JP2012031372A - New arylamine dendrimer-like compound, method for producing the same, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new arylamine dendrimer-like compound having excellent solubility and improved luminous efficiency, and to provide a simple method for producing the compound, and an electronic element using the same.SOLUTION: This arylamine dendrimer-like compound is synthesized by reacting an arylamine polymer represented by general formula (15) with at least one kind of polyhalogenated aromatic compounds (for example, tris(4-bromophenyl) amine or 1,3,5-tribromobenzene) under the presence of a palladium catalyst and a base. (In the formula, Arand Arare each independently aromatic group which may have a substituent, and n represents an integer of ≥1).

Description

  The present invention relates to a novel arylamine dendrimer-like compound, a method for producing the same, and an electronic device using the same.

  Organic EL elements are mainly divided into a light-emitting layer, a carrier transport layer that transports holes or electrons, two electrodes, a cathode and an anode, and other materials.

  As the material of the organic EL element, various low molecular weight materials and high molecular weight materials are used for the light emitting layer and the carrier transport layer. Especially, the low molecular weight material is excellent in terms of efficiency and life of the element. Therefore, many materials have been proposed and commercialized for mobile applications. However, the biggest problem of an organic EL element made of a low molecular material is the manufacturing cost, and as a solution, development of a coating material such as a polymer material is desired.

  As polymer coating materials, for example, poly (p-phenylene vinylene), polyalkylthiophene (see, for example, Patent Document 1), and polyfluorene-based conductive π-conjugated polymers are known.

  Further, PEDOT-PSS, polyarylamine, and the like have been proposed as hole injection (transport) materials. As polyarylamines, non-conjugated polymers having an arylamino group in the side chain (for example, see Patent Documents 2 to 6) and conjugated polymers having an arylamine structure in the main chain have been reported (for example, Patent Documents 7 to 8). reference).

  Regarding hole transfer, which is an important factor in the efficiency and lifetime of organic EL devices, hole transfer of non-conjugated arylamine polymers proceeds via hopping transport between molecules, whereas in conjugated arylamine polymers, In addition to via hopping transport in between, the holes can advantageously move along the main chain structure. Therefore, a conjugated arylamine polymer is particularly preferable in terms of efficiency.

  Furthermore, according to Patent Documents 7 to 8, it is reported that the device lifetime is improved by protecting the polymer terminal (for example, halogen atom, secondary amino group, etc.).

  As the polymer coating material, in addition to the various polymers as described above, a new organic EL technology using a dendrimer has been developed (for example, see Non-Patent Document 1). Since conventional polymers are linearly linked, it has been a disadvantage that they become difficult to dissolve in a solvent when the molecular weight is increased. However, dendrimers can be used by mixing a large amount of polymer light-emitting materials, so the coating properties are good. It becomes. It has been reported that a dendrimer having an arylamine as a constituent element also exhibits good solubility in an organic solvent (see, for example, Patent Document 9).

JP-A-3-230787 JP-A-8-54833 JP-A-8-259935 Japanese Patent Laid-Open No. 11-35687 JP-A-11-292828 Japanese Patent Laid-Open No. 13-98023 JP 2004-292882 A Special table 2001-527102 Special table 2009-512628 gazette

Dendritic polymer / highly functional world with multi-branched structure, 2005, pages 246-259

  Whether it is a conjugated arylamine polymer with a polymer end protected or an arylamine dendrimer, it does not reach the performance of organic EL devices made of low molecular weight materials, and further performance improvement is expected. It is rare.

  The present invention has been made in view of the above-described problems, and relates to a novel arylamine dendrimer-like compound that is superior in durability and luminous efficiency to conventional materials.

  As a result of intensive studies to solve the above problems, the present inventors have found that arylamine dendrimer-like compounds obtained by specific polymerization reactions are superior to conventional conjugated arylamine polymers in terms of luminous efficiency and durability. As a result, the present invention has been completed.

  That is, the present invention provides the following general formula (1)

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 60 carbon atoms which may have a substituent, and n represents an integer of 1 or more.)
An arylamine polymer skeleton represented by general formulas (2) to (4)

(In the formula, Ar ³ represents an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are Each independently represents an alkyl or alkoxy group having 1 to 18 carbon atoms, or a halogen atom, A represents a nitrogen atom or a phosphorus atom, and a, b, c, d, e, f, and g each independently Represents an integer of 0 to 5. h represents an integer of 3 to 6, and i, j, k, l, o, and p each independently represents an integer of 1 to 5. However, i + j + k and l + o + p represent each Independently represents an integer of 3 to 6. R represents a binding site of the arylamine polymer skeleton represented by the general formula (1).
An arylamine dendrimer-like compound characterized in that it has a structure in which at least one aromatic skeleton represented by the formula is repeatedly bonded, and a production method and use thereof.

In the compound represented by the general formula (1), Ar ¹ is not particularly limited as long as it is an aromatic group having 6 to 60 carbon atoms which may have a substituent. It is preferably any one of 5) to (8).

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 18 carbon atoms or an optionally substituted phenyl group, and m is an integer of 1 to 3) Represents).

Although R ^{8, R 9,} an alkyl group having 1 to 18 carbon atoms represented as ^{R 10} and ^{R 11} or not particularly restricted but includes a phenyl group which may have a substituent group, include C 1-18 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert -Pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, n-octyl group, tert-octyl group, 2-ethylhexyl Group, n-nonyl group, n-decyl group, trifluoromethyl group, etc., and a phenyl group which may have a substituent. Are phenyl group, tolyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, isobutylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, Isopentylphenyl group, neopentylphenyl group, tert-pentylphenyl group, cyclopentylphenyl group, n-hexylphenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, difluorophenyl group, methoxyphenyl group, acetylphenyl group, cyano Examples thereof include a phenyl group, a methylthiophenyl group, a methoxycarbonylphenyl group, and an N, N-dimethylaminophenyl group.

In the compound represented by the general formula (1), Ar ² is not particularly limited as long as it is an aromatic group having 6 to 60 carbon atoms which may have a substituent. It is preferably any one of 9) to (14).

(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ each independently have an alkyl group having 1 to 18 carbon atoms, or a substituent. And q represents an integer of 0 to 5.
^{R 12, R 13, R 14} , R 15, R 16, R 17, R 18, an alkyl group having 1 to 18 carbon atoms represented as ^{R 19} and ^{R 20,} as a phenyl group which may have a substituent Although there is no particular limitation, examples represented as R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ can be given.

  The arylamine dendrimer-like compound of the present invention has the following general formula (15)

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 60 carbon atoms which may have a substituent, and n represents an integer of 1 or more.)
And arylamine polymers represented by general formulas (16) to (18)

(In the formula, Ar ³ represents an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are Each independently represents an alkyl or alkoxy group having 1 to 18 carbon atoms, or a halogen atom, A represents a nitrogen atom or a phosphorus atom, and a, b, c, d, e, f, and g each independently Represents an integer of 0 to 5. h represents an integer of 3 to 6, and i, j, k, l, o, and p each independently represents an integer of 1 to 5. However, i + j + k and l + o + p represent each Independently represents an integer of 3 to 6. X represents a chlorine atom, a bromine atom, or an iodine atom.)
It can manufacture by making the at least 1 sort (s) of polyhalogenated aromatic compound represented by these exist in presence of a palladium catalyst and a base.

In the arylamine polymer represented by the general formula (15), Ar ¹ and Ar ² are the same as described above.

In the polyhalogenated aromatic compound represented by the general formula (16), Ar ³ is not particularly limited as long as it is an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms. However, examples of the arylene group include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthracenylene group, a phenanthrylene group, a fluorenylene group, a pyrenylene group, a chrysenylene group, and the like. Examples of the heteroarylene group include a thienylene group and a pyrrolylene group. N-substituted carbazolylene group and the like.

In the polyhalogenated aromatic compounds represented by the general formulas (16) to (18), 1 to 18 carbon atoms represented as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7. The alkyl group is not particularly limited, and examples represented by R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ can be given. Further, the alkoxy group having 1 to 18 carbon atoms is not particularly limited, but methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl. Examples thereof include an oxy group, a hexyloxy group, and a stearyloxy group.

  The palladium compound that can be used as the catalyst component of the palladium catalyst is not particularly limited. For example, tetravalent palladium compounds (for example, sodium hexachloropalladium (IV) tetrahydrate, hexachloropalladium (IV) acid) Potassium), divalent palladium compounds (for example, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), Dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium (II) triflu Roacetate, etc.), and zero-valent palladium compounds (for example, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0 ) Etc.).

  The amount of the palladium compound used is not particularly limited, but in the reaction between the arylamine polymer represented by the general formula (1) and the polyhalogenated aromatic compound, the halogen of the starting polyhalogenated aromatic compound is used. Since it is usually in the range of 0.00001 to 20 mol% in terms of palladium with respect to 1 mol of atoms and an expensive palladium compound is used, it is in terms of palladium with respect to 1 mol of halogen atoms of the starting polyhalogenated aromatic compound. In general, it is preferably in the range of 0.001 to 5 mol%.

  In the method of the present invention, the ligand that can be used as a catalyst component of the palladium catalyst is not particularly limited, and any ligand that can coordinate to palladium, such as trialkylphosphines, aryl Examples include phosphines and carbene ligands.

  In the method of the present invention, trialkylphosphines are not particularly limited, and examples thereof include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, and tri-sec-butyl. Examples include phosphine and tri-tert-butylphosphine. Of these, tri-tert-butylphosphine is preferably used because of its particularly high reaction activity as a catalyst.

  In the method of the present invention, aryl phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, and tri (p-tolyl). Examples include phosphine, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (BINAP), trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene, and the like.

  Examples of the carbene-based ligand include 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene hydrochloride.

  The amount of the ligand to be used is not particularly limited, but it may be used usually in the range of 0.01 to 10000 times mol of the palladium compound, and expensive trialkylphosphine, arylphosphine, carbene-based coordination. Since a child is used, it is preferably in the range of 0.1 to 10 moles relative to the palladium compound.

  The method for adding the palladium catalyst is not particularly limited, and the palladium catalyst may be added to the reaction system alone as a catalyst component, or a catalyst prepared in advance in the form of a complex composed of these catalyst components may be added.

  The base is not particularly limited, and examples thereof include inorganic bases such as sodium and potassium carbonates, alkali metal alkoxides, and organic bases such as tertiary amines. Of these, preferred are alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, and the like. It may be added to the system as it is, or may be prepared in situ from an alkali metal, an alkali metal hydride or an alkali metal hydroxide and an alcohol and supplied to the reaction system. More preferably, a tertiary alkoxide such as lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide or the like is added to the reaction system as it is.

  The amount of the base used is not particularly limited. For example, in the reaction of the arylamine polymer represented by the general formula (1) and the polyhalogenated aromatic compound, a polyhalogen added to the reaction system is preferable. It is 0.5 times mole or more with respect to the halogen atom of the fluorinated aromatic compound, and the range of 1 to 20 times mole is more preferable in consideration of the post-treatment operation after completion of the reaction.

  The production of the arylamine dendrimer-like compound of the present invention is usually preferably carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane. A solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. can be mentioned. Of these, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred.

  The production of the arylamine dendrimer-like compound of the present invention is preferably carried out under normal pressure and in an inert gas atmosphere such as nitrogen or argon, but can be carried out even under pressurized conditions.

  In the method of the present invention, the reaction temperature is not particularly limited as long as it is a reaction temperature capable of producing an arylamine dendrimer-like compound, but is usually 20 to 300 ° C, preferably 50 to 200 ° C, more preferably It is the range of 100-150 degreeC.

  In the method of the present invention, the reaction time is not particularly limited because it is not constant depending on the arylamine dendrimer-like compound to be produced, the catalyst and / or the reaction temperature, etc., but in many cases, it is selected from the range of several minutes to 72 hours. do it. Preferably it is less than 24 hours.

  The arylamine dendrimer-like compound in the present invention can be purified by reprecipitation. It is also possible to perform adsorption treatment with silica gel, activated alumina or the like for removing impurities.

  The weight average molecular weight of the arylamine dendrimer-like compound of the present invention is not particularly limited, but is in the range of 1,000 to 1,000,000 in terms of polystyrene, more preferably 10,000 to 100,000. Range.

  The arylamine dendrimer-like compound of the present invention is used as a conductive polymer material in electronic devices such as field effect transistors, optical functional devices, dye-sensitized solar cells, and organic electroluminescence devices. In particular, it is extremely useful as a hole transport material, a light emitting material, and a buffer material of an organic electroluminescence device.

  If the organic EL element of this invention is equipped with the organic layer containing the said polymeric material, an element structure will not be specifically limited. Since the arylamine dendrimer-like compound of the present invention is excellent in solubility, for example, a spin coating method, a casting method, a dipping method, a bar coating method, a roll using a solution, a mixed solution or a melt of these materials is used. The element can be easily produced by a conventionally known coating method such as a coating method. It can also be easily produced by an ink jet method, a Langmuir-Blodgett method, or the like.

  The present invention provides a novel arylamine dendrimer-like compound having superior durability and luminous efficiency over conventional materials, an efficient production method thereof, and an application thereof.

  The novel arylamine dendrimer-like compound of the present invention is excellent in solubility and also in light emission efficiency and current efficiency in the case of an organic EL device. Furthermore, it has very good film formability and stability. It is extremely useful as a conductive polymer for use in electronic devices such as field effect transistors, optical functional devices, and dye-sensitized solar cells as well as hole transport materials, light emitting materials, and buffer materials for organic EL devices. The present invention is very significant industrially.

The measurement result of the infrared spectroscopy analysis of the triarylamine polymer represented by General formula (19) is shown. The measurement result of the infrared spectroscopy analysis of the arylamine dendrimer-like compound synthesize | combined from General formula (19) and tris (4-bromophenyl) amine is shown. The measurement result of the infrared spectroscopy analysis of the arylamine dendrimer-like compound synthesize | combined from General formula (19) and 1,3,5- tribromobenzene is shown. The measurement result of the infrared spectroscopy analysis of the arylamine dendrimer-like compound synthesize | combined from General formula (19) and 1,3,5- tris (4-bromophenyl) benzene is shown.

  Examples of the present invention are shown below, but the present invention is not limited to these Examples.

Reaction Example 1 Synthesis of Arylamine Polymer (19) In a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, 4.04 g (10.0 mmol) of 4,4′-diiodobiphenyl, 4- n-Butylaniline 1.56 g (10.5 mmol), sodium-tert-butoxide 2.31 g (24 mmol; 1.2 equivalents with respect to iodine atoms) and 40 ml of o-xylene were charged. To this mixed solution, 46.0 mg (0.050 mmol; 0.25 mol% with respect to iodine atom) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and 80.9 mg of tri-tert-butylphosphine (0 .40 mmol; 4 equivalents of atoms per palladium atom) in o-xylene (5 ml) was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  After 3 hours, 0.30 g (2.0 mmol) of 4-n-butylaniline was added, and the reaction was further performed for 3 hours. After completion of the reaction, the reaction mixture was cooled to about 80 ° C. and then slowly added to a stirred solution of 90% aqueous acetone (1000 ml). The solid was collected by filtration, washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain a pale yellow powder (yield 92%).

  When the obtained powder was measured by elemental analysis and infrared spectroscopic analysis (infrared spectrophotometer: SYSTEM2000FT-IR, manufactured by Perkin Elmer), it was a triarylamine polymer represented by the following general formula (19). Was confirmed. The measurement result of infrared spectroscopy is shown in FIG. The obtained polymer was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220; column: TSKgelSuperH3000-TSKgelSuperH2000-TSKgelSuperH1000 (both manufactured by Tosoh)). The molecular weight was 7,500 (dispersion degree 1.7).

Reaction Example 2 Synthesis of Arylamine Polymer (20) During cooling, an arylamine polymer represented by the general formula (19) synthesized in Reaction Example 1 was added to a 200 mL four-necked round bottom flask equipped with a thermometer at room temperature. 0.000 g, 0.51 g (5.33 mmol) of sodium-tert-butoxide, and 100 mL of o-xylene were charged. To this mixed solution, 12.2 mg (0.013 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 21.0 mg (0.104 mmol) of o-xylene prepared in advance under a nitrogen atmosphere (5 mL) solution was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, 167.5 mg (1.07 mmol) of bromobenzene was added, and the mixture was aged for 3 hours while heating and stirring at 120 ° C. Subsequently, a solution of 0.362 g (2.14 mmol) of diphenylamine in o-xylene (3 mL) was added, and the mixture was further aged for 3 hours.

  After the reaction, the reaction mixture was cooled to about 80 ° C., 30 g of pure water was added, and slowly added to a stirring solution of 90% acetone aqueous solution (1000 mL). The solid was collected by filtration, purified by silica gel column chromatography using toluene as a developing solvent, and then purified by alumina column chromatography. The eluate was concentrated under reduced pressure and slowly added to a stirred solution of 90% aqueous acetone (1000 mL). The solid was collected by filtration and dried under reduced pressure to obtain 1.75 g of a pale yellow solid (yield 86%).

When the obtained powder was measured by infrared spectroscopic analysis, the peak of 3398 cm ⁻¹ derived from the secondary amine observed in the triarylamine polymer represented by the general formula (19) disappeared, and the general formula (20 It was confirmed that the triarylamine polymer represented by The obtained polymer had a weight average molecular weight of 13,200 and a number average molecular weight of 7,700 (dispersion degree 1.7) in terms of polystyrene.

Example 1
In a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, 1.00 g of arylamine polymer represented by the general formula (19) synthesized in Reaction Example 1 at room temperature (in terms of number average molecular weight: 0.133 mmol) ), 0.77 g (8.0 mmol) of sodium-tert-butoxide, 42.9 mg (0.089 mmol) of tris (4-bromophenyl) amine and 30 ml of o-xylene. To this mixed solution, 46.0 mg (0.050 mmol) of tris (dibenzylideneacetone) dipalladium previously prepared in a nitrogen atmosphere and 80.9 mg (0.40 mmol) of tri-tert-butylphosphine; Equivalents) of o-xylene (5 ml) was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C. A solution of 12.6 mg (0.080 mmol) of bromobenzene in o-xylene (2 ml) was added, and the mixture was further aged at 120 ° C. for 3 hours. Subsequently, a solution of 60.2 mg (0.356 mmol) of diphenylamine in o-xylene (2 ml) was added, followed by further aging for 3 hours.

  After completion of the reaction, the reaction mixture was cooled to about 80 ° C. and then slowly added to a stirred solution of 90% aqueous acetone (1000 ml). The solid was collected by filtration and washed in the order of acetone, water and acetone, and then dried under reduced pressure to obtain a pale yellow powder (yield 80%). The obtained arylamine dendrimer-like compound was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220), and as a result, it had a weight average molecular weight of 463,000 and a number average molecular weight of 26,000 in terms of polystyrene. The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 1 and FIG. 2, respectively.

Example 2
The reaction was performed in the same manner as in Example 1 except that tris (4-bromophenyl) amine was changed to 28.0 mg (0.089 mmol) of 1,3,5-tribromobenzene.

  The obtained arylamine dendrimer-like compound was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220), and as a result, it had a weight average molecular weight of 152,000 and a number average molecular weight of 26,000 in terms of polystyrene. The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 2 and FIG. 3, respectively.

Example 3
The reaction was performed in the same manner as in Example 1 except that tris (4-bromophenyl) amine was changed to 45.9 mg (0.089 mmol) of 1,3,5-tris (4-bromophenyl) benzene.

  The obtained arylamine dendrimer-like compound was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220), and as a result, it had a weight average molecular weight of 534,000 and a number average molecular weight of 18,000 in terms of polystyrene. The measurement results of elemental analysis and infrared spectroscopic analysis are shown in Table 3 and FIG. 4, respectively.

Example 4
In a 100 ml four-necked round bottom flask equipped with a condenser and a thermometer, 0.50 g (1.11 mmol) of N, N′-bis (4-butylphenyl) benzidine and 1.07 g of sodium-tert-butoxide at room temperature. (11.1 mmol), tris (4-bromophenyl) amine 0.36 mg (0.074 mmol) and o-xylene 15 ml were charged. To this mixed solution, 50.8 mg (0.056 mmol) of tris (dibenzylideneacetone) dipalladium previously prepared in a nitrogen atmosphere and 89.0 mg (0.44 mmol) of tri-tert-butylphosphine o-xylene (5 ml) The solution was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C. A solution of 0.35 g (2.22 mmol) of bromobenzene in o-xylene (2 ml) was added, and the mixture was further aged at 120 ° C. for 3 hours. Next, a solution of 0.75 g (4.44 mmol) of diphenylamine in o-xylene (2 ml) was added, followed by further aging for 3 hours.

  After completion of the reaction, the reaction mixture was cooled to about 80 ° C. and then slowly added to a stirred solution of 90% aqueous acetone (1000 ml). The solid was collected by filtration and washed in the order of acetone, water, and acetone, and then dried under reduced pressure to obtain a pale yellow powder (yield 76%). The obtained arylamine dendrimer-like compound was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220), and as a result, it had a weight average molecular weight of 287,000 and a number average molecular weight of 20,300 in terms of polystyrene. Table 4 shows the measurement results of elemental analysis.

Example 5 (Production and Evaluation of Device)
A glass substrate having an ITO transparent electrode having a thickness of 130 nm was ultrasonically washed successively with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Furthermore, what was UV / ozone treated was used as a transparent conductive support substrate.

On this ITO glass substrate, the arylamine dendrimer-like compound synthesized in Example 1 was formed into a film with a thickness of 30 nm by spin coating using the 1.0 wt% chlorobenzene solution. After drying at 160 ° C. for 3 hours, 4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine (2-TNATA, 30 nm) was added on top of 4,4′-bis [N -(1-Naphtyl) -N-phenylamino] biphenyl (α-NPB, 50 nm) and aluminum 8-quinolinol complex (Alq ₃ , 50 nm) were deposited in this order. The organic compound was deposited under the same conditions of a vacuum degree of 1.0 × 10 ⁻⁴ Pa and a deposition rate of 0.3 nm / second.

  Next, lithium fluoride (0.8 nm) and aluminum (150 nm) were deposited in this order to form a metal electrode.

  Furthermore, a protective glass substrate was stacked in a nitrogen atmosphere, and the organic EL sealing agent was heat-cured at 80 ° C. for 3 hours, adhered and sealed.

  Table 5 shows the light emission characteristics when a voltage is applied to the EL element manufactured as described above using the ITO electrode as the positive electrode and the LiF-Al electrode as the negative electrode.

In addition, when the initial luminance of the obtained organic EL element is 2000 cd / m ² , the standardized 50% drive in which the luminance decay time up to 50% of the initial luminance is normalized with the value of Comparative Example 1 described later. Table 6 shows the lifetime. As shown in Table 6, a device having a long lifetime was obtained by using the arylamine dendrimer-like compound of the present invention.

Example 6 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 5 except that the arylamine dendrimer compound synthesized in Example 2 was used instead of the arylamine dendrimer compound synthesized in Example 1. The emission characteristics are shown in Table 5.

Example 7 (Production and Evaluation of Device)
A device was prepared in the same manner as in Example 5 except that the arylamine dendrimer compound synthesized in Example 3 was used instead of the arylamine dendrimer compound synthesized in Example 1. The emission characteristics are shown in Table 5.

Comparative Example 1
In Example 5, an element similar to Example 5 was used except that the arylamine polymer represented by the general formula (20) synthesized in Reaction Example 2 was used instead of the arylamine dendrimer-like compound synthesized in Example 1. The drive life was measured.

  From the above results, the EL device using the arylamine dendrimer-like compound of the present invention can be driven at a low voltage, has improved luminous efficiency and current efficiency, and requires less power consumption.

Claims (8)

The following general formula (1)

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 60 carbon atoms which may have a substituent, and n represents an integer of 1 or more.)
An arylamine polymer skeleton represented by general formulas (2) to (4)

(In the formula, Ar ³ represents an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are Each independently represents an alkyl or alkoxy group having 1 to 18 carbon atoms, or a halogen atom, A represents a nitrogen atom or a phosphorus atom, and a, b, c, d, e, f, and g each independently Represents an integer of 0 to 5. h represents an integer of 3 to 6, and i, j, k, l, o, and p each independently represents an integer of 1 to 5. However, i + j + k and l + o + p represent each Independently represents an integer of 3 to 6. R represents a binding site of the arylamine polymer skeleton represented by the general formula (1).
An arylamine dendrimer-like compound having a structure in which at least one aromatic skeleton represented by 2. The arylamine dendrimer-like compound according to claim 1, wherein Ar ¹ in the general formula (1) is any one of the following general formulas (5) to (8):

(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 18 carbon atoms or an optionally substituted phenyl group, and m is an integer of 1 to 3) Represents). The arylamine dendrimeric compound according to claim 1 or 2, wherein in the general formula (1), Ar ² is any one of the following general formulas (9) to (14).

(Wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ each independently have an alkyl group having 1 to 18 carbon atoms, or a substituent. And q represents an integer of 0 to 5. Ar ^{3 in the} general formula (2) is any one of a phenylene group, a thienylene group, a pyrrolylene group, a naphthylene group, an anthracenylene group, a fluorenylene group, or an N-substituted carbazolylene group, which may have a substituent. The arylamine dendrimer-like compound according to any one of claims 1 to 3. The arylamine dendrimer-like compound according to any one of claims 1 to 4, wherein the weight average molecular weight is in a range of 1,000 to 1,000,000 in terms of polystyrene. The following general formula (15)

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group having 6 to 60 carbon atoms which may have a substituent, and n represents an integer of 1 or more.)
And arylamine polymers represented by general formulas (16) to (18)

(In the formula, Ar ³ represents an arylene group having 6 to 30 carbon atoms or a heteroarylene group having 3 to 30 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ are Each independently represents an alkyl or alkoxy group having 1 to 18 carbon atoms, or a halogen atom, A represents a nitrogen atom or a phosphorus atom, and a, b, c, d, e, f, and g each independently Represents an integer of 0 to 5. h represents an integer of 3 to 6, and i, j, k, l, o, and p each independently represents an integer of 1 to 5. However, i + j + k and l + o + p represent each Independently represents an integer of 3 to 6. X represents a chlorine atom, a bromine atom, or an iodine atom.)
The method for producing an arylamine dendrimer-like compound according to claim 1, wherein at least one polyhalogenated aromatic compound represented by the formula (1) is reacted in the presence of a palladium catalyst and a base. An electronic device using the arylamine dendrimer-like compound according to claim 1. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescence device.

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