WO2012023545A1

WO2012023545A1 - Material for organic electroluminescent element, composition containing the material for organic electroluminescent element, film formed using the composition, and organic electroluminescent element

Info

Publication number: WO2012023545A1
Application number: PCT/JP2011/068530
Authority: WO
Inventors: 早高田; 直之林; 浩二高久
Original assignee: 富士フイルム株式会社
Priority date: 2010-08-17
Filing date: 2011-08-15
Publication date: 2012-02-23
Also published as: JP2012043912A

Abstract

Provided is an organic electroluminescent element in which durability of the element during the driving at a high temperature is improved, the unevenness in in-plane luminance is reduced and the reduction in initial luminance is prevented. A material for an organic electroluminescent element, which is produced by introducing a thermally reactive group into a precursor that has been purified by sublimation. In the material for an organic electroluminescent element, the precursor is a compound having a hydrogen-binding moiety and the introduction of the thermally reactive group is the introduction of a polymerizable group into the hydrogen-binding moiety in the compound having the hydrogen-binding moiety. In the material for an organic electroluminescent element, the hydrogen-binding moiety in the precursor is located in a primary or secondary aryl amine. The material for an organic electroluminescent element is represented by general formula (1). (In general formula (1), R₁'s independently represent a substituent; P₁ represents a vinyl group, an acryl group, a methacryl group, an epoxy group or an oxetane group; l's independently represent an integer of 0-5; l' represents an integer of 0-4; and m3 represents an integer of 0 or more; wherein R₁'s may together form a bond to thereby form a condensed ring which may have a substituent.)

Description

ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, COMPOSITION CONTAINING THE ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, FILM FORMED BY THE COMPOSITION, AND ORGANIC ELECTROLUMINESCENT ELEMENT

The present invention relates to an organic electroluminescent element material, a composition containing the organic electroluminescent element material, a film formed from the composition, and an organic electroluminescent element. The composition of the present invention is useful as a composition for an organic electroluminescence device.

Research has been actively conducted on devices using organic materials, such as organic electroluminescent elements (hereinafter also referred to as OLEDs and organic EL elements) and transistors using organic semiconductors. In particular, the organic electroluminescence device is expected to be developed as a lighting application as a solid light-emitting large-area full-color display device or an inexpensive large-area surface light source. In general, an organic electroluminescent element is composed of an organic layer including a light emitting layer and a pair of counter electrodes sandwiching the organic layer. When a voltage is applied to such an organic electroluminescence device, electrons are injected from the cathode and holes are injected from the anode into the organic layer. The electrons and holes recombine in the light emitting layer, and light is emitted by releasing energy as light when the energy level returns from the conduction band to the valence band.

An organic EL element can be produced by forming a light emitting layer and other organic layers by, for example, a dry method such as vapor deposition or a wet method such as coating. However, wet methods are attracting attention from the viewpoint of productivity. ing.
As a material for producing an organic EL element having an organic layer by a coating method, Patent Document 1 polymerizes by heat or light after coating a material having a polymerizable group from the viewpoint of preventing dissolution at the time of lamination coating. An element using the method is disclosed.
On the other hand, it is known that the performance of an organic EL element material is greatly deteriorated by mixing a small amount of impurities, and it has been studied to sublimate and purify the organic EL element material before film formation.
Patent Document 2 discloses an element that forms an organic layer with a material having a halogen-containing impurity concentration of 1000 ppm or less, and describes that the material is purified by sublimation. Patent Document 3 discloses a device including an active layer, wherein a host material having an HPLC purity of 99.9% or more is used, and the absorbance of impurities is 0.01 or less.

Japanese Unexamined Patent Publication No. 2009-182298 Japanese Unexamined Patent Publication No. 2004-327454 Japan Special Table 2010-50977

However, when a polymerizable monomer is used as a material for an organic EL device, impurities cannot be sufficiently removed because sublimation purification cannot be performed, and an organic electroluminescent device using a polymerizable monomer according to a conventional technique as a material for an organic electroluminescent device. However, the efficiency and durability are insufficient, and further improvement thereof has been demanded.

With respect to these problems of conventional devices, the present inventors have achieved excellent results by using a material for an organic electroluminescent device obtained by introducing a thermally reactive group into a sublimated and purified precursor. I found out that there was an effect. Patent Documents 1 and 2 describe refining an organic electroluminescent element material, but do not disclose sublimation purification of an organic electroluminescent element material precursor. The present inventors effectively removed reaction by-products having a close molecular shape by using a material for an organic electroluminescence device obtained by introducing a thermally reactive group into a sublimated and purified precursor. It was found that the durability of the device during high-temperature driving was improved, and an organic electroluminescent device satisfying the suppression of in-plane luminance unevenness and initial luminance reduction was found, and the invention was completed.
That is, an object of the present invention is to provide an organic electroluminescent device that satisfies the improvement in durability when the device is driven at a high temperature, the suppression of in-plane luminance unevenness, and the suppression of a decrease in initial luminance.
Another object of the present invention is to provide a material and a composition for an organic electroluminescence device useful for the above-mentioned organic electroluminescence device.

In view of the above situation, the present inventors have conducted extensive research and found that by using a material for an organic electroluminescent device obtained by introducing a thermally reactive group into a sublimated and purified precursor, It was found that there was an effect.

That is, the means for solving the problems are as follows.
[1]
A material for an organic electroluminescent element in which a thermally reactive group is introduced into a sublimated and purified precursor.
[2]
The precursor is a compound having a hydrogen bonding site, and the introduction of the thermally reactive group is the introduction of a polymerizable group into the hydrogen bonding site of the compound having the hydrogen bonding site. Materials for organic electroluminescent elements.
[3]
The material for an organic electroluminescent element according to [1] or [2], wherein the hydrogen bonding site of the precursor is in a primary or secondary arylamine.
[4]
The material for an organic electroluminescent element according to any one of [1] to [3], wherein the precursor is a compound represented by the following general formula (A1).

(In general formula (A1), each Q may be independently condensed, and represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent. May combine to form a condensed ring which may have a substituent.
[5]
The material according to any one of [2] to [4], wherein the polymerizable group is a terminal olefin group.
[6]
The organic electroluminescent element material according to any one of [1] to [5], wherein the organic electroluminescent element material is an organic electroluminescent element material represented by the following general formula (1).

(In the general formula (1), each R ₁ independently represents a substituent. P ₁ represents a vinyl group, an acrylic group, a methacryl group, an epoxy group, or an oxetane group. L independently represents an integer of 0 to 5. L ′ represents an integer of 0 to 4. m3 represents an integer of 0 or more, and R ₁ may form a bond to form a condensed ring which may have a substituent. Good.)
[7]
The organic electroluminescent element material according to any one of [1] to [5], wherein the organic electroluminescent element material is an organic electroluminescent element material represented by the following general formula (2).

(In general formula (2), m1 and m2 each independently represents an integer of 0 or more. M1 and m2 do not represent 0 at the same time. N1 and n2 each independently represents an integer of 0 to 10. P ₂ and P ₃ each independently represents a vinyl group, an acryl group, a methacryl group, an epoxy group or an oxetane group, and Q1 to Q4 may each independently be condensed and have a substituent. Represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Q1 and Q3, Q2 and Q4 may be bonded to each other to form a condensed ring which may have a substituent. L is a single bond or a divalent linking group.)
[8]
[1] A composition for an organic electroluminescence device comprising the material for an organic electroluminescence device according to any one of [1] to [7] and a solvent.
[9]
The film | membrane for organic electroluminescent elements formed by apply | coating the composition as described in [8], and heating or light-irradiating this apply | coated composition.
[10]
An organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and at least one organic layer including a light emitting layer between the electrodes,
An organic electroluminescent element comprising the organic electroluminescent element material according to any one of [1] to [7] in at least one of the organic layers.
[11]
The organic layer includes a hole transport layer, a hole injection layer, or an electron block layer, and any one of the hole transport layer, the hole injection layer, and the electron block layer is any one of [1] to [7] [10] The organic electroluminescent element as described in [10] above, comprising the material for an organic electroluminescent element as described in
[12]
The organic electroluminescent device according to [10] or [11], wherein the organic layer includes a light emitting layer, and the light emitting layer includes a phosphorescent metal complex.
[13]
The organic electroluminescence device according to any one of [10] to [12], including the film according to [9].
[14]
[14] The organic electroluminescent element as described in any one of [10] to [13], wherein at least one organic layer between the pair of electrodes is formed by a coating method.

ADVANTAGE OF THE INVENTION According to this invention, the durability at the time of high temperature drive of an element improves, The organic electroluminescent element material which can provide the organic electroluminescent element which satisfies the suppression of in-plane brightness nonuniformity and initial stage brightness fall is provided. Can do.
Moreover, according to this invention, the composition, film | membrane, and organic electroluminescent element containing the said organic electroluminescent element material and this organic electroluminescent element material can be provided.

It is the schematic which shows an example of the layer structure of the organic electroluminescent element which concerns on this invention. It is the schematic which shows an example of the light-emitting device which concerns on this invention. It is the schematic which shows an example of the illuminating device which concerns on this invention.

Hereinafter, the present invention will be described in detail. In the present specification, “to” indicates a range including the numerical values described before and after the values as a minimum value and a maximum value, respectively.
The hydrogen atom in the description of the following general formula (1) includes isotopes (such as deuterium atoms), and further, the atoms constituting the substituents also include the isotopes.
In the present invention, when referred to as “substituent”, the substituent may be substituted. For example, the term “alkyl group” in the present invention includes an alkyl group substituted with a fluorine atom (for example, trifluoromethyl group) and an alkyl group substituted with an aryl group (for example, triphenylmethyl group). When the term “alkyl group having 1 to 6 carbon atoms” is used, it means that all groups including substituted ones have 1 to 6 carbon atoms.

In the present invention, the substituent Z is defined as follows.

<Substituent Z>
An alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n- Butyl, neopentyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, such as vinyl) Aryl group (having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group, anthracenyl group, tetracenyl group, pyrenyl group, perylenyl group, triphenylenyl group, chrysenyl group) Heteroaryl group (preferably having 4 to 30 carbon atoms, more preferably carbon 4 to 20, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiophene, furan, oxazole, thiazole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole and the like, alkoxy group (preferably having 1 carbon atom) To 8, more preferably 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propyloxy, iso-propyloxy, etc.), phenoxy, halogen (preferably fluorine), A silyl group (preferably having 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group), amino group (preferably having 2 to 60 carbon atoms, More preferably, it has 2 to 40 carbon atoms, and dimethyl Amino group, a diethylamino group, and a diphenylamino group), a cyano group or a group formed by combining these groups, a plurality of substituents Z may be bonded to form an aryl ring. Examples of the aryl ring formed by bonding a plurality of substituents Z to each other include a phenyl ring and a pyridine ring, and a phenyl ring is preferable.

[Materials for organic electroluminescent elements]
The organic electroluminescent element material of the present invention is an organic electroluminescent element material in which a heat-reactive group is introduced into a sublimated and purified precursor.
The material for an organic electroluminescent device according to the present invention is a charge transporting material (hole transporting material, electron transporting material, host material) or a light emitting material, preferably hole transporting that can be used for forming a hole transporting layer. It is a material or a luminescent material, and more preferably a hole transport material. Hereinafter, this organic electroluminescent element material will be described.
The reason why the organic electroluminescent element material of the present invention is useful for producing an organic electroluminescent element in which the durability of the element during high temperature driving is improved and in-plane luminance unevenness and initial luminance decrease is suppressed is not clear. Is estimated as follows.
It is already known that the device life can be improved by improving the purity of the organic EL material. In order to improve the purity, it is generally known that the final product is used after purification by sublimation. However, many materials having a heat or photopolymerizable group, which are particularly useful when forming a laminated film with a coating type EL, easily react with heat during sublimation purification and cannot be subjected to sublimation purification. In addition, in the conventional method for sublimation purification of the final product, among the impurities generated as a by-product during the reaction, inorganic salts and low molecular reactants can be efficiently removed, while impurities having a molecular shape close to that of the final product are removed. It is difficult to separate. These impurities often have an energy level in the device close to that of the product, and it is considered that the impurity becomes an active radical charge when the device is driven and causes deterioration in durability.
In the present application, by removing specific impurities contained in the precursor by sublimation, the durability at the time of driving the element is improved, and even when driven at a high temperature, unwanted decomposition and sub-substances based on the impurities in the film are used. It is thought to suppress the reaction. This also revealed that the luminance maintenance rate immediately after energization was excellent. Suppressing the initial deterioration in the element lifetime of the organic EL element is a useful technique particularly for a display that needs to maintain luminance between elements. It is assumed that the drive deterioration at the initial stage of energization is caused by decomposition or reaction of chemically active impurities contained in a small amount in the film due to charges, and these are suppressed.

〔precursor〕
The precursor is a reactive organic compound used when synthesizing a hole transport material, an electron transport material, a host material, and a light emitting material used as a material for an organic electroluminescent device, and is not particularly limited, but a hydrogen bonding site It is preferable that it is a compound which has this. This is because a compound having a hydrogen bonding site has a higher melting point and sublimation point than a compound having no hydrogen bonding site having the same molecular weight and can efficiently remove specific impurities. Moreover, it is preferable that the precursor is a compound having a hydrogen bonding site, and the introduction of the thermally reactive group is the introduction of a polymerizable group into the hydrogen bonding site of the compound. This is because the hydrogen bonding site is reactive as described above and is not desirably included in the element. Here, the hydrogen bonding site refers to a site where hydrogen is directly bonded to nitrogen, oxygen, and sulfur. Does not include hydrogen bonds in a broad sense (such as interactions between carbon-hydrogen bonding sites and electronegative elements). Examples of the hydrogen bond include OH, SH, and NH.

In addition, the precursor preferably has a high boiling point and a sublimation point due to having a hydrogen bonding site, but a material having a boiling point and a sublimation point satisfying the following formula is particularly preferable.
Ts> M / 16.5 + 235 (° C.)
(Ts represents a sublimation point or boiling point (using a 10% weight reduction point) at 0.1 Pa, and M represents a molecular weight.)
The hydrogen bonding site of the precursor is preferably in a primary or secondary arylamine. Materials such as primary and secondary amines have high melting points and sublimation points, and can remove specific impurities more efficiently. Further, it is already known that tertiary arylamine materials synthesized from these precursors are useful as hole transport materials.

It is preferable that the precursor is a compound represented by the following general formula (A1).

(In general formula (A1), each Q may be independently condensed, and represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent. May combine to form a condensed ring which may have a substituent.

The 6-membered aromatic hydrocarbon ring represented by Q may be condensed or may have a substituent.
Examples of the substituent in the case of having a substituent include the above-described substituent Z, and the substituent Z is preferably an alkyl group, an aryl group, a heteroaryl group, a silyl group, or a cyano group, a methyl group, an ethyl group, Isopropyl group, n-propyl group, tert-butyl group, isobutyl group, n-butyl group, neopentyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, Anthracenyl group, pyrenyl group, perylenyl group, triphenylenyl group, pyridyl group, thiophenyl group, furanyl group, imidazolyl group, pyrazolyl group, trimethylsilyl group, triphenylsilyl group, and cyano group are more preferable.
Examples of the 6-membered aromatic hydrocarbon ring represented by Q include a benzene ring. Examples of the ring formed when the 6-membered aromatic hydrocarbon ring represented by Q is condensed include, for example, naphthalene ring, anthracene ring, fluorene ring, phenanthrene ring, acenaphthene ring, carbazole ring, benzoxazole ring, benzothiazole A ring, a benzimidazole ring, a benzopyrazole ring, and the like, and a naphthalene ring, a carbazole ring, and a benzimidazole ring are preferable.
The aromatic heterocycle represented by Q may be condensed or may have a substituent. Examples of the substituent in the case of having a substituent include the above-described substituent Z, and the preferred range is the same as the substituent in the case where Q is an aromatic hydrocarbon ring. Examples of the 6-membered aromatic heterocycle represented by Q include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, and a pyridine ring is preferable. When the aromatic heterocycle represented by Q is condensed, it is preferable that one or more carbons on any six-membered ring be replaced with nitrogen in the structure described in the case where the aromatic hydrocarbon ring is condensed. You can list what you can get.
Q is preferably a condensed ring, a 6-membered aromatic hydrocarbon ring or an aromatic hetero ring which may have a substituent, and more preferably a condensed ring, A 6-membered aromatic hydrocarbon ring which may have a substituent.
Further, Qs may be bonded to each other to form a condensed ring which may have a substituent. As the condensed ring to be formed, an optionally substituted carbazole ring is preferable. The substituent when the condensed ring to be formed has a substituent is the same as the substituent when Q in the general formula (A1) has a substituent, and the preferable ones are also the same. )

Specific examples of the precursor are shown below, but the present invention is not limited thereto.

The compounds exemplified as the precursor can be synthesized by the method described in JP2009-182298A, for example.
As other precursors, a formyl group is introduced into a benzene ring, naphthalene ring or pyridine ring of an iridium complex having a phenyl pyridine, biphenyl pyridine or naphthyl pyridine which may have a substituent as a ligand. The compounds are preferred.

[Sublimation purification of precursors]
As a method for sublimation purification of the precursor, a conventionally known method can be used.For example, a method of putting a material in a boat and heating it under reduced pressure conditions to sublimate or evaporate the material and collect it in a low temperature part. Can be mentioned. At this time, it is preferable to employ a method in which the sublimation boat is maintained at a temperature lower than the temperature at which the target compound sublimes, and the sublimation impurities are removed in advance. Further, it is preferable to apply a temperature gradient to the portion where the sublimate is collected so that the sublimate is dispersed in the impurities and the target product. The pressure at this time is 0.001 Pa to 0.5 Pa as a general apparatus mode, but it is preferably 0.1 Pa or less from the viewpoint of suppressing thermal decomposition of the compound.

(Thermal reactive group)
A thermoreactive group refers to a functional group that undergoes decomposition or reaction upon heating. Heating here means heating the material to 100-400 ° C. In addition to the polymerizable group described below, a condensable group such as silanol, a carboxyl group, an ester group, and the like can be given. The introduction of the thermally reactive group is preferably addition of a compound having a polymerizable group to the hydrogen bonding site of the compound having a hydrogen bonding site.
The polymerizable group refers to a functional group that can react with each other by applying heat or light energy to form a polymer. Specifically, it has an oxygen-containing cyclic group such as a terminal olefin group having an olefin group at the end of a substituent, such as a vinyl group, an allyl group, an acrylic group, and a methacryl group, an epoxy group, an oxetane group, and an oxolane group. Groups, epoxy groups, oxetane groups, alkyl groups having an oxygen-containing cyclic group such as an oxolane group, groups having a small ring group such as cyclobutene, groups having a diazo group, and groups having a thiol. . Of these, a terminal olefin group is preferable, and a vinyl group is more preferable.

The compound having a polymerizable group is preferably a compound represented by the following general formula (B1).

(In the general formula (B1), Q represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may be condensed and may have a substituent. K represents an integer. ₁ and R ₂ each independently represents a hydrogen atom or a substituent, P ₄ represents a vinyl group, an acrylic group, a methacryl group, an epoxy group or an oxetane group, and X represents a substituent having a leaving ability.

Q represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may be condensed, and may have a substituent. Q has the same meaning as Q in formula (A1), and preferred ones are also the same.
k represents an integer, preferably 0 to 6, and more preferably 0 from the viewpoint of improving the reactivity during polymerization.
R ₁ and R ₂ each independently represent a hydrogen atom or a substituent, and examples of the substituent include the above-described substituent Z. Examples of the substituent Z include an alkyl group, an aryl group, a heteroaryl group, a silyl group, and a cyano group. Group is preferred, methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, neopentyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl group, naphthyl group, anthracenyl group, Pyrenyl group, perylenyl group, triphenylenyl group, pyridine, thiophene, furan, imidazole, pyrazole, trimethylsilyl group, triphenylsilyl group, and cyano group are more preferable. CR ₁ may also represent a carbonyl group, in which case R ₂ is absent.
P ₄ represents a vinyl group, an acryl group, a methacryl group, an epoxy group or an oxetane group, preferably a vinyl group.
X represents a substituent having a leaving ability, and is specifically preferably a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group.
Although the specific example of the compound which has a polymeric group is shown below, in this invention, it is not limited to these.
In the following specific examples, Tf represents a trifluoromethanesulfonyl group.

[Introduction of reactive groups]
Introduction of the thermally reactive group can be roughly divided by two methods. One is a functional group conversion reaction of a functional group of the precursor to a thermoreactive group, and the other is an addition and substitution reaction of a compound having a thermoreactive group.
In this reaction, a formyl group is introduced into a benzene ring, naphthalene ring or pyridine ring of an iridium complex having a precursor of phenylpyridine, biphenylpyridine or naphthylpyridine which may have a substituent. In particular, it is particularly effective when converting a formyl group into a vinyl group which is a thermally reactive group.

Examples of the functional group conversion reaction of the functional group of the precursor to a thermally reactive group include a reaction of converting an aldehyde described in paragraph 175 and the subsequent paragraphs of US Publication No. 2008-0220265 into a vinyl group.

Examples of the addition and substitution reaction of the compound having a thermally reactive group include a coupling reaction using a metal catalyst. For example, the aforementioned general formula (A1) and general formula (B1) are reacted in the presence of a metal catalyst and a base. Examples of the metal catalyst include palladium, copper, nickel and platinum-containing catalyst reagents, and palladium catalyst reagents are particularly preferable. A method using a divalent palladium catalyst such as palladium acetate or dichloropalladium as a palladium catalyst and triphenylphosphine, tri (t-butyl) phosphine, diphenylphosphinoferrocene, dicyclohexyl-biphenylphosphine or an analog thereof as a ligand And a method using a zero-valent palladium catalyst such as bis (dibenzylideneacetone) palladium or tetrakis (triphenylphosphine) palladium alone, and a method using a combination of the above-mentioned zero-valent palladium catalyst and a ligand. Any of these can be suitably used. As the base, any of inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide and potassium phosphate, and organic bases such as potassium t-butoxide, triethylamine, pyridine and sodium ethoxide can be preferably used. The reaction can be carried out in the presence of a solvent, and examples of the solvent include ether solvents such as tetrahydrofuran, diisopropyl ether and dioxane, and aromatic hydrocarbon solvents such as toluene, xylene and mesitylene. From the viewpoint of suppressing side reactions, toluene or xylene is preferable. When these solvents are used, the compound of the general formula (A1) is preferably reacted at a concentration of 1 mol / L to 0.01 mol / L, more preferably 0.5 to 0.1 mol / L. The temperature in the reaction is preferably from room temperature to 250 ° C, more preferably from 60 ° C to 150 ° C.
The amount of the compound represented by the general formula (B1) to be used with respect to the compound represented by the general formula (A1) is preferably 100 mol% to 500 mol%, and the compound represented by the general formula (B1) is From the viewpoint of suppressing an excessive reaction, it is more preferably 100 mol% to 120 mol%.

Examples of the addition and substitution reaction of a compound having a thermally reactive group include a nucleophilic substitution reaction using a base. For example, the above general formula (A1) and general formula (B1) can be reacted in the presence of a base. Examples of the base include alkyl metal reagents such as alkylmagnesium and alkyllithium, hydride reagents such as sodium hydride, and strong inorganic bases such as potassium hydroxide. The reaction can be performed in the presence of a solvent. As a solvent, amide solvents such as N, N-dimethylformamide and N-methylpiperidinone, ether solvents such as tetrahydrofuran, diisopropyl ether and dioxane, toluene, xylene, mesitylene and the like The aromatic hydrocarbon solvent is preferably an amide solvent from the viewpoint of improving the reactivity. When these solvents are used, the compound of the general formula (A1) is preferably reacted at a concentration of 1 mol / L to 0.01 mol / L, more preferably 0.5 to 0.1 mol / L. The temperature in the reaction is preferably room temperature to 250 ° C, more preferably 100 ° C to 180 ° C.
The amount of the compound represented by the general formula (B1) to be used with respect to the compound represented by the general formula (A1) is preferably 100 mol% to 500 mol%, and the compound represented by the general formula (B1) From the viewpoint of sufficient reaction, it is more preferably from 120 mol% to 250 mol%.

In one embodiment of the present invention, the organic electroluminescent element material is preferably an organic electroluminescent element material represented by the following general formula (1).
The compound represented by the general formula (1) has a triarylamine moiety, and has high hole injecting property and transporting property.

(In the general formula (1), each R ₁ independently represents a substituent. P ₁ represents a vinyl group, an acrylic group, a methacryl group, an epoxy group, or an oxetane group. L independently represents an integer of 0 to 5. L ′ represents an integer of 0 to 4. m3 represents an integer of 0 or more, and R ₁ may form a bond to form a condensed ring which may have a substituent. Good.)

The substituent represented by R ₁ is the same as the substituent that the ring Q of the general formula (A1) may have, and the preferred range is also the same.
In addition, R ₁ may form a bond to form a condensed ring which may have a substituent. As the condensed ring to be formed, an optionally substituted carbazole ring is preferable. The substituent when the condensed ring to be formed has a substituent is the same as the substituent when Q in the general formula (A1) has a substituent, and the preferable ones are also the same.
P ₁ represents a vinyl group, an acryl group, a methacryl group, an epoxy group or an oxetane group, preferably a vinyl group.
l independently represents an integer of 0 to 5, and l ′ represents an integer of 0 to 4. l and l ′ are preferably 0 or 1.
m3 represents an integer of 0 or more, and 0 or 1 is preferable.

In another embodiment of the present invention, the organic electroluminescent element material is preferably an organic electroluminescent element material represented by the following general formula (2).
Since the compound represented by the general formula (2) has a plurality of arylamine units and a plurality of polymerizable sites, it is particularly excellent in uniform film forming properties and hole transportability.

(In general formula (2), m1 and m2 each independently represents an integer of 0 or more. M1 and m2 do not represent 0 at the same time. N1 and n2 each independently represents an integer of 0 to 10. Q1 to Q4 each independently represent a condensed ring and each represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent, and P ₂ and P ₃ each independently Represents a vinyl group, an acrylic group, a methacryl group, an epoxy group or an oxetane group, and Q1 and Q3, Q2 and Q4 may be bonded to each other to form a condensed ring which may have a substituent. L is a single bond or a divalent linking group.)

Q1 to Q4 each independently represent a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may be condensed, and may have a substituent. Q1 to Q4 have the same meanings as Q in formula (A1), and preferred ones are also the same.
Q1 and Q3, and Q2 and Q4 may be bonded to each other to form a condensed ring which may have a substituent. As the condensed ring to be formed, an optionally substituted carbazole ring is preferable. The substituent when the condensed ring to be formed has a substituent is the same as the substituent when Q in the general formula (A1) has a substituent, and the preferable ones are also the same.
P ₂ and P ₃ are each independently a vinyl group, acryl group, methacryl group, an epoxy group or an oxetane group, it is preferable that at least one of P ₂ and P ₃ is a vinyl group, both of P ₂ and P ₃ Is more preferably a vinyl group.
n1 and n2 each independently represents an integer of 0 to 10 and have the same meaning as m3 in formula (1), and the preferred range is also the same.
m1 and m2 each independently represents an integer of 0 or more, preferably 1 to 4, and more preferably 1.

L represents a single bond or a divalent linking group. The divalent linking group represented by L is preferably a divalent hydrocarbon group that may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom. An alkylene group, a cycloalkylene group, a silylene group, an arylene group, and a divalent group obtained by combining these are more preferable, and a single bond is more preferable.
The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a dimethylmethylene group, a diethylmethylene group, and a diphenylmethylene group. And preferably a dimethylmethylene group, a diethylmethylene group, or a diphenylmethylene group.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 10 carbon atoms, and specific examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and the like. , Cyclopentylene group, cyclohexylene group, and cycloheptylene group.

The silylene group is preferably a silylene group substituted by an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene group, A diphenylsilylene group is preferred.
Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, a fluorenylene group, a phenanthrylene group, a pyrenylene group, a triphenylenylene group, and the like. Includes a phenylene group, a naphthylene group, a biphenylene group, a fluorenylene group, a phenanthrylene group, and the like, and most preferably a phenylene group and a naphthylene group.

L may include a charge transport site. Here, the charge transport site means a structural site having a hole mobility of 10 ⁻⁶ to 100 cm / Vs or an electron mobility of 10 ⁻⁶ to 100 cm / Vs. Examples of the charge transport site include a hole transport site, an electron transport site, and a bipolar transport site.
As a hole transporting site, a monovalent group derived from a known compound such as a triarylamine derivative such as NPD or TPD, a carbazole derivative, a metal phthalocyanine derivative, a pyrrole derivative, or a thiophene derivative, or a divalent linkage. Groups.
Examples of the electron transport site include monovalent groups or divalent linking groups derived from known compounds such as oxadiazole derivatives, triazine derivatives, phenanthrene derivatives, triphenylene derivatives, silole derivatives, Al complexes, Zn complexes, and the like. .
Examples of the bipolar transporting site include a monovalent group or a divalent linking group derived from a known compound such as a benzoxazole derivative, anthracene derivative, perylene derivative, or tetracene derivative.
Specific examples of L are shown below, but the present invention is not limited thereto.

The material for an organic electroluminescent element of the present invention has a reactive group and may be used after being polymerized by polymerization, or may be used as a monomer. Alternatively, the polymer film may be formed and polymerized in a monomer state to form a polymer film. As the polymerization method at this time, any conventionally known method can be suitably used, and several polymerization means may be used in combination. For example, after the material of the present invention is polymerized by heat, the polymerization may be further accelerated by light irradiation. It is preferable to perform polymerization with heat from the viewpoint of simplifying the production process.
When polymerized by polymerization, the polymer can be used alone or as a copolymer with other monomers.
The content of the structure (repeating unit) corresponding to the organic electroluminescent device material of the present invention in the polymer is preferably 5 to 99 mol%, more preferably 50 to 95 mol%, based on all repeating units in the copolymer. More preferably, it is 75 to 90 mol%.

The weight average molecular weight of the polymer containing the organic electroluminescent element material of the present invention is preferably in the range of 1000 to 100,000, more preferably 1200 to 50000, and still more preferably 2000 to 2000 as a polystyrene conversion value by GPC method. 30000. By setting the weight average molecular weight to 1,000 to 100,000, both solubility in a solvent and improvement in film formability can be achieved.

The dispersity (molecular weight distribution) is usually 1.1 to 3.0, preferably 1.2 to 2.0. The smaller the molecular weight distribution, the better the mobility of charge (hole / electron) transport.

Specific examples of the organic electroluminescent element material of the present invention are shown below, but the present invention is not limited thereto.

[Composition comprising organic electroluminescent element material and solvent]
The content of the organic electroluminescent element material in the composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass based on the total solid content of the composition. It is.

〔solvent〕
Examples of the solvent that can be used when preparing the composition by dissolving the material for organic electroluminescent elements include, for example, aromatic hydrocarbon solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents. And known organic solvents such as amide solvents.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, cumeneethylbenzene, methylpropylbenzene, methylisopropylbenzene, and the like, and toluene, xylene, cumene, and trimethylbenzene are more preferable. preferable. The relative dielectric constant of the aromatic hydrocarbon solvent is usually 3 or less.

Examples of the alcohol solvent include methanol, ethanol, butanol, benzyl alcohol, cyclohexanol, and the like, butanol, benzyl alcohol, and cyclohexanol are more preferable. The relative dielectric constant of the alcohol solvent is usually 10 to 40.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methyl Examples include isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like, and methyl isobutyl ketone and propylene carbonate are preferred. The relative permittivity of the ketone solvent is usually 10 to 90.
Examples of the aliphatic hydrocarbon solvent include pentane, hexane, octane, decane and the like, and octane and decane are preferable. The relative dielectric constant of the aliphatic hydrocarbon solvent is usually 1.5 to 2.0.
Examples of amide solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone and the like. N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferred. The relative dielectric constant of the amide solvent is usually 30 to 40.
In the present invention, the above solvents may be used alone or in combination of two or more.

In the present invention, an aromatic hydrocarbon solvent (hereinafter also referred to as “first solvent”) and a second solvent having a relative dielectric constant higher than that of the first solvent may be mixed and used. By using such a mixed solvent, hydrolysis of alkoxysilane is promoted, and condensation reactivity is improved.
As the second solvent, an alcohol solvent, an amide solvent, or a ketone solvent is preferably used, and an alcohol solvent is more preferably used.
The mixing ratio (mass) of the first solvent and the second solvent is generally 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 70/30. is there. A mixed solvent containing 60% by mass or more of the first solvent is particularly preferable from the viewpoint of preventing polymer precipitation.

(Formation of film)
The present invention also relates to a film formed by applying the composition of the present invention and heating or irradiating the applied composition. A film formed from the composition of the present invention is useful as a charge transport layer. The charge transport layer can be formed by applying the composition of the present invention and heating the applied composition.
The charge transport layer is preferably used in a thickness of 5 to 50 nm, more preferably in a thickness of 5 to 40 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The charge transport layer is preferably a hole transport layer, an electron transport layer, an exciton block layer, a hole block layer, or an electron block layer, more preferably a hole transport layer or an exciton block layer, More preferred is a hole transport layer.
The total solid content concentration in the composition of the present invention is generally 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 10% by mass.
The viscosity of the composition of the present invention is generally 1 to 30 mPa · s, more preferably 1.5 to 20 mPa · s, and still more preferably 1.5 to 15 mPa · s.

The composition of the present invention is used by dissolving the above components in a predetermined organic solvent, filtering the solution, and then applying the solution on a predetermined support or layer as follows. The pore size of the filter used for filter filtration is 2.0 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less made of polytetrafluoroethylene, polyethylene, or nylon.

The coating method of the composition of the present invention is not particularly limited, and can be formed by any conventionally known coating method. Examples thereof include an ink jet method, a spray coating method, a spin coating method, a bar coating method, a transfer method, and a printing method.

After application of the composition of the present invention, by heating or light irradiation, the polymerization reaction proceeds and a polymer can be formed.
The heating temperature and time after coating are not particularly limited as long as the polymerization reaction proceeds, but the heating temperature is generally 100 ° C to 200 ° C, and more preferably 120 ° C to 160 ° C. The heating time is generally 1 minute to 120 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 30 minutes.

Further, a polymerization reaction by UV irradiation, a polymerization reaction by a platinum catalyst, a polymerization reaction by an iron catalyst such as iron chloride, and the like can be mentioned. These polymerization methods may be used in combination with a polymerization method by heating.

[Organic electroluminescence device]
The organic electroluminescent element in the present invention will be described in detail.
The organic electroluminescent element in the present invention is an organic electroluminescent element having a pair of electrodes consisting of an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on a substrate,
It is an organic electroluminescent element which contains the organic electroluminescent element material of this invention in at least one layer of the said organic layer. The organic layer includes a hole transport layer, a hole injection layer, or an electron block layer, and the organic electroluminescent element material of the present invention may be included in any of the hole transport layer, hole injection layer, or electron block layer. preferable.
The present invention also relates to an organic electroluminescent device having a film formed from the composition of the present invention.
Furthermore, it is preferable that at least one of the organic layers between the pair of electrodes is formed by a coating method.
More specifically, the organic electroluminescent element in the present invention is an organic electroluminescent element having a pair of electrodes including an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on a substrate. The at least one organic layer has a charge transport layer formed from the composition of the present invention.

In the organic electroluminescent element of the present invention, the light emitting layer is an organic layer, and further includes at least one organic layer between the light emitting layer and the anode, but may further have an organic layer in addition to these.
In view of the properties of the light-emitting element, at least one of the anode and the cathode is preferably transparent or translucent.
FIG. 1 shows an example of the configuration of an organic electroluminescent device according to the present invention.
In the organic electroluminescent element 10 according to the present invention shown in FIG. 1, a light emitting layer 6 is sandwiched between an anode 3 and a cathode 9 on a support substrate 2. Specifically, a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7, and an electron transport layer 8 are laminated in this order between the anode 3 and the cathode 9.

<Structure of organic layer>
There is no restriction | limiting in particular as a layer structure of the said organic layer, Although it can select suitably according to the use and objective of an organic electroluminescent element, It is preferable to form on the said transparent electrode or the said back electrode. . In this case, the organic layer is formed on the front surface or one surface of the transparent electrode or the back electrode.
There is no restriction | limiting in particular about the shape of a organic layer, a magnitude | size, thickness, etc., According to the objective, it can select suitably.

Specific examples of the layer configuration include the following, but the present invention is not limited to these configurations.
Anode / hole transport layer / light-emitting layer / electron transport layer / cathode Anode / hole transport layer / light-emitting layer / block layer / electron transport layer / cathode Anode / hole transport layer / light-emitting layer / block layer / electron Transport layer / electron injection layer / cathode ・ Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode ・ Anode / hole injection layer / hole transport layer / light emitting layer / block Layer / electron transport layer / cathode • anode / hole injection layer / hole transport layer / light emitting layer / blocking layer / electron transport layer / electron injection layer / cathode • anode / hole injection layer / hole transport layer / exciton Block layer / light emitting layer / electron transport layer / electron injection layer / cathode The element configuration of the organic electroluminescence device, the substrate, the cathode and the anode are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736. The matters described can be applied to the present invention.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

Regarding the substrate, anode, and cathode, the matters described in paragraph numbers [0070] to [0089] of JP-A-2008-270736 can be applied to the present invention.

<Organic layer>
The organic layer in the present invention will be described.

[Formation of organic layer]
In the organic electroluminescent device of the present invention, each organic layer is formed by a solution coating process such as a dry film forming method such as an evaporation method or a sputtering method, a transfer method, a printing method, a spin coating method, a bar coating method, an ink jet method, or a spray method. Any of these can be suitably formed.

In addition to the charge transport layer formed from the composition of the present invention, any one of the organic layers is particularly preferably formed by a wet method. The other layers can be formed by appropriately selecting a dry method or a wet method. When the wet method is used, the organic layer can be easily increased in area, and a light-emitting element having high luminance and excellent light emission efficiency can be obtained efficiently at low cost, which is preferable. Vapor deposition, sputtering, etc. can be used as dry methods, and dipping, spin coating, dip coating, casting, die coating, roll coating, bar coating, gravure coating, and spray coating as wet methods. An ink jet method or the like can be used. These film forming methods can be appropriately selected according to the material of the organic layer. When the film is formed by a wet method, it may be dried after the film is formed. Drying is performed by selecting conditions such as temperature and pressure so that the coating layer is not damaged.

The coating solution used in the wet film-forming method (coating process) usually comprises an organic layer material and a solvent for dissolving or dispersing it. A solvent is not specifically limited, What is necessary is just to select according to the material used for an organic layer. Specific examples of the solvent include halogen solvents (chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, cyclohexanone, etc.), Aromatic solvents (benzene, toluene, xylene, etc.), ester solvents (ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, diethyl carbonate, etc.), ether solvents (Tetrahydrofuran, dioxane, etc.), amide solvents (dimethylformamide, dimethylacetamide, etc.), dimethyl sulfoxide, alcohol solvents (methanol, propanol, butanol, etc.), water and the like.
The solid content with respect to the solvent in the coating solution is not particularly limited, and the viscosity of the coating solution can be arbitrarily selected according to the film forming method.

[Light emitting layer]
In the organic electroluminescent device of the present invention, the light emitting layer contains a light emitting material, and the light emitting material preferably contains a phosphorescent compound. The phosphorescent compound is not particularly limited as long as it is a compound that can emit light from triplet excitons. As the phosphorescent compound, an orthometalated complex or a porphyrin complex is preferably used, and an orthometalated complex is more preferably used. Of the porphyrin complexes, a porphyrin platinum complex is preferred. The phosphorescent compounds may be used alone or in combination of two or more.

The ortho-metalated complex referred to in the present invention refers to Akio Yamamoto's “Organic Metal Chemistry Fundamentals and Applications”, pages 150 and 232, Hankabo (1982), H.C. Yersin's “Photochemistry and Photophysics of Coordination Compounds”, pages 71 to 77 and pages 135 to 146, Springer-Verlag (1987), etc. The ligand forming the orthometalated complex is not particularly limited, but a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2- (2-thienyl) pyridine derivative, a 2- (1-naphthyl) pyridine derivative or A 2-phenylquinoline derivative is preferred. These derivatives may have a substituent. Moreover, you may have another ligand other than these essential ligands for ortho metalation complex formation. As the central metal forming the orthometalated complex, any transition metal can be used. In the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. Of these, iridium is particularly preferable. An organic layer containing such an orthometalated complex is excellent in light emission luminance and light emission efficiency. Specific examples of ortho-metalated complexes are also described in paragraphs 0152 to 0180 of Japanese Patent Application No. 2000-254171.

It is preferable that at least one of the light emitting materials is a platinum complex material or an iridium complex material.
In the present invention, a platinum complex material or an iridium complex material is preferably included, more preferably a platinum complex material or an iridium complex material having a tetradentate ligand, and further preferably an iridium complex material.
The fluorescent light-emitting material and the phosphorescent light-emitting material are described in detail in paragraph numbers [0100] to [0164] of JP-A-2008-270736 and paragraph numbers [0088] to [0090] of JP-A-2007-266458, for example. The matters described in these publications can be applied to the present invention.
The iridium complex is preferably an iridium complex represented by the following general formula (T-2).
[Compound represented by formula (T-2)]
The compound represented by formula (T-2) will be described.

(In the general formula (T-2), R _T3 ′ to R _T6 ′ and R _T3 to R _T6 are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cyano group, perfluoroalkyl group, trifluorovinyl. Group, —CO ₂ R _T , —C (O) R _T , —N (R _T ) ₂ , —NO ₂ , —OR _T , a halogen atom, an aryl group or a heteroaryl group, and further having a substituent T You may do it.
R _T3 , R _T4 , R _T5 and R _T6 may be any two adjacent to each other to form a condensed 4- to 7-membered ring, which is a cycloalkyl, aryl or hetero ring It is aryl, and the condensed 4- to 7-membered ring may further have a substituent T.
R _T3 ′ and R _T6 are —C (R _T ) ₂ —C (R _T ) ₂ —, —CR _T = CR _T —, —C (R _T ) ₂ —, —O—, —NR _T —, A ring may be formed by linking with a linking group selected from —O—C (R _T ) ₂ —, —NR _T —C (R _T ) ₂ —, and —N═CR _T —.
R _T each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent T.
The substituents T are each independently a fluorine atom, —R ′, —OR ′, —N (R ′) ₂ , —SR ′, —C (O) R ′, —C (O) OR ′, —C ( O) represents N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, and each R ′ independently represents a hydrogen atom, alkyl Represents a group, a perfluoroalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
(XY) represents a ligand. m represents an integer of 1 to 3, and n represents an integer of 0 to 2. m + n is 3. )

The alkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Group, for example, methyl group, ethyl group, i-propyl group, cyclohexyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent T. The cycloalkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a cycloalkyl group having 4 to 7 ring members, and more preferably a cycloalkyl group having 5 to 6 total carbon atoms. Examples of the alkyl group include a cyclopentyl group and a cyclohexyl group.
The alkenyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Examples thereof include vinyl, allyl, 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
The alkynyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, and particularly preferably 2-10 carbon atoms. For example, ethynyl, propargyl, 1-propynyl, 3-pentynyl and the like.

_Examples of the heteroalkyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , and R _T6 include a group in which at least one carbon of the alkyl group is replaced with O, NR _T , or S.

Examples of the halogen atom represented by R _T3 ′, R _T3 , R _T4 , R _T5 , and R _T6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The aryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably 6 to 6 carbon atoms. 20 aryl groups. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a terphenyl group, a fluorenyl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, and a tolyl group. Group, biphenyl group, anthryl group or terphenyl group is preferable, and phenyl group, fluorenyl group and naphthyl group are more preferable.

The heteroaryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituent. Or an unsubstituted heteroaryl group, for example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, pyrrolyl group, indolyl group , Furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzisothiazolyl group , Thiadiazolyl group, isoxazoly Group, a benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group, a sulfolanyl group, a carbazolyl group, a dibenzofuryl group, dibenzothienyl group, a pyrido-indolyl group. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.

R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluorine atom, an aryl group or a heteroaryl group. And more preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluorine atom or an aryl group, and still more preferably a hydrogen atom, an alkyl group or an aryl group. As the substituent T, an alkyl group, an alkoxy group, a fluorine atom, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom is more preferable.

R _T3 , R _T4 , R _T5 and R _T6 may be any two adjacent to each other to form a condensed 4- to 7-membered ring, which is a cycloalkyl, aryl or hetero ring It is aryl, and the condensed 4- to 7-membered ring may further have a substituent T. The condensed 4- to 7-membered ring may be further condensed with a 4- to 7-membered ring. The definition and preferred range of cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 .

R _T4 ′ is preferably a hydrogen atom, an alkyl group, an aryl group or a fluorine atom, more preferably a hydrogen atom.
R _T5 ′ and R _T6 ′ represent a hydrogen atom or are preferably bonded to each other to form a condensed 4- to 7-membered cyclic group, and the condensed 4- to 7-membered cyclic group includes cycloalkyl, cyclohetero More preferred is alkyl, aryl, or heteroaryl, and even more preferred is aryl.
The substituent T in R _T4 ′ to R _T6 ′ is preferably an alkyl group, an alkoxy group, a fluorine atom, a cyano group, an alkylamino group, or a diarylamino group, and more preferably an alkyl group.

One of the preferred forms of the compound represented by the general formula (T-2) is R _T3 ′, R _T4 ′, R _T5 ′, R _T6 ′, R _T3 , R _{T4 in} the general formula (T-2). , R _T5 and R _T6 , any two adjacent to each other are not bonded to each other to form a condensed ring.

M is preferably 1 to 3, and more preferably 2 or 3. That is, n is preferably 0 or 1. It is preferable that the kind of ligand in a complex is comprised from 1 or 2 types, More preferably, it is 1 type. When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis.

The metal complex represented by the general formula (T-2) includes a ligand represented by the following general formula (T-1-A) in the general formula (T-2) or a tautomer thereof, and (X -Y) or a combination with a tautomer thereof, or all of the ligands of the metal complex are represented by the following general formula (T-1-A) Or a tautomer thereof.

(In the general formula (T-1-A), R T3 '~ R T6' and R _T3 ~ R _T6 are in the general formula (T-2), and R _T3 '~ R _T6' and R _T3 ~ R _T6 (It is synonymous. * Represents the coordination position to iridium.)

Further, as a so-called ligand used for forming a conventionally known metal complex, a ligand (also referred to as a coordination compound) well known by those skilled in the art is optionally used as a ligand represented by (XY). You may do it.

There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Included in ligands (eg, halogen ligands (preferably chlorine ligands), etc., published in 1987, published by Yersin, “Organometallic Chemistry-Fundamentals and Applications-” Nitrogen heteroaryl ligands (for example, bipyridyl, phenanthroline, etc.), diketone ligands (for example, acetylacetone, etc.) The ligand represented by (XY) is preferably a diketone or a picolinic acid. The derivative is most preferably acetylacetonate (acac) shown below from the viewpoint of obtaining stability of the complex and high luminous efficiency.

* Represents a coordination position to iridium.
Specific examples of the ligand represented by (XY) are given below, but the present invention is not limited thereto.

In the example of the ligand represented by the above (XY), * represents a coordination position to iridium in the general formula (T-2). Rx, Ry and Rz each independently represents a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the substituent group A. Preferably, Rx and Rz are each independently an alkyl group, a perfluoroalkyl group, a fluorine atom or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, A fluorine atom and an optionally substituted phenyl group are most preferred, and a methyl group, an ethyl group, a trifluoromethyl group, a fluorine atom and a phenyl group are most preferred. Ry is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, a fluorine atom or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. And most preferably a hydrogen atom or a methyl group. Since these ligands are considered not to be sites where electrons are transported in the device or where electrons are concentrated by excitation, Rx, Ry, and Rz may be any chemically stable substituent, and the effects of the present invention can be achieved. Also has no effect.
Since complex synthesis is easy, (I-1), (I-4) and (I-5) are preferred, and (I-1) is most preferred. Complexes having these ligands can be synthesized in the same manner as in known synthesis examples by using corresponding ligand precursors. For example, in the same manner as described in International Publication No. 2009-073245, page 46, it can be synthesized by the following method using commercially available difluoroacetylacetone.

In addition, a monoanionic ligand represented by the general formula (I-15) can also be used as the ligand.

R _T7 to R _T10 in general formula (I-15) have the same _{meanings as} R _T3 to R _T6 in general formula (T-2), and the preferred ranges are also the same. R _T7 ′ to R _T10 ′ have the same _{meanings as} R _T3 ′ to R _T6 ′ in formula (T-2), and their preferred ranges are also the same as R _T3 ′ to R _T6 ′. * Represents a coordination position to iridium.

One preferred form of the compound represented by the general formula (T-2) is a case represented by the following general formula (T-3).

R _T3 '~ R _T6' in the general formula _{(T3), R T3 ~ R} T6 is, R _T3 in the general formula (T-2) '~ R T6', have the same meaning as R _T3 ~ R _T6, preferably The range is the same.
R _T7 to R _T10 have the same _{meanings as} R _T3 to R _T6 in formula (T-2), and preferred ranges are also the same. R _T7 ′ to R _T10 ′ have the same _{meanings as} R _T3 ′ to R _T6 ′ in formula (T-2), and preferred ranges are also the same.

Another preferred embodiment of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-4).

R _T3 ′ to R _T6 ′, R _T3 to R _T6 , (XY), m and n in the general formula (T-4) are R _T3 ′ to R _T6 ′, R in the general formula (T-2). _T3 to R _{T6 have the same meanings} as (XY), m and n, and the preferred ranges are also the same. Among R _T3 ′ to R _T6 ′ and R _T3 to R _T6 , it is particularly preferred that 0 to 2 are alkyl groups or phenyl groups and the rest are all hydrogen atoms, and R _T3 ′ to R _T6 ′ and R _T3 to R More preferably, one or two of _T6 are alkyl groups and the rest are all hydrogen atoms.

Another preferred embodiment of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-5).

R _T3 ′ to R _T7 ′, R _T3 to R _T6 , (XY), m and n in the general formula (T-5) are R _T3 ′ to R _T6 ′, R in the general formula (T-2). _T3 to R _{T6 have the same meanings} as (XY), m and n, and the preferred ones are also the same.

Another preferred embodiment of the compound represented by the general formula (T-2) is a case represented by the following general formula (T-6).

In general formula (T-6), the definitions and preferred ranges of R _1a to R _1i are the same as those in R _T3 to R _T6 in general formula (T-2). Further, it is particularly preferable that 0 to 2 of R _1a to R _1i are alkyl groups or aryl groups and the rest are all hydrogen atoms. The definitions and preferred ranges of (XY), m, and n are the same as (XY), m, and n in formula (T-2).

Preferred specific examples of the iridium complex material are listed below, but are not limited thereto.

The compounds exemplified as the compound represented by the general formula (T-2) can be synthesized by the method described in JP2009-99783A, various methods described in US Pat. No. 7,279,232 and the like. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

The compound represented by the general formula (T-2) is contained in the light emitting layer, but its use is not limited and may be further contained in any layer in the organic layer.

Specific examples of the platinum complex include compounds described in [0143] to [0152], [0157] to [0158] and [0162] to [0168] of JP-A-2005-310733, and JP-A-2006-256999. Nos. [0065] to [0083], No. 2006-93542, Nos. [0065] to [0090], No. 2007-33891, Nos. [0063] to [0071] The compounds described in [0079] to [0083] of JP-A-2007-324309, the compounds described in [0065] to [0090] of JP-A-2006-93542, and JP-A-2007-96255 Nos. [0055] to [0071], and JP-A-2006-313796 [0043] to [004] ] And the like, platinum complexes exemplified other following can be mentioned.

These platinum complex compounds are described in, for example, Journal of Organic Chemistry 53,786, (1988), G.M. R. Newkome et al. ), Page 789, method described in left column 53 to right column 7, line 790, method described in left column 18 to 38, method 790, method described in right column 19 to 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26 to 35, and the like.

The light emitting material in the light emitting layer is generally contained in the light emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound forming the light emitting layer. From the viewpoint of durability and external quantum efficiency. The content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.

The orthometalated complex used in the present invention is Inorg. Chem. 30, 1685, 1991, Inorg. Chem. 27, 3464, 1988, Inorg. Chem. 33, 545, 1994, Inorg. Chim. Acta, 181, 245, 1991; Organomet. Chem. , 335, 293, 1987; Am. Chem. Soc. , 107, 1431, 1985 and the like.

The content of the phosphorescent compound in the light emitting layer is not particularly limited, but is, for example, 0.1 to 70% by mass, and preferably 1 to 20% by mass. If the content of the phosphorescent compound is less than 0.1% by mass or exceeds 70% by mass, the effect may not be sufficiently exhibited.

In the present invention, the light emitting layer may contain a host compound as necessary.

The host compound is a compound that causes energy transfer from the excited state to the phosphorescent compound, and as a result, causes the phosphorescent compound to emit light. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide oxide Derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, and heterocyclic tetra Rubonic acid anhydride, phthalocyanine derivative, metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complex having benzoxazole or benzothiazole as a ligand, polysilane compound, poly (N-vinylcarbazole) derivative, aniline copolymer , Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like. A host compound may be used individually by 1 type, or may use 2 or more types together.

The thickness of the light emitting layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(Charge transport layer)
The charge transport layer is a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. A hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer is preferable. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer, it is possible to manufacture an organic electroluminescent element with low cost and high efficiency. The charge transport layer is more preferably a hole injection layer, a hole transport layer, or an electron block layer.

(Hole injection layer, hole transport layer)
The organic electroluminescent element of the present invention may have a hole injection layer and a hole transport layer. The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
The hole injection layer and the hole transport layer are described in detail, for example, in JP-A-2008-270736 and JP-A-2007-266458, and the matters described in these publications can be applied to the present invention.

(Electron injection layer, electron transport layer)
The organic electroluminescent element of the present invention may have an electron injection layer and an electron transport layer. The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
The electron injection layer and the electron transport layer are described in detail, for example, in JP-A-2008-270736 and JP-A-2007-266458, and the matters described in these publications can be applied to the present invention.

(Hole blocking layer)
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
Examples of organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP), triphenylene derivatives, carbazole derivatives, and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

(Electronic block layer)
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
As an example of the organic compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(Description of exciton block layer)
The exciton blocking layer is a layer formed at one or both of the interface between the light emitting layer and the hole transport layer, or the interface between the light emitting layer and the electron transport layer, and the excitons generated in the light emitting layer are holes. It is a layer that diffuses into the transport layer and the electron transport layer and prevents deactivation without emitting light. The exciton blocking layer is preferably made of a carbazole derivative.

[Other organic layers]
The organic electroluminescence device of the present invention has a protective layer described in JP-A-7-85974, 7-192866, 8-22891, 10-275682, 10-106746, etc. Also good. The protective layer is formed on the uppermost surface of the light emitting element. Here, when the base material, the transparent electrode, the organic layer, and the back electrode are laminated in this order, the top surface refers to the outer surface of the back electrode, and the base material, the back electrode, the organic layer, and the transparent electrode are laminated in this order. In some cases, it refers to the outer surface of the transparent electrode. The shape, size, thickness and the like of the protective layer are not particularly limited. The material for forming the protective layer is not particularly limited as long as it has a function of suppressing intrusion or permeation of a light-emitting element such as moisture or oxygen into the element. Silicon, germanium oxide, germanium dioxide or the like can be used.

The method for forming the protective layer is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular sensing epitaxy, cluster ion beam, ion plating, plasma polymerization, plasma CVD, laser CVD Thermal CVD method, coating method, etc. can be applied.

[Sealing]
The organic electroluminescent element is preferably provided with a sealing layer for preventing moisture and oxygen from entering. As a material for forming the sealing layer, a copolymer of tetrafluoroethylene and at least one comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, polyethylene, polypropylene, polymethyl methacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene or a copolymer of dichlorodifluoroethylene and another comonomer, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0. less than 1% moisture-proof material, metal (in, Sn, Pb, Au , Cu, Ag, Al, Tl, Ni , etc.), metal oxides _{(MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, _{_{CaO, BaO, Fe 2 O 3}} , Y 2 O 3, TiO 2 , etc.), metal fluorides (MgF _2, L F, AlF _3, CaF _2, etc.), liquid fluorinated carbon (perfluoroalkane, perfluoro amine, perfluoro ether), etc. are available that in the liquid fluorinated carbon was dispersed adsorbent moisture or oxygen It is.

The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.

The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

(Use of the element of the present invention)
The element of the present invention can be suitably used for a display element, a display, a backlight, electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication. In particular, it is preferably used for a device driven in a region having a high light emission luminance, such as a lighting device or a display device.

Next, the light emitting device of the present invention will be described with reference to FIG.
FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention. The light-emitting device 20 in FIG. 2 includes a transparent substrate (substrate) 2, an organic electroluminescent element 10, a sealing container 16, and the like.

The organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2. A protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween. In addition, a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate | omitted.
Here, as the adhesive layer 14, a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.

The use of the light-emitting device of the present invention is not particularly limited, and for example, it can be a display device such as a television, a personal computer, a mobile phone, and electronic paper in addition to a lighting device.

(Lighting device)
Next, the illumination device of the present invention will be described with reference to FIG.
FIG. 3 is a cross-sectional view schematically showing an example of the illumination device of the present invention. As shown in FIG. 3, the illumination device 40 of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
The light scattering member 30 is not particularly limited as long as it can scatter light. In FIG. 3, the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31. As the transparent substrate 31, for example, a glass substrate can be preferably cited. As the fine particles 32, transparent resin fine particles can be preferably exemplified. As the glass substrate and the transparent resin fine particles, known ones can be used. In such an illuminating device 40, when light emitted from the organic electroluminescent element 10 is incident on the light incident surface 30A of the scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, reagents, substance amounts and ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

α-naphthylamine 25.0 g, 4,4′-dibromobiphenyl 22.7 g, bis (dibenzylideneacetone) palladium 0.21 g, diphenylphosphinoferrocene 0.3 g, and t-butoxy sodium 21.0 g in toluene (200 mL) Heated to reflux for 8.5 hours. After completion of the reaction, 300 mL of ethanol was added and stirred at room temperature for 30 minutes, and the resulting precipitate was filtered off. This was washed with water and then with 150 mL of ethanol, and then twice with 150 mL of ethyl acetate to obtain compound P-1. The mass after drying was 48.8 g (yield 64%).
Compound P-1 (20 g) was purified by sublimation at 0.07 Pa. The 10% mass reduction point was 295 ° C., and after sublimation, the mass of compound P-1 was 14.2 g (71%).

Sublimation-purified compound P-1 10.0 g, p-bromostyrene 10.1 g, bis (dibenzylideneacetone) palladium 0.53 g, 2-dimethylamino-2′-dicyclohexylphosphinobiphenyl 0.39 g, t-butoxy sodium 6.6 g was stirred in toluene (115 mL) at 80 ° C. for 1.5 hours. The reaction solution was cooled and extracted with ethyl acetate. The obtained organic phase was concentrated and purified by column chromatography using hexane / ethyl acetate as a developing solvent to obtain Compound 1 (hereinafter referred to as Compound 1-1). The mass after drying was 7.4 g (yield 50.2%).
In the same manner, 10.0 g of compound P-1 before sublimation purification was similarly reacted to obtain compound 1 (hereinafter referred to as compound 1-2). The mass after drying was 7.0 g (yield 47.5%).

The structures of the compounds used in the following examples and comparative examples are described below.
Compounds 1 to 4 were all synthesized using P-1 as a precursor, and sublimated and purified P-1 was synthesized as a compound 1-1 to 4-1, and P-1 that was not sublimated and purified was used as a precursor. The synthesized compounds are referred to as compounds 1-2 to 4-2, respectively.

Compounds

5 and 6 were synthesized using P-5 as a precursor, synthesized using sublimation-purified P-5 as a precursor, and then synthesized as compounds 5-1 and 6-1, respectively, and P-5 not sublimated and purified as a precursor. These were referred to as compounds 5-2 to 6-2, respectively.
Compound HI-2 was synthesized using P-HI-1 as a precursor and synthesized by sublimation-purified P-HI-1 as a precursor, HI-2-1, and P-HI-1 not subjected to sublimation purification as a precursor Is synthesized as HI-2-2.

[A. Examples A-1 to A-5 and Comparative Examples A-1 to A-5 (Production of Green Light-Emitting Element)]
Example A-1
<Preparation of Coating Solution A for Hole Transport Layer Formation>
Compound 1-1 was dissolved in xylene for electronic industry to give a total solid content concentration of 0.4% by mass, and this was filtered through a PTFE (polytetrafluoroethylene) filter having a pore size of 0.22 μm to obtain a hole transport layer. A forming coating solution A was prepared.

<Preparation of light emitting layer forming coating solution A>
95% by mass of the host compound H-1 and 5% by mass of the luminescent material E-1 are dissolved in methyl ethyl ketone (MEK) to a solid content concentration of 1.0% by mass, which has a pore size of 0.22 μm. It filtered with the PTFE filter and the coating liquid A for light emitting layer formation was prepared.

<Element fabrication>
A transparent support substrate was obtained by depositing ITO with a thickness of 150 nm on a glass substrate of 25 mm × 25 mm × 0.7 mm. This transparent support substrate was placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes.
On this ITO-attached glass substrate, PTPDES represented by the following structural formula (weight average molecular weight Mw = 13,100, manufactured by Chemipro Kasei Co., Ltd., n represents the number of repetitions of the structure in parentheses and is an integer) 2 mass Part was dissolved in 98 parts by mass of cyclohexanone for electronics industry (manufactured by Kanto Chemical Co., Inc.), spin-coated (2500 rpm, 20 seconds), then dried at 120 ° C. for 10 minutes and annealed at 160 ° C. for 60 minutes, resulting in a thickness of about A hole injection layer was formed to a thickness of 40 nm.

On the hole injection layer, the coating liquid A for forming a hole transport layer prepared as described above is spin-coated (1500 rpm, 20 seconds) and then dried at 120 ° C. for 30 minutes, so that the thickness is about 10 nm. A hole transport layer was formed as described above.

On the hole transport layer, the light emitting layer forming coating solution A prepared as described above was spin coated (1500 rpm, 20 seconds) in a glove box (dew point -68 degrees, oxygen concentration 10 ppm), and the thickness was about 30 nm. A light emitting layer was formed as described above.
Next, BAlq (bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolato) -aluminum (III)) represented by the following structural formula is formed on the light emitting layer as an electron transport layer with a thickness of It formed by the vacuum evaporation method so that it might become 40 nm.

Lithium fluoride (LiF) was formed as an electron injection layer on the electron transport layer by a vacuum deposition method so as to have a thickness of 1 nm. Furthermore, 70 nm of metal aluminum was vapor-deposited to make a cathode.
The laminate produced as described above is placed in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, an organic electroluminescent element of Example A-1 was produced.

(Example A-2, Example A-3 and Comparative Examples A-1 to A-3)
In the preparation of the coating liquid A for forming a hole transport layer in Example A-1, Example A-2 was prepared in the same manner as in Example A-1, except that the hole transport material shown in Table 1 below was used. Thus, organic electroluminescent elements of Example A-3 and Comparative Examples A-1 to A-3 were obtained.

(Example A-4, Comparative Example A-4)
In producing the devices of Example A-1 and Comparative Example A-1, instead of forming the light emitting layer by coating using the light emitting layer forming coating solution A, 95% by mass of the host compound H-1 and 5% A light emitting layer having a film thickness of 30 nm was formed by vapor-depositing the light emitting material E-1 in mass% by a vacuum evaporation method, and the drying time of the hole transport layer was changed to the drying time shown in Table 1. The devices of Example A-4 and Comparative Example A-4 were obtained in the same manner as Example A-1 and Comparative Example A-1, except for the above.

(Example A-5, Comparative Example A-5)
In the formation of the hole transport layer in Example A-1 and Comparative Example A-1, Example A- was conducted in the same manner as in Example A-1 and Comparative Example A-1, except that the drying temperature was changed to 200 ° C. 5. An organic electroluminescent device of Comparative Example A-5 was obtained.

<Element evaluation>
(A) High temperature driving durability The direct current was adjusted so that the initial luminance was 1000 cd / m ² at 80 ° C., and the time taken until the luminance was reduced by half was used as an index of durability.
(B) Durability at the beginning of driving The direct current was adjusted so that the initial luminance at room temperature was 1000 cd / m ² , and the time taken for the luminance to reach 900 cd / m ² was used as an index of the initial driving durability. .
(C) Evaluation of in-plane luminance unevenness In-plane luminance distribution when the manufactured device was made to emit light at a current density of ^2.5 mA / cm ² was measured using CA-1500 manufactured by Minolta. The luminance ratio Lmin / Lmax at the measurement point with the highest luminance was used as an index of in-plane luminance unevenness.

The above results are shown in Table 1. In Table 1, the results of the high temperature driving durability and the durability at the initial stage of driving are described as relative values when the value of Comparative Example A-1 is 1. Moreover, it described about the drying time and drying temperature at the time of forming a positive hole transport layer.

[B. Examples B-1 to B-3 and Comparative Examples B-1 to B-3 (Production of Red Light Emitting Element)]
Example B-1
<Preparation of light emitting layer forming coating solution B>
95% by mass of the host compound H-2 and 5% by mass of the luminescent material E-2 are dissolved in methyl ethyl ketone (MEK) to a solid content concentration of 1.0% by mass, which has a pore size of 0.22 μm. It filtered with the PTFE filter and prepared the coating liquid B for light emitting layer formation.

<Element fabrication>
A transparent support substrate was obtained by depositing ITO with a thickness of 150 nm on a glass substrate of 25 mm × 25 mm × 0.7 mm. This transparent support substrate was placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes.
On this glass substrate with ITO, 0.5 part by mass of compound A (described in US2008 / 0220265) represented by the following structural formula was dissolved in 99.5 parts by mass of cyclohexanone and spin-coated (4000 rpm, 30 seconds). By drying at 200 ° C. for 30 minutes, a hole injection layer was formed to a thickness of about 5 nm.

On the hole injection layer, the hole transport layer forming coating solution A used in Example A-1 was spin-coated (1500 rpm, 20 seconds), and then dried at 150 ° C. for 20 minutes to obtain a thickness of about A hole transport layer was formed to have a thickness of 10 nm.

The light emitting layer forming coating solution B prepared as described above is spin-coated on the hole transport layer in a glove box (dew point -68 degrees, oxygen concentration 10 ppm) to a thickness of about 30 nm (1500 rpm, 20 seconds). And a light emitting layer.
Next, on the light emitting layer, as in Example A-1, BAlq was formed as an electron transport layer, lithium fluoride (LiF) was formed as an electron injection layer, and metallic aluminum was formed as a cathode.
The laminate produced as described above is placed in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, an organic electroluminescent element of Example B-1 was produced.

(Example B-2, Comparative Example B-1 and Comparative Example B-2)
Example B-2 was carried out in the same manner as Example B-1, except that the hole transport material shown in Table 2 below was used in the preparation of the coating liquid A for forming a hole transport layer in Example B-1. Thus, organic electroluminescent elements of Comparative Example B-1 and Comparative Example B-2 were obtained.

(Example B-3, Comparative Example B-3)
In the formation of the hole injection layer in Example B-1 and Comparative Example B-1, Example B- was performed in the same manner as Example B-1 and Comparative Example B-1, except that the drying temperature was changed to 200 ° C. 3. An organic electroluminescent device of Comparative Example B-3 was obtained.

Each element obtained as described above was evaluated in the same manner as in Example A-1, and the results are shown in Table 2. In Table 2, the results of the high temperature driving durability and the durability at the initial stage of movement are shown as relative values when the value of Comparative Example B-1 is 1. Moreover, it described about the drying time and drying temperature at the time of forming a positive hole transport layer.

[C. Examples C-1 to C-3 and Comparative Examples C-1 to C-3 (Production of Green Light-Emitting Element)] (Example C-1)
<Preparation of Coating Solution C for Hole Transport Layer Formation>
The hole transport material 4-1 was dissolved in xylene / benzyl alcohol for electronic industry (= mass ratio 60/40) to a total solid content concentration of 0.4% by mass, and this was filtered with a PTFE filter having a pore size of 0.22 μm. Filtration was performed to prepare a coating liquid C for forming a hole transport layer.

<Preparation of light emitting layer forming coating solution C>
85% by mass of the host compound H-3 and 15% by mass of the luminescent material E-3 are dissolved in methyl ethyl ketone (MEK) to obtain a solid content concentration of 1.0% by mass, which has a pore size of 0.22 μm. The mixture was filtered with a PTFE filter to prepare a light emitting layer forming coating solution C.

<Element fabrication>
In the same manner as in Example B-1, a hole injection layer containing Compound A was formed on a glass substrate with ITO.

On the hole injection layer, the hole transport layer forming coating solution C prepared as described above is spin-coated (1500 rpm, 20 seconds), dried at 100 ° C. for 30 minutes, and annealed at 150 ° C. for 10 minutes. Thus, a hole transport layer was formed to have a thickness of about 10 nm.

On the hole transport layer, the light emitting layer forming coating solution C prepared as described above was spin-coated (1500 rpm, 20 seconds) in a glove box (dew point -68 degrees, oxygen concentration 10 ppm), and the thickness was about 30 nm. A light emitting layer was formed as described above.
Next, on the light emitting layer, as in Example A-1, BAlq was formed as an electron transport layer, lithium fluoride (LiF) was formed as an electron injection layer, and metallic aluminum was formed as a cathode.
The laminate produced as described above is placed in a glove box substituted with argon gas, and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, an organic electroluminescent element of Example C-1 was produced.

(Examples C-2 and C-3 Comparative Examples C-1 to C-3)
Example C-2 was carried out in the same manner as Example C-1, except that the hole transport material shown in Table 3 below was used in the preparation of the coating liquid C for forming a hole transport layer in Example C-1. C-3 and organic electroluminescent elements of Comparative Examples C-1 to C-3 were obtained.

Each element obtained as described above was evaluated in the same manner as in Example A-1, and the results are shown in Table 3. In Table 3, the results of the high temperature driving durability and the durability in the initial stage of movement are shown as relative values when the value of Comparative Example C-1 is 1.

[D to F. Examples D-1 to D-3, Comparative Examples D-1 to D-3, Example E-4, Comparative Example E-4, Examples F-1 to F-3, Comparative Examples F-1 to F- 3]
A device was fabricated in the same manner as in Example A-1, except that the material used for each layer was changed to the materials listed in Tables 4 to 6, respectively. Note that the element is manufactured with a constant concentration of the solvent and the solid content with respect to the solvent unless otherwise specified.

The durability at high temperature driving of each element obtained as described above was evaluated in the same manner as in Example A-1, and the results are shown in Tables 4-6. The high temperature driving durability is described as a relative value when the values of Comparative Examples D-1, E-4, and F-1 are 1.

The structures of compounds other than the above used in the examples are described below.

As is clear from the results in Tables 1 to 6, when the element synthesized after sublimation purification of the precursor is included in the element, the element is compared with the element using the material synthesized without sublimation purification. It can be seen that the driving durability at high temperatures is excellent. Further, it can be seen that the durability at the initial stage of driving is excellent and the in-plane luminance is uniform.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on Aug. 17, 2010 (Japanese Patent Application No. 2010-182647), the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 2 ... Substrate 3 ... Anode 4 ... Hole injection layer 5 ... Hole transport layer 6 ... Light emitting layer 7 ... Hole block layer 8 ... Electron transport layer 9 ...・ Cathode 10: Organic electroluminescent device (organic EL device)
DESCRIPTION OF SYMBOLS 11 ... Organic layer 12 ... Protective layer 14 ... Adhesive layer 16 ... Sealing container 20 ... Light-emitting device 30 ... Light scattering member 30A ... Light incident surface 30B ... Light Output surface 31 ... Transparent substrate 32 ... Fine particle 40 ... Illumination device

Claims

An organic electroluminescent element material in which a thermally reactive group is introduced into a sublimated and purified precursor.
2. The precursor according to claim 1, wherein the precursor is a compound having a hydrogen bonding site, and the introduction of the thermally reactive group is introduction of a polymerizable group into the hydrogen bonding site of the compound having the hydrogen bonding site. Materials for organic electroluminescent elements.
The organic electroluminescent element material according to claim 1 or 2, wherein the hydrogen bonding site of the precursor is a primary or secondary arylamine.
The material for an organic electroluminescent element according to any one of claims 1 to 3, wherein the precursor is a compound represented by the following general formula (A1).

(In general formula (A1), each Q may be independently condensed, and represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent. May combine to form a condensed ring which may have a substituent.
The material according to any one of claims 2 to 4, wherein the polymerizable group is a terminal olefin group.
The organic electroluminescent element material according to any one of claims 1 to 5, wherein the organic electroluminescent element material is an organic electroluminescent element material represented by the following general formula (1).

(In the general formula (1), each R 1 independently represents a substituent. P 1 represents a vinyl group, an acrylic group, a methacryl group, an epoxy group, or an oxetane group. L independently represents an integer of 0 to 5. L ′ represents an integer of 0 to 4. m3 represents an integer of 0 or more, and R 1 may form a bond to form a condensed ring which may have a substituent. Good.)
The organic electroluminescent element material according to any one of claims 1 to 5, wherein the organic electroluminescent element material is an organic electroluminescent element material represented by the following general formula (2).

(In general formula (2), m1 and m2 each independently represents an integer of 0 or more. M1 and m2 do not represent 0 at the same time. N1 and n2 each independently represents an integer of 0 to 10. P 2 and P 3 each independently represents a vinyl group, an acryl group, a methacryl group, an epoxy group or an oxetane group, and Q1 to Q4 may each independently be condensed and have a substituent. Represents a 6-membered aromatic hydrocarbon ring or aromatic heterocycle, and Q1 and Q3, Q2 and Q4 may be bonded to each other to form a condensed ring which may have a substituent. L is a single bond or a divalent linking group.)
A composition for an organic electroluminescence device comprising the material for an organic electroluminescence device according to any one of claims 1 to 7 and a solvent.
The film | membrane for organic electroluminescent elements formed by apply | coating the composition of Claim 8, and heating or light-irradiating this apply | coated composition.
An organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and at least one organic layer including a light emitting layer between the electrodes,
An organic electroluminescent element comprising the organic electroluminescent element material according to any one of claims 1 to 7 in at least one of the organic layers.
The organic layer includes a hole transport layer, a hole injection layer, or an electron block layer, and the hole transport layer, the hole injection layer, or the electron block layer is any one of claims 1 to 7. The organic electroluminescent element according to claim 10, comprising a material for an organic electroluminescent element.
The organic electroluminescent element according to claim 10 or 11, wherein the organic layer includes a light emitting layer, and the light emitting layer includes a phosphorescent metal complex.
The organic electroluminescent element according to any one of claims 10 to 12, comprising the film according to claim 9.
14. The organic electroluminescence device according to claim 10, wherein at least one organic layer between the pair of electrodes is formed by a coating method.