. If the anode 2 is too thin, the electrical resistance may increase. Moreover, when too thick, transparency will fall.

  On the other hand, when the anode 2 may be opaque, the thickness of the anode 2 is arbitrary.

  For the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property, the surface of the anode 2 is subjected to ultraviolet (UV) treatment, ozone treatment, It is preferable to perform plasma treatment such as oxygen plasma or argon plasma.

<Hole injection layer 3>
A hole injection layer 3 can be formed on the anode 2.
The hole injection layer 3 is a layer that transports holes to a layer adjacent to the cathode side of the anode 2.
The organic electroluminescent element 10 of the present invention may have a configuration in which the hole injection layer 3 is omitted.

  The hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, the hole injection layer 3 preferably contains a cation radical compound, and particularly preferably contains a cation radical compound and a hole transporting compound.

  The hole injection layer 3 may contain a binder resin and a coating property improving agent as necessary. The binder resin is preferably one that hardly acts as a charge trap.

  The hole injection layer 3 can be formed by depositing only the electron-accepting compound on the anode 2 by a wet film-forming method, and directly applying and laminating the charge transport material composition thereon. In this case, a part of the charge transport material composition interacts with the electron-accepting compound, so that a layer excellent in hole injecting property is formed.

(Hole transporting compound)
As said hole transportable compound, the compound which has the ionization potential of 4.5 eV-6.0 eV is preferable. However, when used in the wet film forming method, it is preferable that the solubility in the solvent used in the wet film forming method is high.

  Examples of the hole transporting compound include aromatic amine compounds, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, and the like. Of these, aromatic amine compounds are preferred from the viewpoints of amorphousness and visible light transmittance.

  The type of the aromatic amine compound is not particularly limited, and may be a low molecular compound or a high molecular compound. From the viewpoint of the surface smoothing effect, the high molecular compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less. (Polymerized hydrocarbon compound in which repeating units are continuous) is preferred.

  Of the aromatic amine compounds, an aromatic tertiary amine compound is particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.

（上記式（ｉ）中、Ａｒ^ａ１、Ａｒ^ａ２は各々独立して、置換基を有していてもよい芳香族炭化水素基、または置換基を有していてもよい芳香族複素環基を表わす。Ａｒ^ａ３〜Ａｒ^ａ５は、各々独立して、置換基を有していてもよい２価の芳香族炭化水素基、または置換基を有していてもよい２価の芳香族複素環基を表わす。Ｚ^ａは、下記の連結基群の中から選ばれる連結基を表わす。また、Ａｒ^ａ１〜Ａｒ^ａ５のうち、同一のＮ原子に結合する二つの基は互いに結合して環を形成してもよい。）

（上記各式中、Ａｒ^ａ６〜Ａｒ^ａ１６は、各々独立して、置換基を有していてもよい芳香族炭化水素環、または置換基を有していてもよい芳香族複素環由来の１価または２価の基を表わす。Ｒ^ａ１およびＲ^ａ２は、各々独立して、水素原子または任意の置換基を表わす。） Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (i).

(In the above formula (i), Ar ^a1 and Ar ^a2 each independently represent an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. Ar ^{a3 to} Ar ^a5 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent. Z ^a represents ^a linking group selected from the following group of linking groups, and two groups bonded to the same N atom among Ar ^{a1 to} Ar ^a5 are bonded to each other to form a ring. You may do it.)

(In the above formulas, Ar ^{a6 to} Ar ^a16 are each independently an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent. R ^a1 and R ^a2 each independently represents a hydrogen atom or an arbitrary substituent.

As Ar ^{a1 to} Ar ^a16 , any monovalent or divalent group derived from any aromatic hydrocarbon ring or aromatic heterocyclic ring is applicable. These groups may be the same or different from each other. Further, these groups may further have an arbitrary substituent. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less.

Ar ^a1 and Ar ^a2 are preferably monovalent groups derived from a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, or a pyridine ring from the viewpoints of solubility, heat resistance, and hole injection / transport properties of the polymer compound. More preferred are a phenyl group and a naphthyl group.

Ar ^{a3 to} Ar ^a5 are preferably divalent groups derived from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring from the viewpoint of heat resistance and hole injection / transport properties including redox potential. A group, a biphenylene group, and a naphthylene group are more preferable.

Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the general formula (i) include compounds described in International Publication No. 2005/089024 pamphlet.
The hole transporting compound used as the material for the hole injection layer may contain any one of these compounds alone, or may contain two or more.
When two or more hole transporting compounds are contained, the combination thereof is arbitrary, but one or more aromatic tertiary amine polymer compounds and one or two other hole transporting compounds are used. It is preferable to use the above together.

(Electron-accepting compound)
As the electron-accepting compound, a compound having an oxidizing power and an ability to accept one electron from the above-described hole-transporting compound is preferable. Specifically, a compound with an electron affinity of 4 eV or more is preferable, and a compound with a compound of 5 eV or more is more preferable.

  Examples of the electron-accepting compound include onium salts substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, iron (III) chloride (Japanese Patent Laid-Open No. 11-251067). Publication), high valence inorganic compounds such as ammonium peroxodisulfate, cyano compounds such as tetracyanoethylene, aromatic boron compounds such as tris (pentafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365), fullerene derivatives, iodine Etc.

  Of the above-mentioned compounds, an onium salt substituted with an organic group, a high-valence inorganic compound, and the like are preferable because they have strong oxidizing power. In addition, an onium salt substituted with an organic group, a cyano compound, an aromatic boron compound, or the like is preferable because it is soluble in various solvents and can be applied to wet coating.

Specific examples of onium salts, cyano compounds and aromatic boron compounds substituted with an organic group suitable as an electron-accepting compound include those described in International Publication No. 2005/089024, and the preferred examples thereof are also the same. is there. Examples thereof include compounds represented by the following structural formulas, but are not limited thereto.
In addition, an electron-accepting compound may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and a ratio.

(Cation radical compound)
As the cation radical compound, an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion is preferable. However, when the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.

  The cation radical is preferably a chemical species obtained by removing one electron from the compound described above as the hole transporting compound. A chemical species obtained by removing one electron from a compound preferable as a hole transporting compound is preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility, and the like.

  Here, the cation radical compound can be generated by mixing the hole transporting compound and the electron accepting compound. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical and the counter anion of the hole transporting compound A cation ion compound consisting of

  Cationic radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, 12, 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, 94, 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization).

  The oxidative polymerization referred to here is a method in which a monomer is chemically or electrochemically oxidized using peroxodisulfate or the like in an acidic solution. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is polymerized by oxidation, and a cation radical that is removed from the polymer repeating unit by using an anion derived from an acidic solution as a counter anion is removed. Generate.

(Method for producing hole injection layer 3)
The hole injection layer 3 can be formed by any method as long as the effects of the present invention are not significantly impaired. For example, the hole injection layer 3 is formed on the anode 2 by a wet film formation method or a vacuum evaporation method.

  In the case of layer formation by a wet film formation method, one or more predetermined amounts of each of the above-described materials (hole transporting compound, electron accepting compound, cation radical compound) act as a charge trap if necessary. First, a coating solution is prepared by dissolving it in a solvent together with a difficult binder resin and coating property improver. Subsequently, the positive hole injection layer 3 can be formed by applying on the anode by a wet film forming method such as spin coating, spray coating, dip coating, die coating, flexographic printing, screen printing, and ink jet method, and drying.

As the solvent used for the layer formation by the wet film forming method, any solvent can be used as long as it can dissolve the above-mentioned materials (hole transporting compound, electron accepting compound, cation radical compound). Is not particularly limited. In addition, the material used for the hole injection layer (a hole transporting compound, an electron accepting compound, a cation radical compound) does not contain a deactivating substance or a substance that generates a deactivating substance that may deactivate the material. Is preferred.
Specific examples of the preferable solvent include those exemplified as the solvent contained in the charge transport material composition for wet film formation according to the present invention, and among them, aromatic ethers, aromatic esters, aliphatic ethers. Ether solvents or ester solvents such as are preferred.

  The concentration of the solvent in the coating solution is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, and usually 99.999% by weight or less, preferably 99.99% by weight or less. More preferably, it is 99.9% by weight or less. In addition, when using 2 or more types of solvents in mixture, the total of these solvents should just satisfy this range.

In the case of layer formation by vacuum deposition, first, one or more of the above-mentioned materials (hole transporting compound, electron accepting compound, cation radical compound) are placed in a crucible placed in a vacuum vessel. Put (into each crucible when two or more materials are used), and then evacuate the inside of the vacuum vessel to about 10 ⁻⁴ Pa with a suitable vacuum pump. After that, the crucible is heated (each crucible is heated when two or more materials are used), and the amount of evaporation is controlled and evaporated (when two or more materials are used, the amount of evaporation is controlled independently). Evaporation) and a hole injection layer can be formed on the anode of the substrate placed facing the crucible. In addition, when using 2 or more types of materials, they can also be put into a crucible, can be heated and evaporated, and can be used for hole injection layer formation.

  The film thickness of the hole injection layer 3 formed as described above is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. If the hole injection layer 3 is too thin, the hole injection property may be insufficient. Moreover, when it is too thick, resistance may become high.

  The hole injection layer 3 may have a single layer structure, or may have a structure in which a plurality of layers are stacked. In the latter case, the plurality of layers may be layers made of the same material or layers made of different materials.

<Hole transport layer 4>
The hole transport layer 4 can be formed on the hole injection layer 3 when the hole injection layer 3 is provided, and on the anode 2 when the hole injection layer 3 is not provided.
Holes can be transported and efficiently injected into the light-emitting layer 5 by the hole transport layer 4.
The organic electroluminescent element 10 of the present invention may have a configuration in which the hole transport layer 4 is omitted.

The material that can be used for the hole transport layer 4 is preferably a material that has high hole transportability and can efficiently transport injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and impurities that become traps are not easily generated during manufacturing or use.
Further, in many cases, it is in contact with the light emitting layer 5, so it is preferable not to quench the light emitted from the light emitting layer 5 or form an exciplex with the light emitting layer 5 to reduce the efficiency.

  Examples of such a hole transport material include 4,4′-bis [N- (1-naphthyl) -N-phenyl in addition to the hole transport compound used for the hole injection layer 3 described above. Aromatic diamines containing two or more tertiary amines typified by amino] biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4, 4 ′, 4 '' -Tris (1-naphthylphenylamino) triphenylamine and other aromatic amine compounds having a starburst structure (J. Lumin., 72-74, 985, 1997), tetraphenylamine tetramer Aromatic amine compounds consisting of (Chem. Commun., 2175, 1996), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene, etc. Spiro compounds (Synth. Metals, 91, pp. 209 pp., 1997), 4,4'-N, such as a carbazole derivative such as N'- dicarbazole biphenyl.

  Furthermore, after forming a thin film by a film forming method to be described later, it is also possible to use a compound that is polymerized by heating, irradiation with electromagnetic waves such as light or magnetism, or a polymer in which a plurality of arbitrary compounds are polymerized in advance.

  Examples of such a polymer include polyvinyl carbazole, polyvinyl triphenylamine (JP-A-7-53953), and polyarylene ether sulfone (Polym. Adv. Tech., Vol. 7, p. 33) containing tetraphenylbenzidine. 1996). One of these may be used alone, or two or more may be used in any combination and ratio.

  The hole transport layer 4 is formed by, for example, a normal coating method such as a spray method, a printing method, a spin coating method, a dip coating method, or a die coating method, or a wet film forming method such as various printing methods such as an ink jet method or a screen printing method. It can be formed by a dry film formation method such as a vacuum evaporation method.

  In the case of the coating method, one or more of the hole transport materials are mixed with additives such as binder resin and coating property improving agent that do not trap holes if necessary and dissolved in a suitable solvent. A solution is prepared, applied onto the anode 2 or the hole injection layer 3 by a method such as spin coating, and dried to form the hole transport layer 4.

  Examples of the binder resin include polycarbonate, polyarylate, and polyester. When the amount of the binder resin added is large, the hole mobility is lowered. Therefore, the smaller amount is desirable, and the content in the hole transport layer is usually preferably 50% by weight or less.

  In the case of the vacuum deposition method, for example, the hole transport material is put in a crucible installed in a vacuum vessel, the pressure inside the vacuum vessel is reduced with an appropriate vacuum pump, and then the crucible is heated to form a hole transport material. The hole transport layer 4 can be formed on the anode 2 or the hole injection layer 3 placed opposite to the crucible.

  The thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less. In order to form such a thin film uniformly, spin coating or vacuum deposition is generally used in many cases.

<Light emitting layer 5>
The light emitting layer 5 is formed on the hole transport layer 4 when the hole transport layer 4 is provided, and on the hole injection layer 3 when the hole transport layer 4 is not provided and the hole injection layer 3 is provided. In the case where the hole transport layer 4 and the hole injection layer 3 are not provided, they are formed on the anode 2.
The light emitting layer 5 may be an independent layer from the hole injection layer 3 and the hole transport layer 4 described above, and the hole blocking layer 6 and the electron transport layer 7 described later. Other organic layers such as the hole transport layer 4 and the electron transport layer 7 may serve as the light emitting layer without being formed.

The light-emitting layer 5 includes holes injected directly from the anode 2 or through the hole injection layer 3 or the hole transport layer 4 between the electrodes to which an electric field is applied, and directly from the cathode 9 or a cathode buffer. It is a layer which is excited by recombination with electrons injected through the layer 8, the electron transport layer 7, the hole blocking layer 6 and the like and becomes a main light emitting source.
In addition, it is preferable that the light emitting layer 5 is formed using the charge transport material for wet film-forming of this invention, or the charge transport material composition for wet film-forming of this invention.

  The light emitting layer 5 can be formed by any method as long as the effects of the present invention are not significantly impaired. For example, the light emitting layer 5 is formed on the anode 2 by a wet film forming method or a vacuum deposition method. However, when manufacturing the light emitting element 10 with a large area, the wet film forming method is preferable. The wet film forming method and the vacuum deposition method can be performed using the same method as that for the hole injection layer 3.

In general, in an organic electroluminescent device, when compared with the same material, the thinner the film thickness between the electrodes, the larger the effective electric field and the larger the injected current, so the driving voltage decreases. For this reason, the total film thickness between the electrodes is preferably thin. However, if the film thickness is too thin, shorting due to protrusions due to electrodes such as ITO, quenching due to exciton diffusion near adjacent layer interfaces, and the like occur. Therefore, a certain film thickness is required.
Therefore, when it has organic layers, such as the positive hole injection layer 3 and the positive hole transport layer 4, and the positive hole blocking layer 6 and the electron carrying layer 7 mentioned later other than the light emitting layer 5, the light emitting layer 5 and other organic layers are match | combined. The total film thickness is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more, 1000 nm or less, preferably 500 nm or less, and more preferably 300 nm or less.

Further, when the organic layers other than the light emitting layer 5 have high conductivity, the amount of charge injected into the light emitting layer 5 increases. For example, by increasing the thickness of the hole injection layer 3 and decreasing the thickness of the light emitting layer 4, it is possible to reduce the driving voltage while maintaining a certain thickness as the total thickness. In such a case, the thickness of the light emitting layer 5 is usually 10 nm or more, preferably 20 nm or more, and usually 300 nm or less, preferably 200 nm or less.
In addition, as the film thickness of the light emitting layer 5 when the organic electroluminescent element 10 of this Embodiment has only the light emitting layer 5 between both electrodes of the anode 2 and the cathode 9, it is 30 nm or more normally, Preferably it is 50 nm or more, Moreover, it is 500 nm or less normally, Preferably it is 300 nm or less.

<Hole blocking layer 6>
The hole blocking layer 6 can be formed on the light emitting layer 5.
The hole blocking layer 6 can block the holes injected from the anode 2 and moving from reaching the cathode 9, and efficiently transport and inject electrons injected from the cathode 9 to the light emitting layer 5. It is desirable to be formed by a compound that can.
The organic electroluminescent element 10 of the present invention may have a configuration in which the hole blocking layer 6 is omitted.

  A material that can be used for the hole blocking layer 6 preferably has a high electron mobility and a low hole mobility. In addition, the energy gap (difference between HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital)) and the energy of excitons generated in the light emitting layer 5 are large. It is more preferable not to move to the material for forming the hole blocking layer 6, or to form an exciplex with the light emitting layer 5 so as not to lower the efficiency.

Examples of the material for the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum. Mixed ligand complexes such as, metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Of styryl compounds (JP-A-11-242996), triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole 7-41759); phenanthroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297); Position is a compound having at least one pyridine ring substituted (WO 2005/022962 pamphlet); and the like.
One of these may be used alone, or two or more may be used in any combination and ratio.

  The thickness of the hole blocking layer 6 is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. The hole blocking layer 6 can be formed by the same method as each layer from the hole injection layer 3 to the light emitting layer 5, and a wet film-forming method, a vacuum evaporation method, etc. can be used.

<Electron transport layer 7>
The electron transport layer 7 can be formed on the hole blocking layer 6 when the hole blocking layer 6 is provided, and on the light emitting layer 5 when there is no hole blocking layer.
The electron transport layer 7 is preferably formed of a compound that can efficiently transport electrons injected from the cathode 6 between the electrodes to which an electric field is applied in the direction of the light emitting layer 4.
The organic electroluminescent element 10 of the present invention may have a configuration in which the electron transport layer 7 is omitted.

  As an electron transporting compound that can be used for the electron transport layer 7, the electron injection efficiency from the cathode 9 or the cathode buffer layer 8 is high, and the injected electrons having high electron mobility can be efficiently transported. A compound is preferred.

As an electron transporting compound satisfying such conditions, a metal complex such as an aluminum complex of 8-hydroxyquinoline (JP 59-194393 A), a metal complex of 10-hydroxybenzo [h] quinoline, oxadiazole Derivatives, distyrylbiphenyl derivatives, silole derivatives, 3- or 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds (special (Kaihei 6-207169), phenanthroline derivatives (JP-A-5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthracenediimine, n-type hydrogenated amorphous silicon carbide, Examples include n-type zinc sulfide and n-type zinc selenide.
One of these may be used alone, or two or more may be used in any combination and ratio.

  The film thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less. The electron transport layer 7 can be formed by the same method as each layer from the hole injection layer 3 to the hole blocking layer 6, and can be formed by, for example, a wet film forming method or a vacuum evaporation method. Of these, vacuum deposition is preferred.

<Cathode buffer layer 8>
The cathode buffer layer 8 is formed on the electron transport layer 7 when the electron transport layer 7 is provided, and on the hole block layer 6 when the electron transport layer 7 is not provided and the hole block layer 6 is provided. When there is no transport layer 7 and hole blocking layer 6, it can be formed on the light emitting layer 5.
The cathode buffer layer 8 is a layer that efficiently injects electrons injected from the cathode 9 into an adjacent organic layer.
The organic electroluminescent element 10 of the present invention may have a configuration in which the cathode buffer layer 8 is omitted.

As a material that can be used for the cathode buffer layer 8, it is preferable to use a metal having a low work function. This is because electrons are efficiently injected into the organic layer.
Specifically, for example, alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium are used. _{Further, LiF, MgF 2, Li 2} O, may also be used a metal salt such as _Cs 2 CO ₃ (Appl.Phys.Lett, 70 vol, 152 pp., 1997;. Hei 10-74586 JP; IEEE Trans. Electron. Devices, 44, 1245, 1997; SID 04 Digest, 154). One of these may be used alone, or two or more may be used in any combination and ratio.

  The thickness of the cathode buffer layer 8 is usually 0.01 nm or more, preferably 0.1 nm or more, usually 10 nm or less, more preferably 5 nm or less.

The cathode buffer layer 8 can be formed by the same method as each of the layers from the hole injection layer 3 to the electron transport layer 7 described above, and can be formed by, for example, a wet film formation method or a vacuum evaporation method.
In the case of the vacuum deposition method, for example, a deposition source is put in a crucible or a metal boat installed in the vacuum vessel, and the inside of the vacuum vessel is depressurized by a suitable vacuum pump. Thereafter, the crucible or metal boat is heated and evaporated to form the cathode buffer layer 8 on the substrate placed facing the crucible or metal boat.

  The alkali metal can be deposited using, for example, an alkali metal dispenser in which nichrome is filled with an alkali metal chromate and a reducing agent. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced and the alkali metal is evaporated. When the organic electron transport material and the alkali metal are co-evaporated, the organic electron transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is depressurized with a suitable vacuum pump. Thereafter, each crucible and dispenser can be simultaneously heated and evaporated to form a cathode buffer layer 8 on the substrate placed facing the crucible and dispenser. At this time, co-evaporation is uniformly performed in the film thickness direction of the cathode buffer layer 8, but there may be a concentration distribution in the film thickness direction.

<Cathode 9>
The cathode 9 is formed on the cathode buffer layer 8 when the cathode buffer layer 8 is provided, and on the electron transport layer 7 when the cathode buffer layer 8 is not provided and the electron transport layer 7 is provided. When there is no electron transport layer 7 and there is a hole blocking layer 6, when there is no cathode buffer layer 8, electron transport layer 7 and hole blocking layer 6 on the hole blocking layer 6, the light emitting layer 5. Formed on.
The cathode 9 serves to inject electrons into adjacent anode-side layers (cathode buffer layer 8, electron transport layer 7 and the like).

The material used for the anode 2 can be used for forming the cathode 9. In order to perform electron injection efficiently, it is preferable to use a metal having a low work function, and metals such as tin, magnesium, indium, calcium, aluminum, silver, or alloys thereof are used.
Specific examples of the material for forming the low work function alloy electrode include aluminum, magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

  The thickness of the cathode 9 is usually the same as that of the anode 2, but for the purpose of protecting the cathode made of a low work function metal, a metal layer having a higher work function and being stable to the atmosphere is further formed on the cathode 9. Can be stacked. Examples of metals suitable for this purpose include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.

<Other constituent layers>
As mentioned above, although it demonstrated centering on the element of the layer structure shown in FIG. 1, the organic electroluminescent element of this invention is between the anode 2 and the cathode 9, and the light emitting layer 5, unless the performance is impaired, You may have arbitrary layers other than the layer in the said description. Moreover, you may abbreviate | omit arbitrary layers other than the lowest layer organic layer which plays the role of a light emitting layer.

  Further, for the same purpose as the hole blocking layer 6, it is possible to provide an electron blocking layer adjacent to the anode side of the light emitting layer 5. The electron blocking layer increases the probability of recombination with holes in the light emitting layer 5 by preventing electrons moving from the light emitting layer 5 from reaching the hole injection layer 3 or the hole transport layer 4. There are a role of confining the generated excitons in the light emitting layer 5 and a role of efficiently injecting holes injected from the layer on the anode side into the light emitting layer 5.

Furthermore, it is possible to adopt a structure in which a plurality of layers shown in FIG. 1 are stacked (a structure in which a plurality of light emitting units are stacked). In this case, if V ₂ O ₅ or the like is used as the charge generation layer (CGL) instead of the interfacial layer (between the light emitting units) (two layers when the anode is ITO and the cathode is Al), the step This is more preferable from the viewpoint of luminous efficiency and driving voltage.

The organic electroluminescent element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix.
Moreover, in the organic electroluminescent element of the present invention, by using a transparent cathode, it is possible to form a top emission type element that takes out light emission from above (from the surface opposite to the substrate 1).

<Advantages of the organic electroluminescence device of the present invention>
The organic electroluminescent element of the present invention is a highly efficient light emitting element, and an organic electroluminescent element having high durability and a long lifetime can be obtained.

[5. Organic EL display]
Next, the organic EL display of the present invention is a display having the above-described organic electroluminescent element of the present invention in a configuration for display.
The organic EL display of the present invention has at least an organic electroluminescent element laminated on a substrate. By using the above-described organic electroluminescent element of the present invention as the organic electroluminescent element, for example, “organic EL display” It is possible to form an organic EL display (organic EL display) as described in (Ohm Co., issued on August 20, 2004, by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata).

[6. Advantages of the present invention]
According to the present invention, a novel anthracene compound can be provided. The compound has high solubility in a solvent, and is excellent in all of heat resistance, solubility in a solvent, electrochemical stability, and stability in the atmosphere. Therefore, it is suitable for an organic layer of an organic electroluminescence device formed by a wet film formation method, and is suitably used as a charge transport material for wet film formation.
Further, when a wet film-forming organic layer is produced using the compound, an organic electroluminescent element having a high efficiency and a long lifetime can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example, unless it deviates from the summary. In addition, unless otherwise indicated, in the following description, a part refers to a weight part.

[Measurement and evaluation method]
(Method for evaluating solubility in solvents)
Into a glass sample bottle having an internal volume of 2 mL to 10 mL, solute Xg (usually in the range of 3 to 10 mg) and solvent (for example, toluene) Yg are charged, and after closing the lid of the sample bottle, stirring, ultrasonic irradiation or heating Treat and promote dissolution as much as possible. Thereafter, when the precipitate, suspension or layer separation was not confirmed by visual observation or microscopic observation when allowed to stand at room temperature (usually 10 to 30 ° C.) for 10 hours or more, the solubility was (X / (X + Y) When the precipitate was confirmed, the solubility was determined to be less than (X / (X + Y) × 100)%.

[Example 1]
A kind of anthracene compound represented by the formula (I) was synthesized. The synthesis was performed by a multi-step reaction using 1,3,5-tribromobenzene as a starting material to obtain the target compound 4 (corresponding to the anthracene compound represented by the formula (I)).

(Reaction from starting material to target 1)
The following formula represents a synthetic route to the target product 3 corresponding to the first half of the multi-step reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

  In a nitrogen stream, a mixed solution of 1,3,5-tribromobenzene (25.18 g), 2-naphthylboronic acid (10.32 g), toluene (160 mL), and ethanol (80 mL) was prepared. Tetrakis (triphenylphosphine) palladium (0) (2.77 g) was mixed therewith, and then a mixed solution of sodium carbonate (25.44 g) and water (40 mL) was mixed. Stir for hours.

  After stirring, the mixture is filtered to remove insoluble components and concentrated, and then purified by suspension washing in methanol and silica gel column chromatography (n-hexane solvent) to obtain the desired product 1 (12.8 g). It was.

(Reaction from target 1 to target 2)
In a nitrogen stream, toluene (45 mL: represented as “Toluene” in the above synthesis route), tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.155 g: “Pd ₂ (dba) in the above synthesis route) . ₃ represents the CHCl ₃ "), and 1,1'-bis (diphenylphosphino) ferrocene (0.163 g:. in the above synthetic route represented as" dppf ") were mixed, at room temperature and stirred for 20 minutes .

  The target product 1 (5.431 g), diphenylamine (2.538 g), and tert-butoxy sodium (1.730 g: represented by “NaOtBu” in the above synthesis route) were mixed in that order, and an oil at 115 ° C. was mixed. Stir in the bath for 9 hours.

  After stirring, washing with brine, drying over anhydrous magnesium sulfate, filtration and concentration, the resulting solid was purified by silica gel column chromatography (n-hexane / methylene chloride = 9/1 mixed solvent). Product 2 (2.79 g) was obtained.

(Reaction from target 2 to target 3)
In a nitrogen stream, the target compound 2 (2.79 g), bis (pinacolato) diborane (2.05 g), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II), dichloromethane complex (1: 1 ) (0.0354 g: represented as “PdCl ₂ (dppf) CH ₂ Cl ₂ ” in the above synthesis route), potassium acetate (2.07 g: represented as “KOAc” in the above synthesis route), and dehydrated dimethyl Sulfoxide (40 mL: represented as “DMSO” in the above synthetic route) was mixed and stirred at 80 ° C. for 5.3 hours.

  After stirring, the insoluble component was removed by filtration, and the filtrate was concentrated and purified by silica gel column chromatography to obtain the intended product 3 (1.43 g).

(Reaction from target 3 to target 4)
The following formula represents a synthetic route to the target product 4 corresponding to the latter half of the multi-step reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

In a nitrogen stream, the target compound 3 (1.426 g), 9-bromo-10- (2-naphthyl) anthracene (1.154 g), toluene (20 mL: represented as “Toluene” in the above synthesis route), and 1 , 2-dimethoxyethane (20 ml: represented by “DME” in the above synthesis route) was mixed to prepare a mixed solution.
Tetrakis (triphenylphosphine) palladium (0) (0.265 g: represented by “Pd (PPh ₃ ) ₄ ” in the above synthesis route) was mixed therewith, and then tripotassium phosphate (2.433 g). ) And water (40 mL) (represented as “2M K ₃ PO _4aq. ” In the above synthesis route) were mixed, and the mixture was stirred for 11 hours while heating under reflux.

  After stirring, the mixture was washed with brine and 1N aqueous hydrochloric acid solution, dried over anhydrous magnesium sulfate, filtered, and concentrated. Next, it is purified by silica gel column chromatography (n-hexane / methylene chloride = 3/1 mixed solvent), recrystallized using a mixed solvent of methylene chloride / ethyl acetate / ethanol, and purified by sublimation (highest heating). The product was purified at a temperature of 350 ° C. to obtain the desired product 4 (1.08 g).

(Physical properties of target 4)
As a result of performing DEI-MS (Desorption electron ionization mass spectrum) on the obtained target product 4, m / z = 673 (M +) was obtained.

Further, the glass transition point of the target product 4 was 136 ° C., the crystallization temperature and the melting point were not observed, and the weight reduction starting temperature was 559 ° C.
At room temperature, the solubility in toluene was 7% by weight or more.

[Example 2]
A kind of anthracene compound represented by the formula (I) was synthesized. The synthesis was carried out by a multi-step reaction using 4-phenoxyaniline as a starting material to obtain the target compound 7 (corresponding to an anthracene compound represented by the formula (I)).

(Reaction from starting material to target product 5)
The following formula represents a synthetic route to the target product 6 which corresponds to the first half of the multistage reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

  In a nitrogen stream, dehydrated toluene (100 mL), tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.816 g), and 1,1′-bis (diphenylphosphino) ferrocene (0.88 g) were mixed. And stirred at 50 ° C. for 20 minutes.

  4-phenoxyaniline (14.60 g), bromobenzene (12.99 g), and tert-butoxy sodium (9.09 g) were sequentially mixed there and stirred in an oil bath at 115 ° C. for 7.3 hours.

  After stirring, the insoluble component was removed by filtration and then concentrated. Next, the product was purified by silica gel column chromatography (n-hexane / methylene chloride mixed solvent), and further purified by reprecipitation using a methylene chloride / methanol mixed solvent to obtain Target 5 (15.5 g).

(Reaction from target 5 to target 6)
In a nitrogen stream, toluene (25 mL: represented as “Toluene” in the above synthesis route), tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.086 g: “Pd ₂ (dba) in the above synthesis route) ₃ CHCl ₃ ”) and 1,1′-bis (diphenylphosphino) ferrocene (0.09 g: represented as“ dppf ”in the above synthesis route) and mixed at 50 ° C. for 20 minutes. did.

  Thereto, target product 5 (2.17 g), target product 1 (3.01 g), tert-butoxy sodium (0.96 g: represented as “NaOtBu” in the above synthesis route) were sequentially mixed. Stir in an oil bath for 5 hours.

  After stirring, the insoluble component was removed by filtration and then concentrated. Next, it is purified by silica gel column chromatography (n-hexane / methylene chloride = 9/1 mixed solvent), re-precipitated using a mixed solvent of methylene chloride / methanol, and then suspended in a mixed solvent of methanol / water. Purification by washing yielded the desired product 6 (1.965 g).

(Reaction from target 6 to target 7)
The following formula represents a synthetic route to the target product 7 which corresponds to the latter half of the multistage reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

  In a nitrogen stream, the target product 6 (1.965 g), 10- (2-naphthyl) anthracene-9-boronic acid (1.640 g), toluene (28 mL: represented as “Toluene” in the above synthesis route), and Ethanol (14 mL: represented as “EtOH” in the above synthesis route) was mixed to prepare a mixed solution.

There, tetrakis (triphenylphosphine) palladium (0) (0.335 g: represented as “Pd (PPh ₃ ) ₄ ” in the above synthesis route), tripotassium phosphate (3.08 g) and water (7 mL) ) Solution (represented as “2M K ₃ PO _4aq. ” In the above synthesis route) was sequentially mixed and stirred for 3.3 hours while heating under reflux.

  After stirring, the mixture was washed with brine and 1N aqueous hydrochloric acid solution, dried over anhydrous magnesium sulfate, filtered, and concentrated. Next, the product was purified by silica gel column chromatography (n-hexane / methylene chloride = 3/1 mixed solvent), and further purified by sublimation purification (maximum heating temperature 390 ° C.) under high vacuum to obtain the intended product 7 (2.27 g). )

(Physical properties of target 7)
As a result of performing DEI-MS on the obtained target product 7, m / z = 765 (M ⁺ ) was obtained.

Moreover, the glass transition point of the target object 7 was 122 degreeC, the crystallization temperature and melting | fusing point were not observed, and the weight reduction start temperature was 499 degreeC.
At room temperature, the solubility in toluene was 5% by weight or more.

[Example 3]
A kind of anthracene compound represented by the formula (I) was synthesized. The synthesis includes a reaction stage in which 10- (2-naphthyl) anthracene-9-boronic acid is used as a starting material to obtain the target product 8, a reaction stage in which aniline and 4-bromobiphenyl are used as starting materials, and a reaction stage in which the target product 9 is obtained. A multi-stage reaction comprising a reaction stage to obtain the target product 10 (corresponding to the anthracene compound represented by the formula (I)) using 8 and the target product 9 as starting materials was performed.

(Reaction from starting material to target product 8)
The following formula represents a synthetic route for obtaining target product 8 using 10- (2-naphthyl) anthracene-9-boronic acid as a starting material, which is a part of the multistep reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

  In a nitrogen stream, 10- (2-naphthyl) anthracene-9-boronic acid (3.0 g), target 1 (5.3 g), toluene (110 mL: represented as “Toluene” in the above synthesis route), ethanol (55 mL: represented as “EtOH” in the above synthesis route) was mixed to prepare a mixed solution.

A mixed solution of sodium carbonate (20 g) and water (100 mL) (referred to as “2M Na ₂ CO _3aq. ” In the above synthesis route), tetrakis (triphenylphosphine) palladium (0) (0. 51 g: “Pd (PPh ₃ ) ₄ ” in the above synthesis route) was sequentially mixed, and stirred for 2 hours under heating and reflux.

After stirring, the solid content crystallized after cooling was collected by filtration (hereinafter referred to as “crystal A”). After the filtrate was separated, the organic layer was washed with water, and the solid obtained by concentrating the obtained solution was washed with ethanol to obtain crystals (hereinafter referred to as “crystal B”). ).
The crystals A and B were combined and purified by silica gel column chromatography (n-hexane / methylene chloride 85/15), and after concentration and drying, the desired product 9 (3.4 g) was obtained.

(Reaction from starting material to target 9)
The following formula represents a synthetic route for obtaining the target product 9 using aniline and 4-bromobiphenyl as starting materials, which is a part of the multistage reaction. Hereinafter, the implementation content in each reaction stage is demonstrated.

In a nitrogen stream, dehydrated toluene (5 mL: expressed as “Toluene” in the above synthesis route), tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.21 g: “Pd ₂ (dba in the above synthesis route) ) ₃ CHCl ₃ )), and 1,1′-bis (diphenylphosphino) ferrocene (0.45 g: represented as “dppf” in the above synthetic route) and mixed at 60 ° C. for 7 minutes. did. This was designated as liquid A.

  Next, in a nitrogen stream, dehydrated toluene (205 mL: represented as “Toluene” in the above synthesis route), aniline (11 g), 4-bromobiphenyl (25 g), and tert-butoxy sodium (14.4 g: In the synthesis route, it is expressed as “NaOtBu”) to prepare a mixed solution. The above solution A was added thereto and stirred in an oil bath at 100 ° C. for 4 hours.

  After stirring, the insoluble component was removed by filtration, followed by concentration, and methanol (200 mL) was added to precipitate crystals to obtain a suspension. The suspension was heated to reflux, cooled to room temperature, and the resulting crystals were collected by filtration and dried to give the intended product 9 (16.9 g).

(Reaction from object 8 and object 9 to object 10)
The following formula represents a synthetic route for obtaining the target product 10 (corresponding to the anthracene compound represented by the formula (I)) using the target product 8 and target product 9 as starting materials, which is a part of the multi-step reaction. It is a representation. Hereinafter, the implementation content in each reaction stage is demonstrated.

In a nitrogen stream, dehydrated toluene (15 mL: represented as “Toluene” in the above synthesis route) and tris (dibenzylideneacetone) dipalladium (0) complex (0.69 g: “Pd ₂ (dba in the above synthesis route) ₃ ) ”and tri-t-butylphosphine (0.15 g: represented as“ ttBP ”in the above synthesis route) were added and stirred at 60 ° C. for 10 minutes. This was designated as solution B.

  Next, in a nitrogen stream, dehydrated toluene (72 ml: represented as “Toluene” in the above synthesis route), target product 8 (1.77 g), target product 9 (0.81 g), and tert-butoxy sodium (1 .74 g: represented by “NaOtBu” in the above synthesis route) to prepare a mixed solution. The above solution B was added thereto and stirred in an oil bath at 100 ° C. for 4 hours.

  After stirring, the insoluble component is removed by filtration and then concentrated, purified by silica gel column chromatography (n-hexane / methylene chloride = 5/1 mixed solvent), and further purified by sublimation under high vacuum (maximum heating temperature 390 ° C. The target product 10 (1.2 g) was obtained.

(Physical properties of target 7)
As a result of performing DEI-MS on the obtained target product 10, m / z = 749 (M ⁺ ) was obtained.

Further, the glass transition point of the target product 10 was 136 ° C., the crystallization temperature and the melting point were not observed, and the weight reduction starting temperature was 499 ° C.
At room temperature, the solubility in toluene was 6% by weight or more.

[Comparative Example 1]
As a comparative example, the solubility of the following compounds in toluene was measured and found to be less than 1% by weight.

[Comparative Example 2]
As a comparative example, the solubility of the following compounds in toluene was measured and found to be less than 1% by weight.

[Comparative Example 3]
As a comparative example, the solubility of the following compounds in toluene was measured and found to be less than 1% by weight.

[Example 4]
An organic electroluminescent element was produced by the following production method.

(Formation of anode)
An indium tin oxide (ITO) transparent conductive film was formed on a glass substrate with a thickness of 150 nm (sputtered film product, sheet resistance 15Ω). An anode was formed by patterning into a stripe having a width of 2 mm by a normal photolithography technique.
The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, followed by drying with nitrogen blow and ultraviolet ozone cleaning.

(Formation of hole injection layer)
A hole injection layer was formed on the anode. As a material for the hole injection layer, an aromatic tertiary amine polymer compound (PB-1 having a weight average molecular weight of 29,400 and a number average molecular weight of 12,600) having the structural formula shown below is used. Spin-coated with 1).

The spin coating was performed under the conditions shown in [Table 1]. The use ratio of PB-1 and A-1 was PB-1: A-1 = 10: 4 (weight ratio).
After spin coating, drying was performed at 260 ° C. for 180 minutes to form a uniform hole injection layer thin film having a thickness of 30 nm.

(Hole transport layer)
A hole transport layer was formed on the hole injection layer. A light emitting layer was formed by spin coating using the following compound (HT-1) as a material for the hole transport layer.

The spin coating was performed under the conditions shown in [Table 2]. After spin coating, drying was performed at 230 ° C. for 60 minutes to form a uniform hole transport layer thin film having a thickness of 20 nm.

(Light emitting layer)
A light emitting layer was formed on the hole transport layer. A light emitting layer was formed by spin coating using the following compound 1 (the anthracene compound of the present invention, the target product 4) and a fluorescent light emitting dopant (D-1) as materials for the light emitting layer.

The spin coating was performed under the conditions shown in [Table 3]. Moreover, the use ratio of the compound 1 and D-1 was made into the compound 1: D-1 = 10: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light emitting layer thin film having a thickness of 50 nm.

(Hole blocking layer / electron transport layer)
A hole blocking layer was formed on the light emitting layer, and an electron transporting layer was formed on the hole blocking layer.
A hole blocking layer having a thickness of 10 nm was formed by vacuum deposition using HB-1 shown below as a material for the hole blocking layer.
Next, an electron transport layer having a film thickness of 30 nm was formed by vacuum deposition using ET-1 shown below as a material for the electron transport layer.

(Cathode buffer layer / cathode)
A cathode buffer layer was formed on the electron transport layer, and a cathode was formed on the cathode buffer layer.
Using a vacuum evaporation method, a cathode buffer layer having a thickness of 0.5 nm using lithium fluoride (LiF) as a material of the cathode buffer layer, and an anode having a thickness of 80 nm using aluminum as the cathode material are anodes. The stripes were stacked in a 2 mm width shape orthogonal to the ITO stripes.

  As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Blue light emission having an EL peak wavelength of 462 nm was obtained from this device. The characteristics and driving lifetimes of the organic EL elements obtained in [Example 4] to [Example 6] are summarized in [Table 5].

[Example 5]
As a composition for forming the light emitting layer, in addition to the compounds 1 and D-1 of the present invention, the light emitting layer was formed by spin coating using the compound E-1 as a charge transporting auxiliary agent.

Specifically, spin coating was performed under the conditions of [Table 4]. Moreover, the use ratio of the compound 1, D-1, and E-1 was made into the compound 1: E-1: D-1 = 2.5: 7.5: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light emitting layer thin film having a thickness of 50 nm.

An organic electroluminescent element was obtained in the same manner as in Example 4 except that the light emitting layer was formed as described above. Blue light emission having an EL peak wavelength of 467 nm was obtained from this device.

[Example 6]
An organic electroluminescent element was obtained in the same manner as in Example 5 except that the mixing ratio of Compound 1: E-1: D-1 in Example 5 was changed to 5: 5: 1. Blue light emission having an EL peak wavelength of 467 nm was obtained from this device.

[Example 7]
On the thin film of the hole injection layer obtained by the same operation as in Example 4, compound HT-1 was used as the material for the hole transport layer, and spin coating was performed under the conditions of [Table 6] to form a hole transport layer. Formed.
After spin coating, drying was performed at 230 ° C. for 60 minutes to form a uniform hole transport layer thin film having a thickness of 20 nm.

  Next, a light emitting layer was formed on the hole transport layer. A light emitting layer was formed by spin coating using Compound 1 and a fluorescent light emitting dopant D-1 as materials of the light emitting layer.

The spin coating was performed under the conditions of [Table 7]. Moreover, the use ratio of the compound 1 and D-1 was made into the compound 1: D-1 = 10: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light-emitting layer thin film having a thickness of 10 nm.

An organic electroluminescent element was obtained in the same manner as in Example 4 except that the hole transport layer and the light emitting layer were formed as described above. Blue light emission having an EL peak wavelength of 461 nm was obtained from this device.
The characteristics and driving life of the organic electroluminescent elements obtained in [Example 7] and [Comparative Example 4] are summarized in [Table 9].

[Comparative Example 4]
A light emitting layer was formed by spin coating using Compound E-1 and a fluorescent light emitting dopant D-1 as the material of the light emitting layer.

The spin coating was performed under the conditions of [Table 8]. Moreover, the use ratio of compound E-1 and D-1 was made into compound E-1: D-1 = 10: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light-emitting layer thin film having a thickness of 20 nm.

An organic electroluminescent element was obtained in the same manner as in Example 7 except that the light emitting layer was formed as described above.
In this organic electroluminescent element, although the EL peak wavelength was a blue region of 459 nm, the emission half-width of the spectrum was as wide as 77 nm and the emission efficiency was low.

  As described above, by using the compound of the present invention, it was possible to construct an organic electroluminescent device having high luminance and long life.

[Example 8]
A light emitting layer was formed by spin coating using the following compound 2 (anthracene compound of the present invention, the target product 7) and a fluorescent light emitting dopant D-1 as materials for the light emitting layer.

The spin coating was performed under the conditions shown in [Table 10]. The ratio of compound 2 to D-1 was 10: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light-emitting layer thin film having a thickness of 10 nm.

An organic electroluminescent element was obtained in the same manner as in Example 7 except that the light emitting layer was formed as described above.
In addition, the characteristics and drive life of the organic electroluminescent elements obtained in [Example 8] to [Example 10] are summarized in [Table 12].

[Example 9]
A light emitting layer was formed by spin coating using the following compound 3 (anthracene compound of the present invention, the target product 10) and a fluorescent light emitting dopant D-1 as materials for the light emitting layer.

The spin coating was performed under the conditions shown in [Table 11]. The ratio of compound 3 to D-1 used was 10: 1 (weight ratio).
After spin coating, drying was performed at 100 ° C. for 60 minutes to form a uniform light-emitting layer thin film having a thickness of 10 nm.

  An organic electroluminescent element was obtained in the same manner as in Example 7 except that the light emitting layer was formed as described above.

[Example 10]
In the formation of the light emitting layer, an organic electroluminescent element was obtained in the same manner as in Example 7 except that toluene was used instead of cyclohexylbenzene as a solvent and the coating solution concentration was changed to 0.75% by weight.

The characteristics and drive life of the organic electroluminescent elements obtained in [Example 8] to [Example 10] are as shown in [Table 12] below.

  The anthracene compound of the present invention is excellent in solubility in a solvent. Therefore, it can be suitably used for a composition for an organic electroluminescence device excellent in film formability and wet process suitability, and further suitable for use in a high-efficiency, long-life organic electroluminescence device using the composition. it can.

It is sectional drawing which shows typically an example of the structure of the organic electroluminescent element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Hole blocking layer 7 Electron transport layer 8 Cathode buffer layer 9 Cathode 10 Organic electroluminescent device

Claims (10)

An anthracene compound represented by the following formula (I):

(In formula (I), Ar ¹ represents a phenyl group, 1-naphthyl group, or 2-naphthyl group, which may have an aromatic hydrocarbon group having 6 to 26 carbon atoms as a substituent, and Ar ² is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 10-aryl-9-anthryl group, or 1-, which may have an aromatic hydrocarbon group having 6 to 16 carbon atoms as a substituent. represents a pyrenyl group, Ar ^3, Ar ⁴ are each independently, an aromatic hydrocarbon group having 6 to 16 carbon atoms which may have a substituent, a phenyl group, a 1-naphthyl group or a 2- Represents a naphthyl group, G ¹ represents a direct bond .) Amino group in the ^{molecule, -G 1 N (Ar 3)} (Ar 4) , characterized in that only, claim 1 anthracene compound according. A charge transport material for wet film formation, comprising the anthracene compound according to claim 1. The charge transport material for wet film formation according to claim 3, wherein the glass transition point is 120 ° C or higher and the solubility in toluene is 5% by weight or higher. A charge transport material composition for wet film formation, comprising the anthracene compound according to claim 1 or 2. 6. The charge transport material composition for wet film formation according to claim 5, wherein the light-emitting material is contained in an amount of 1 to 50 parts by weight. The charge transport material composition for wet film formation according to claim 5 or 6, wherein the composition contains a solvent. An organic electroluminescent device having an anode, a cathode, and an organic light emitting layer provided between the two electrodes,
An organic electroluminescent device comprising a layer containing the charge transport material for wet film formation according to claim 3. An organic electroluminescent device having an anode, a cathode, and an organic light emitting layer provided between the two electrodes,
It has a layer containing the charge transport material composition for wet film-forming as described in any one of Claims 5-7, The organic electroluminescent element characterized by the above-mentioned. An organic EL display comprising the organic electroluminescent element according to claim 8.

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