JP2012082136A - Triazine derivative, method for producing the same, and organic semi-conductor element containing the same as constituent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which is used as an electron transport material in an organic semiconductor element to reduce a driving voltage and simultaneously has high heat resistance.SOLUTION: The triazine derivative represented by general formula (1) (wherein, Ar is a di to tetra-cyclic aromatic hydrocarbon group) is produced, and an organic semi-conductor element containing the same as a constituent is produced.

Description

  The present invention relates to a triazine derivative having a polycyclic aromatic group, a method for producing the same, and an organic semiconductor device containing the triazine derivative, for example, a novel material for improving an organic transistor and an organic EL device. More particularly, the present invention relates to a triazine derivative having an anthryl group, a phenanthryl group, and a pyrenyl group useful as a constituent component of an organic semiconductor element and a method for producing the same, and relates to a low voltage and high heat resistance organic material using the triazine derivative in at least one organic compound layer. The present invention relates to a semiconductor element.

  In recent years, research on organic semiconductor elements using organic semiconductor materials has been extensively performed, and it has become possible to realize flexible devices. Examples of the organic semiconductor element include an organic electroluminescent element, an organic transistor, and an organic solar cell. In particular, the organic electroluminescent element has attracted attention as a favorite of the next generation flat panel display and has already been put into practical use. An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the excitons generated are deactivated. Organic transistors are expected as an alternative to current silicon transistors.

In particular, from the viewpoint of reducing the environmental load, conversion from inorganic to organic is expected. There is mobility as a material required as a material for an organic transistor, and mobility (1 cm ² / V · SEC) comparable to amorphous silicon is required. Furthermore, a high glass transition temperature (Tg) that can withstand high temperature driving is required.

  Patent Document 1 discloses an example in which a 1,3,5-triazine derivative is used for an organic electroluminescent device, but these do not have a polycyclic aromatic group and are different from the triazine derivative of the present invention.

  Examples in which a 1,3,5-triazine derivative having a polycyclic aromatic group is used in an organic electroluminescence device are disclosed in Patent Documents 2 and 3, but the triazine derivative described in Patent Document 2 is a polycyclic aromatic compound. It is limited to those causing structural isomerism due to steric hindrance of the group, and is different from the triazine derivative of the present invention.

  In addition, the triazine derivative described in Patent Document 3 has methyl on the phenyl group substituted at the 2,4,6 position of 1,3,5-triazine, and the triazine derivative of the present invention Are different.

  Further, Documents 1 to 3 describe only examples having the same substituents at the 2,4,6 positions of 1,3,5-triazine, and specific examples relating to the electron mobility and Tg of the triazine derivative. There is no description. In order to be used in organic electroluminescent devices, amorphousness without unevenness in the thin film state is important. However, a highly symmetric triazine derivative having the same substituents at the 2, 4 and 6 positions has high crystallinity. There is a point.

  The compound described in Patent Document 4 includes a 1,3,5-triazine derivative having a condensed ring, but does not include a compound having two biphenyl groups on the triazine ring. Different from derivatives. In addition, although the compound 6-13 described in the document refers to a 1,3,5-triazine derivative having a pyrenyl group, there is no specific example, and there is no description about Tg and mobility. .

JP 2008-280330 A JP 2001-143869 A Japanese Patent No. 4106974 Japanese Patent Laid-Open No. 2004-2297

  A conventional organic semiconductor element has a high driving voltage, and heat generated by a high driving voltage promotes the decomposition of the organic semiconductor element, thereby causing the life of the element to be shortened.

  The reason why a high drive voltage is required is that the electron mobility of the material constituting the organic semiconductor element is low. Further, in order to improve the durability of the element, it is necessary to suppress the crystallinity of the material and to use a highly amorphous material. Therefore, a material having a high electron mobility, a high Tg, and a high amorphous property is required, but none of them satisfies these simultaneously.

  As a result of intensive studies to solve the above problems, the present inventors have a biphenylyl group at the 2,4 position of the 1,3,5-triazine ring and a different substituent at the 6 position. The triazine derivative (1) having an asymmetric structure can form an amorphous thin film by vacuum deposition, and when these are used for an organic semiconductor element such as an organic electroluminescent element, a general-purpose material is used. It has been found that higher electron mobility can be achieved than in the case, and the present invention has been completed.

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

（式中、Ａｒは２〜４環の多環芳香族炭化水素基を表す。）で示されるトリアジン誘導体に関するものである。

(Wherein Ar represents a 2- to 4-ring polycyclic aromatic hydrocarbon group).

  The present invention also provides a general formula (2)

（式中、Ａｒは２〜４環の多環芳香族炭化水素基を表す。Ｒは水素原子、炭素数１〜４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ）_２の２つのＲは同一又は異なっていてもよい。又、２つのＲは一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）で示される化合物と、一般式（３）

(In the formula, Ar represents a polycyclic aromatic hydrocarbon group having 2 to 4 rings. R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and two Rs of B (OR) ₂ are The two Rs may be combined to form an oxygen atom and a boron atom to form a ring.) And a compound represented by the general formula (3)

（式中、Ｘは脱離基を表す。）で示される化合物とを、塩基及びパラジウム触媒の存在下にカップリング反応させることを特徴とする一般式（１）

(Wherein X represents a leaving group) and a coupling reaction in the presence of a base and a palladium catalyst.

（式中、Ａｒは２〜４環の多環芳香族炭化水素基を表す。）で示されるトリアジン誘導体の製造方法に関するものである。

(Wherein Ar represents a 2- to 4-ring polycyclic aromatic hydrocarbon group).

  Furthermore, the present invention relates to a general formula (1)

（式中、Ａｒは２〜４環の多環芳香族炭化水素基を表す。）で示されるトリアジン誘導体を構成成分とすることを特徴とする有機半導体素子に関するものである。

The present invention relates to an organic semiconductor element characterized by comprising a triazine derivative represented by the formula (wherein Ar represents a 2- to 4-ring polycyclic aromatic hydrocarbon group).

  Hereinafter, the present invention will be described in detail.

  Examples of the 2- to 4-ring polycyclic aromatic hydrocarbon group represented by Ar include a naphthyl group, an anthryl group, a tetracenyl group, a phenanthryl group, a triphenylenyl group, and a pyrenyl group.

  Examples of the naphthyl group represented by Ar include a 1-naphthyl group and a 2-naphthyl group. A 1-naphthyl group is preferable in terms of easy synthesis.

  Examples of the anthryl group represented by Ar include a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group. From the viewpoint of easy synthesis, a 9-anthryl group is more preferable.

  Examples of the phenanthryl group represented by Ar include a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. A 9-phenanthryl group is more preferable in terms of easy synthesis.

  Examples of the pyrenyl group represented by Ar include a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group. A 1-pyrenyl group is more preferable in terms of easy synthesis.

  Examples of the tetracenyl group represented by Ar include a 1-tetracenyl group, a 2-tetracenyl group, and a 5-tetracenyl group.

  Examples of the triphenylenyl group represented by Ar include a 1-triphenylenyl group and a 2-triphenylenyl group.

  Next, the manufacturing method of this invention is demonstrated. The triazine derivative (1) of the present invention can be produced by the method shown by the following reaction formula.

（式中、Ａｒは２〜４環の多環芳香族炭化水素基を表す。Ｘは脱離基を表す。Ｒは水素原子、炭素数１〜４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ）_２の２つのＲは同一又は異なっていてもよい。又、２つのＲは一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）
化合物（２）におけるＢ（ＯＲ）_２としては、Ｂ（ＯＨ）_２、Ｂ（ＯＭｅ）_２、Ｂ（Ｏ^ｉＰｒ）_２、Ｂ（ＯＢｕ）_２、Ｂ（ＯＰｈ）_２等が例示できる。又、２つのＲ^１が一体となって酸素原子及びホウ素原子を含んで環を形成した場合のＢ（ＯＲ）_２の例としては、次の（Ｉ）から（ＶＩ）で示される基が例示でき、収率がよい点で（ＩＩ）で示される基が好ましい。

(In the formula, Ar represents a 2-4 ring polycyclic aromatic hydrocarbon group, X represents a leaving group, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; OR) The _two Rs in 2 may be the same or different, and the two Rs may together form an oxygen atom and a boron atom to form a ring.
Examples of B (OR) ₂ in the compound (2) include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , and B (OPh) ₂ . Examples of B (OR) ₂ in the case where two R ^1s are combined to form a ring containing an oxygen atom and a boron atom include the following groups (I) to (VI). The group represented by (II) is preferable in that the yield is good.

化合物（２）の好ましい例としては、次の２−１から２−１３（式中、Ｒは水素原子、炭素数１〜４のアルキル基又はフェニル基を表し、Ｂ（ＯＲ）_２の２つのＲは同一又は異なっていてもよい。又、２つのＲは一体となって酸素原子及びホウ素原子を含んで環を形成することもできる。）を例示できるが、本発明はこれらに限定されるものではない。

Preferable examples of the compound (2) include the following 2-1 to 2-13 (wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and _two of B (OR) ₂ R may be the same or different, and two Rs may be combined to form an oxygen atom and a boron atom to form a ring), but the present invention is limited to these. It is not a thing.

一般式（２）で示される化合物は、例えば、特開２００１−３３５５１６号公報に開示されている方法を用いて製造することができる。

The compound represented by the general formula (2) can be produced, for example, using a method disclosed in JP-A No. 2001-335516.

  The compound represented by the general formula (3) can be produced, for example, according to the method described in JP-A-2006-62962.

  The leaving group represented by X in the compound (3) represents a chlorine atom, a bromine atom or an iodine atom. A bromine atom is preferable in terms of a good yield.

  “Step 1” is a method for producing the triazine derivative (1) of the present invention by reacting the compound (2) with the compound (3) in the presence of a base and a palladium catalyst, and a general Suzuki-Miyaura reaction. By applying the above reaction conditions, the target product can be obtained in good yield.

  Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Furthermore, complex such as π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium and dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium. A compound can be illustrated.

  These palladium catalysts can be used alone or by adding a tertiary phosphine in a reaction system containing a palladium catalyst to prepare a complex compound. The tertiary phosphine that can be used in this case includes triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4, 5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 ′-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) ) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 '-Bis (diphenylphosphino Ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl And 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl. A combination of palladium acetate and tri (tert-butyl) phosphine is preferable because it is easily available and yields are good.

  Further, the molar ratio of the tertiary phosphine and the palladium catalyst used in “Step 1” is not particularly limited, but is preferably 1:10 to 10: 1, and 1: 2 to 5: 1 in terms of good yield. More desirable. Although there is no restriction | limiting in particular in the molar ratio of the palladium catalyst used for reaction, and a compound (3), 1: 200 to 1: 2 is desirable, and 1: 100 to 1:10 is further more desirable at the point with a sufficient yield.

  It is essential to carry out the reaction of “Step 1” for the presence of a base. At this time, the base that can be used is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride. Etc., and cesium carbonate, potassium carbonate, and sodium hydroxide are desirable in terms of good yield. Although there is no restriction | limiting in particular in the molar ratio of a base and a compound (2), 1: 2 to 10: 1 is desirable, and 1: 1 to 3: 1 is further more desirable at the point with a sufficient yield.

  The molar ratio of the compound (2) and the compound (3) used in “Step 1” is not particularly limited, but 2: 1 to 5: 1 is desirable, and 2: 1 to 3: 1 is preferable in terms of a good yield. More desirable.

  The reaction of “Step 1” can also be carried out in a solvent. In this case, examples of the solvent that can be used include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, toluene, benzene, diethyl ether, and xylene, and these may be used in appropriate combination. It is desirable to use tetrahydrofuran in terms of a good yield.

  The reaction of “Step 1” can be carried out at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably carried out at 40 ° C. to 80 ° C. in terms of a good yield.

  The triazine derivative (1) can be obtained by performing a normal treatment after completion of “Step 1”. You may refine | purify by recrystallization, a column, or sublimation as needed.

Although the manufacturing method of the thin film for organic semiconductor elements which consists of the triazine derivative (1) of this invention is not specifically limited, the film-forming by a vacuum evaporation method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is determined by a commonly used diffusion pump, turbo molecular pump, cryopump, etc. in consideration of the manufacturing tact time and manufacturing cost of manufacturing the organic semiconductor element. About 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa that can be reached is desirable. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed. Further, since the triazine derivative (1) has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran or the like, a spin coating method, an inkjet method, a cast using a general-purpose apparatus. It is also possible to form a film by the dip method or the like.

  The thin film comprising the triazine derivative (1) of the present invention has high heat resistance and electron transport capability, and is therefore useful as a material for organic semiconductor elements, and particularly used as an electron transport material, a hole blocking material, a light emitting host material, and the like. The thin film comprising the triazine derivative (1) of the present invention can be used as a component of the organic electroluminescence device. Furthermore, since it has high mobility and high Tg, it is also useful as an organic transistor.

It is sectional drawing of the organic-semiconductor element produced by embodiment (element evaluation).

EXAMPLES Hereinafter, although an Example and a test example are given and this invention is demonstrated further in detail, this invention is not limited to these.
Example-1

アルゴン気流下、９−フェナントレンボロン酸（０．９９ｇ，４．４６ｍｍｏｌ）、２，４−ビス（４−ビフェニリル）−６−（４−ブロモフェニル）−１，３，５−トリアジン（２．００ｇ，３．７０ｍｍｏｌ）、酢酸パラジウム（１６．６ｍｇ，０．０７４ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン（０．０２２ｍｍｏｌ）を含むトルエン溶液（０．０２２ｍＬ）をテトラヒドロフラン（１６６ｍＬ）に懸濁し、７０℃に昇温した。これに４Ｎ−ＮａＯＨ水溶液（６．９４ｍＬ，２７．８ｍｍｏｌ）を滴下した後、３時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた固体をｏ−キシレンから再結晶し、目的物の２，４−ビス（４−ビフェニリル）−６−［４−（９−フェナントリル）フェニル］−１，３，５−トリアジンの灰色固体（収量１．４７ｇ，収率６２％）を得た。

Under an argon stream, 9-phenanthreneboronic acid (0.99 g, 4.46 mmol), 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine (2.00 g) , 3.70 mmol), palladium acetate (16.6 mg, 0.074 mmol) and a toluene solution (0.022 mL) containing tri-tert-butylphosphine (0.022 mmol) are suspended in tetrahydrofuran (166 mL) and heated to 70 ° C. The temperature rose. 4N-NaOH aqueous solution (6.94 mL, 27.8 mmol) was dripped at this, Then, it recirculate | refluxed for 3 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained solid was recrystallized from o-xylene, and the desired 2,4-bis (4-biphenylyl) -6- [4- (9-phenanthryl) phenyl] -1,3,5-triazine gray solid (Yield 1.47 g, 62% yield) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.42 (t, J = 7.3 Hz, 2H), 7.52 (t, J = 7.6 Hz, 4H), 7.58 (t, J = 7.2 Hz, 1H), 7.66 (t , J = 7.5 Hz, 1H), 7.72 (t, J = 7.0 Hz, 2H), 7.73 (d, J = 7.1 Hz, 4H), 7.80 (s, 1H), 7 .80 (d, J = 8.3 Hz, 2H), 7.84 (d, J = 8.5 Hz, 4H), 7.96 (d, J = 7.8 Hz, 1H), 8.00 (d, J = 8.3 Hz, 1H), 8.76 (d, J = 8.3 Hz, 1H), 8.82 (d, J = 8.2 Hz, 1H), 8.91 (d, J = 8.3 Hz) , 4H), 8.96 (d, J = 8.3 Hz, 2H).
The Tg of the obtained compound was 107 ° C.
Example-2

アルゴン気流下、９−アントラセンボロン酸（０．７０ｇ，３．１５ｍｍｏｌ）、２，４−ビス（４−ビフェニリル）−６−（４−ブロモフェニル）−１，３，５−トリアジン（１．４２ｇ，２．６３ｍｍｏｌ）、酢酸パラジウム（５．９０ｍｇ，０．０２６ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン（０．０７９ｍｍｏｌ）を含むトルエン溶液（０．０７９ｍＬ）をテトラヒドロフラン（１２８ｍＬ）に懸濁し、７０℃に昇温した。これに４Ｎ−ＮａＯＨ水溶液（４．９３ｍＬ，１９．７ｍｍｏｌ）を滴下した後、１．５時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた固体をｏ−キシレンから再結晶し、目的物の２−［４−（９−アントリル）フェニル］−４，６−ビス（４−ビフェニリル）−１，３，５−トリアジンの灰色固体（収量０．７２ｇ，収率４３％）を得た。

Under an argon stream, 9-anthraceneboronic acid (0.70 g, 3.15 mmol), 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine (1.42 g) , 2.63 mmol), palladium acetate (5.90 mg, 0.026 mmol) and tri-tert-butylphosphine (0.079 mmol) in toluene solution (0.079 mL) was suspended in tetrahydrofuran (128 mL) and heated to 70 ° C. The temperature rose. A 4N-NaOH aqueous solution (4.93 mL, 19.7 mmol) was added dropwise thereto, and the mixture was refluxed for 1.5 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained solid was recrystallized from o-xylene, and the desired 2- [4- (9-anthryl) phenyl] -4,6-bis (4-biphenylyl) -1,3,5-triazine gray solid (Yield 0.72 g, yield 43%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.37-7.45 (m, 4H), 7.48-7.53 (m, 6H), 7.69-7.77 (m, 8H), 7.85 (d, J = 8.8 Hz) , 4H), 8.09 (d, J = 8.5 Hz, 2H), 8.56 (s, 1H), 8.93 (d, J = 8.6 Hz, 4H), 9.03 (d, J = 8.5 Hz, 2H).
The Tg of the obtained compound was 100 ° C.
Example-3

アルゴン気流下、１−ピレンボロン酸（０．５５ｇ，２．２４ｍｍｏｌ）、２，４−ビス（４−ビフェニリル）−６−（４−ブロモフェニル）−１，３，５−トリアジン（１．００ｇ，１．８５ｍｍｏｌ）、酢酸パラジウム（４．１５ｍｇ，０．０１８ｍｍｏｌ）及びトリ−ｔｅｒｔ−ブチルホスフィン（０．０５６ｍｍｏｌ）を含むトルエン溶液（０．０５６ｍＬ）をテトラヒドロフラン（７５ｍＬ）に懸濁し、７０℃に昇温した。これに４ＮーＮａＯＨ水溶液（３．４７ｍＬ，１３．９ｍｍｏｌ）を滴下した後、３時間還流した。室温まで冷却後、減圧下で低沸点成分を留去した後、メタノールを加え、析出した固体をろ別した。得られた固体をｏ−キシレンから再結晶し、目的物の２，４−ビス（４−ビフェニリル）−６−［４−（１−ピレニル）フェニル］−１，３，５−トリアジンの灰色固体（収量０．８６ｇ，収率７０％）を得た。

Under an argon stream, 1-pyreneboronic acid (0.55 g, 2.24 mmol), 2,4-bis (4-biphenylyl) -6- (4-bromophenyl) -1,3,5-triazine (1.00 g, 1.85 mmol), palladium acetate (4.15 mg, 0.018 mmol) and tri-tert-butylphosphine (0.056 mmol) in toluene solution (0.056 mL) were suspended in tetrahydrofuran (75 mL), and the temperature was raised to 70 ° C. Warm up. A 4N-NaOH aqueous solution (3.47 mL, 13.9 mmol) was added dropwise thereto, and the mixture was refluxed for 3 hours. After cooling to room temperature, low-boiling components were distilled off under reduced pressure, methanol was added, and the precipitated solid was filtered off. The obtained solid was recrystallized from o-xylene, and the desired 2,4-bis (4-biphenylyl) -6- [4- (1-pyrenyl) phenyl] -1,3,5-triazine gray solid (Yield 0.86 g, yield 70%) was obtained.

¹ H-NMR (CDCl ₃ ): δ. 7.43 (t, J = 7.5 Hz, 2H), 7.52 (t, J = 7.8 Hz, 4H), 7.74 (d, J = 7.2 Hz, 4H), 7.85 (d , J = 8.5 Hz, 4H), 7.89 (d, J = 8.2 Hz, 2H), 8.03-8.14 (m, 5H), 8.20-8.30 (m, 4H) , 8.92 (d, J = 8.7 Hz, 4H), 9.01 (d, J = 8.3 Hz, 2H).
The resulting compound had a Tg of 113 ° C.
Test Example-1
First, a method for manufacturing a mobility element will be described. As the substrate, a glass substrate with an ITO transparent electrode in which an ITO (indium tin oxide) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning.

2,4-bis (4-biphenylyl) -6- [4- (1-pyrenyl) phenyl] -1, heated by a resistance heating method after depressurizing the inside of the vacuum evaporation tank to 3.6 × 10 ⁻⁶ Torr, 3,5-Triazine was vacuum deposited on the substrate at a deposition rate of 3-5 kg / SEC. The film thickness after film formation was 1.6 μm as measured with a stylus film thickness meter (DEKTAK). Next, a metal mask was disposed on the substrate so as to be orthogonal to the ITO stripe, and a 2 mm wide Al film was vacuum-deposited with a thickness of 100 nm. As a result, an operation area of 2 mm square for mobility measurement was obtained. This substrate was sealed in a nitrogen atmosphere glove box having an oxygen / water concentration of 1 ppm or less. For the sealing, an epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) was used.

  Next, a method for measuring the mobility of the mobility element will be described. The mobility of the charge transport material can be measured by any method, but this time, a time-of-flight mobility measurement method, which is a general measurement method, was used. The mobility measuring apparatus manufactured by Optel Co., Ltd. was used. The measurement was performed at room temperature, and the mobility was determined from the moving speed of the charge generated when the nitrogen laser was irradiated from the ITO transparent electrode side to the Al electrode.

As a result, the mobility of 2,4-bis (4-biphenylyl) -6- [4- (1-pyrenyl) phenyl] -1,3,5-triazine was 4.3 × 10 ⁻⁴ cm ² / V ·. It was SEC. This value was higher than 1 × 10 ⁻⁶ cm ² / V · SEC of a hydroxyquinoline aluminum complex (Alq) that is a general electron transport material described in JP-A No. 2002-158091.
Test example-2
The mobility of 2,4-bis (4-biphenylyl) -6- [4- (9-phenanthryl) phenyl] -1,3,5-triazine was measured in the same manner as in Test Example-1. As a result, the mobility was 4.0 × 10 ⁻⁴ cm ² / V · SEC.

  It was confirmed that the organic thin film using the triazine derivative (1) of the present invention has higher electron mobility and Tg compared to the existing materials. Furthermore, the thin film comprising the triazine derivative (1) of the present invention has high surface smoothness and amorphous properties, and is useful as a material for organic semiconductor elements. Accordingly, the thin film comprising the triazine derivative (1) of the present invention is expected to be used as a constituent component of the organic electroluminescence device. Furthermore, since it has high mobility and high Tg, it is also useful as an organic transistor.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. 4. Light emitting layer Electron transport layer 6. Cathode layer

Claims (7)

General formula (1)

(Wherein Ar represents a 2- to 4-ring polycyclic aromatic hydrocarbon group).   The triazine derivative according to claim 1, wherein Ar is a phenanthryl group, an anthryl group or a pyrenyl group.   The triazine derivative according to claim 1 or 2, wherein Ar is a 9-phenanthryl group, a 9-anthryl group, or a 1-pyrenyl group. General formula (2)

(In the formula, Ar represents a polycyclic aromatic hydrocarbon group having 2 to 4 rings. R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and two Rs of B (OR) ₂ are The two Rs may be combined to form an oxygen atom and a boron atom to form a ring.) And a compound represented by the general formula (3)

(Wherein X represents a leaving group) and a coupling reaction in the presence of a base and a palladium catalyst, the compound represented by the general formula (1)

(In the formula, Ar represents a 2-4 ring polycyclic aromatic hydrocarbon group).   The production method according to claim 4, wherein the palladium catalyst is a palladium catalyst having a tertiary phosphine as a ligand.   The production method according to claim 5, wherein the tertiary phosphine is triphenylphosphine or tri-tert-butylphosphine. General formula (1)

An organic semiconductor element comprising a triazine derivative represented by the formula (wherein Ar represents a 2- to 4-ring polycyclic aromatic hydrocarbon group).

Images