JP2000072722A - Manufacture of tertiary aryl amine polymer - Google Patents
Manufacture of tertiary aryl amine polymerInfo
- Publication number
- JP2000072722A JP2000072722A JP10240167A JP24016798A JP2000072722A JP 2000072722 A JP2000072722 A JP 2000072722A JP 10240167 A JP10240167 A JP 10240167A JP 24016798 A JP24016798 A JP 24016798A JP 2000072722 A JP2000072722 A JP 2000072722A
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- JP
- Japan
- Prior art keywords
- tertiary
- reaction
- aryl amine
- solvent
- polymer
- Prior art date
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子写真の感光体
や電界発光素子などの電荷輸送性物質として広く用いら
れている３級アリールアミンの重合物を選択性良く、且
つ高収率で簡便に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tertiary arylamine polymer widely used as a charge-transporting substance such as a photoreceptor for electrophotography and an electroluminescent device, which has a high selectivity, a high yield and a simple process. To a manufacturing method.
【０００２】[0002]
【従来の技術】従来、電子写真や有機電界発光素子に用
いられる電荷輸送層として、トリフェニルアミンや、
Ｎ，Ｎ，Ｎ’，Ｎ’−テトラフェニルジアミノベンゼン
（ＴＰＢ）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラフェニルジア
ミノビフェニル（ＴＰＤ）などの芳香族第３級アミン及
びその誘導体が用いられている。ＴＰＢやＴＰＤのよう
に窒素原子やこれに付いたフェニル基の数が多く、共役
長が長いほど電荷輸送能が向上する。これらの化合物は
芳香族第２級アミンと沃化フェニル、沃化トリル、沃化
ナフチルのような芳香族沃化物とのウルマン反応により
合成されている。2. Description of the Related Art Conventionally, as a charge transporting layer used in electrophotography and organic electroluminescent devices, triphenylamine,
Aromatic tertiary amines such as N, N, N ', N'-tetraphenyldiaminobenzene (TPB) and N, N, N', N'-tetraphenyldiaminobiphenyl (TPD) and derivatives thereof have been used. I have. As in the case of TPB and TPD, the number of nitrogen atoms and the number of phenyl groups attached thereto are large, and the longer the conjugation length, the better the charge transport ability. These compounds are synthesized by the Ullmann reaction of an aromatic secondary amine with an aromatic iodide such as phenyl iodide, tolyl iodide and naphthyl iodide.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、ウルマ
ン反応は、２００度以上の高温を必要とし、収率が低い
などの問題があった。さらに、共役長の長い化合物の合
成には多段階の反応を必要とし、収率が低下する欠点が
あった。However, the Ullmann reaction requires a high temperature of 200 ° C. or more and has a problem such as a low yield. Furthermore, the synthesis of a compound having a long conjugate length requires a multi-step reaction, and has the disadvantage of reducing the yield.
【０００４】本発明が解決しようとする課題は、容易に
入手あるいは製造可能な原料から、穏和な条件下に高収
率で３級アリールアミン重合物を製造する方法を提供す
ることにある。An object of the present invention is to provide a method for producing a tertiary arylamine polymer from a readily available or readily available raw material in a high yield under mild conditions.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の観
点から鋭意検討した結果、３級アリールアミンを酸化カ
ップリングすることにより目的とする化合物を収率良く
簡便に合成できることを見出し、本発明を完成するに至
った。Means for Solving the Problems The present inventors have conducted intensive studies from the above viewpoints and found that the desired compound can be easily synthesized in good yield by oxidative coupling of a tertiary arylamine. The present invention has been completed.
【０００６】即ち、本発明は一般式That is, the present invention relates to the general formula
【化３】 （式中、Ｒは置換または無置換のアリール基又は低級ア
ルキル基を示す。）で表される３級アリールアミンを塩
化鉄の存在下で酸化重合させて、一般式Embedded image (Wherein, R represents a substituted or unsubstituted aryl group or a lower alkyl group). The tertiary arylamine represented by the general formula is oxidized and polymerized in the presence of iron chloride.
【化４】 （式中、Ｒは前記の一般式（１）におけるＲと同一であ
り、ｎは０以上の整数であって、ｎの異なる化合物の混
合物も含む）で表される重合物を製造する方法である。Embedded image (Wherein, R is the same as R in the above general formula (1), n is an integer of 0 or more, and also includes a mixture of compounds having different n). is there.
【０００７】[0007]
【発明の実施の形態】本発明において使用できる上記一
般式（１）で示される３級アリールアミンを例示する
と、メチルジフェニルアミン、トリフェニルアミン、Ｎ
−ｐ−トリルジフェニルアミン、Ｎ−ｍ−トリルジフェ
ニルアミン、Ｎ−ｐ−メトキシフェニルジフェニルアミ
ン、Ｎ−ｍ−メトキシフェニルジフェニルアミンなどが
挙げられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Tertiary arylamines represented by the above general formula (1) which can be used in the present invention include, for example, methyldiphenylamine, triphenylamine, N
-P-tolyldiphenylamine, Nm-tolyldiphenylamine, Np-methoxyphenyldiphenylamine, Nm-methoxyphenyldiphenylamine and the like.
【０００８】本発明においては、酸化剤として塩化鉄
（ＦｅＣｌ3 ）が使用される。上記３級アリールアミン
と塩化鉄のモル比は特に限定されないが、１：０．０５
〜１：２０、好ましくは１：１〜１：１０の範囲で使用
するのが好適である。In the present invention, iron chloride (FeCl 3 ) is used as an oxidizing agent. The molar ratio between the tertiary arylamine and iron chloride is not particularly limited, but is 1: 0.05.
It is suitable to use in the range of １ ： 1: 20, preferably 1: 1１〜1: 10.
【０００９】また、本発明は、溶媒としてベンゼン，ト
ルエン，キシレンなどの芳香族炭化水素，四塩化炭素，
クロロホルム，メチレンクロリド，クロロベンゼン，ジ
クロロベンゼンなどのハロゲン化炭化水素，ジエチルエ
ーテル，テトラヒドロフランなどのエーテルなどを用い
ることができる。この他、アセトニトリル，ジメチルフ
ォルムアミド，ジメチルアセトアミド，プロピレンカー
ボネート，ジメチルスルフォキシドなども用いることが
できる。反応条件は特に限定はされず、反応温度は−２
０度から溶媒の沸点の範囲、反応時間は３０分以上で適
宜選定される。[0009] The present invention also relates to a solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride,
Halogenated hydrocarbons such as chloroform, methylene chloride, chlorobenzene and dichlorobenzene, and ethers such as diethyl ether and tetrahydrofuran can be used. In addition, acetonitrile, dimethylformamide, dimethylacetamide, propylene carbonate, dimethylsulfoxide and the like can also be used. The reaction conditions are not particularly limited, and the reaction temperature is -2.
The range from 0 degree to the boiling point of the solvent and the reaction time are appropriately selected at 30 minutes or more.
【００１０】また、この出願の発明においては、反応条
件を選択することにより、３級アリールアミン２量体の
収量を大きくすることができる。後述の実施例に記載の
ように、３級アリールアミンと酸化剤である塩化鉄との
モル比を約１：４〜１：６とし、反応温度０℃〜４０
℃、反応時間３０分から２時間で反応させると２量体が
選択的に多量に生成され、２量体の生成割合を９５％と
することもできる。In the invention of this application, the yield of the tertiary arylamine dimer can be increased by selecting the reaction conditions. As described in the examples below, the molar ratio of the tertiary arylamine to the oxidizing agent iron chloride is about 1: 4 to 1: 6, and the reaction temperature is 0 ° C. to 40 ° C.
When the reaction is carried out at 30 ° C. for a reaction time of 30 minutes to 2 hours, a large amount of dimer is selectively produced, and the production ratio of the dimer can be 95%.
【００１１】この出願の発明によって得られる３級アリ
ールアミン重合物は、重合度が２から２０位のものが得
られ、特に２量体は有機電界発光素子等に広く用いられ
ている。また、２，３，４量体は、蒸着でアモルファス
フィルムを作成可能であり、１０量体以下のものはポリ
マーに分子分散が可能である。更に、高分子ポリマー
は、単独で薄膜を形成することが出来、新しい用途が考
えられる。The tertiary arylamine polymer obtained by the invention of the present application has a degree of polymerization of 2 to 20. Particularly, the dimer is widely used in organic electroluminescent devices and the like. The dimer, trimer and tetramer can form an amorphous film by vapor deposition, and the dimer and dimer can be molecularly dispersed in a polymer. Furthermore, a high-molecular polymer can form a thin film by itself, and new applications are considered.
【００１２】[0012]
【実施例】以下の実施例によりこの出願の発明を更に詳
細に説明するが、本発明は実施例に限定されるものでは
ない。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１３】〔実施例１〕三口フラスコにトリフェニル
アミン２．４５ｇ（１０ｍｍｏｌ）、クロロホルム８０
ｍｌを入れ、マグネッチックスターラーにより攪拌し、
０℃に保った恒温槽中に設置した。続いて、無水塩化鉄
（III ）６．４８ｇ（４０ｍｍｏｌ）を加えて、１時間
攪拌した。ここでＧＰＣにより反応組成を分析した。Ｇ
ＰＣによる分析条件は以下の通りである。 カラム：スチレン−ジビニルベンゼンゲルビーズ充填
７．６mmφ×３００mm 溶理液：クロロホルム（０．５ｍｌ／ｍｉｎ） 検出器：ＵＶ（２５４ｎｍ） その結果、トリフェニルアミンの２量体９５．６％、ト
リフェニルアミンの３量体以上の混合物が３．４％であ
った。尚、上記合成において使用した原料アミンに対す
る酸化剤（ＦｅＣｌ3 ）のモル当量は４．０，原料アミ
ン１ｍｍｏｌに対する溶媒の仕込量は８ｍｌである。Example 1 In a three-necked flask, 2.45 g (10 mmol) of triphenylamine and 80 parts of chloroform were added.
ml, stirred with a magnetic stirrer,
It was set in a thermostat kept at 0 ° C. Subsequently, 6.48 g (40 mmol) of anhydrous iron (III) chloride was added, and the mixture was stirred for 1 hour. Here, the reaction composition was analyzed by GPC. G
The analysis conditions by PC are as follows. Column: packed with styrene-divinylbenzene gel beads
7.6 mmφ × 300 mm Solution: chloroform (0.5 ml / min) Detector: UV (254 nm) As a result, a mixture of 95.6% of triphenylamine dimer and triphenylamine trimer or more is obtained. It was 3.4%. The molar equivalent of the oxidizing agent (FeCl 3 ) with respect to the raw material amine used in the above synthesis was 4.0, and the charged amount of the solvent with respect to 1 mmol of the raw material amine was 8 ml.
【００１４】反応液をメタノール４００ｍｌ中に入れ攪
拌後、吸引瀘過し、沈殿物をメタノールと水で洗浄し
た。沈殿物をトルエン２００ｍｌに溶かし、不溶物を吸
引瀘過により除去した。トルエンを留去後、白色固体で
あるＮ，Ｎ，Ｎ’，Ｎ’，−テトラフェニル−１，１’
−ビフェニル−４，４’−ジアミンが２．１０ｇ得られ
た。収率は８５．４％であった。得られた化合物のＨ−
１核磁気共鳴スペクトル（Ｈ−１ＮＭＲチャート）を図
１に、Ｃ−１３核磁気共鳴スペクトル（Ｃ−１３ＮＭＲ
チャート）を図２に示した。The reaction solution was placed in 400 ml of methanol, stirred, filtered by suction, and the precipitate was washed with methanol and water. The precipitate was dissolved in 200 ml of toluene, and insolubles were removed by suction filtration. After distilling off toluene, white solid N, N, N ', N',-tetraphenyl-1,1 '
2.10 g of -biphenyl-4,4'-diamine were obtained. The yield was 85.4%. H- of the compound obtained
FIG. 1 shows the 1 nuclear magnetic resonance spectrum (H-1NMR chart), and the C-13 nuclear magnetic resonance spectrum (C-13NMR).
Chart) is shown in FIG.
【００１５】〔実施例２〜１２〕原料として実施例２〜
８においてトリフェニルアミンを使用し、実施例９〜１
２においてはトリルジフェニルアミンを使用した。実施
例１と同様に酸化剤として無水塩化鉄（III ）を、溶媒
としてクロロホルムを使用し、反応時間は１時間、その
他の実験条件を適宜変更して合成を行い、反応液をＧＰ
Ｃにて分析した。この結果を表１に示す。尚、以下の表
における記載、酸化剤仕込当量（ｅｑ）は原料アミンに
対する酸化剤（ＦｅＣｌ3 ）のモル当量であり、溶媒仕
込量（ｍｌ）は、、原料アミン１ｍｍｏｌに対する溶媒
の仕込量である。Examples 2 to 12 Examples 2 to 12 were used as raw materials.
Example 8 using triphenylamine in Example 8
In 2, tolyldiphenylamine was used. Synthesis was carried out in the same manner as in Example 1 except that anhydrous iron (III) chloride was used as the oxidizing agent, chloroform was used as the solvent, the reaction time was 1 hour, the other experimental conditions were appropriately changed, and the reaction solution was GP.
Analyzed at C. Table 1 shows the results. In the following table, the oxidizing agent charge equivalent (eq) is the molar equivalent of the oxidizing agent (FeCl 3 ) with respect to the raw material amine, and the solvent charging amount (ml) is the charged amount of the solvent with respect to 1 mmol of the raw material amine. .
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１から原料アミンと酸化剤のモル比が
１：４〜１：６であって、反応温度０℃〜４０℃、反応
時間１時間で反応を行った場合、２量体の収率が７０〜
９７％となることがわかる。According to Table 1, when the molar ratio of the raw material amine to the oxidizing agent is 1: 4 to 1: 6, and the reaction is carried out at a reaction temperature of 0 ° C. to 40 ° C. and a reaction time of 1 hour, the yield of dimer is obtained. Rate is 70 ~
It turns out that it becomes 97%.
【００１８】〔実施例１３〜１６〕原料アミンとしてｍ
−トリルジフェニルアミンを使用し、酸化剤は無水塩化
鉄（III ）、溶媒としてクロロホルムを使用して、反応
時間を６時間とし、その他の実験条件を適宜変更して実
施例１と同様の方法で合成を行った。この結果を表２に
示す。[Examples 13 to 16]
-Synthesis using the same method as in Example 1 using tolylphenylamine, anhydrous iron (III) chloride as an oxidizing agent, chloroform as a solvent, a reaction time of 6 hours, and other experimental conditions appropriately changed. Was done. Table 2 shows the results.
【００１９】[0019]
【表２】 [Table 2]
【００２０】この結果から、原料である３級アリールア
ミン、反応時間，反応温度等を適宜選択することによっ
て、２量体のみならず３量体以上の３級アリールアミン
重合物を製造することができることが判明した。From these results, it is possible to produce not only a dimer but also a tertiary arylamine polymer of not less than a trimer by appropriately selecting a starting material, a tertiary arylamine, a reaction time, a reaction temperature and the like. It turns out that it can be done.
【００２１】〔実施例１７〜２２〕原料アミンとしてメ
チルジフェニルアミンを使用し、酸化剤は無水塩化鉄
（III ）、溶媒としてプロピレンカーボネートを使用し
て、溶媒の仕込量１０ｍｌとし、その他の実験条件を適
宜変更して実施例１と同様の方法で合成を行った。この
結果を表３に示す。[Examples 17 to 22] Methyldiphenylamine was used as a raw material amine, anhydrous iron (III) chloride was used as an oxidizing agent, and propylene carbonate was used as a solvent. The synthesis was performed in the same manner as in Example 1 with appropriate changes. Table 3 shows the results.
【００２２】[0022]
【表３】 [Table 3]
【００２３】この結果から、原料である３級アリールア
ミン、反応時間、反応温度等の反応条件を適宜選択する
ことによって、生成する３級アリールアミン重合物の重
合度を高くすることができることが判明した。From these results, it was found that the degree of polymerization of the resulting tertiary arylamine polymer can be increased by appropriately selecting the starting material, the tertiary arylamine, the reaction time, the reaction temperature and other reaction conditions. did.
【００２４】〔実施例２３〕原料アミンとしてトリフェ
ニルアミンを使用し、酸化剤として無水塩化鉄（III ）
を仕込み当量４．０で使用した。反応条件は、反応時間
１時間，反応温度４０℃，アミンの濃度２．５ｍｍｏｌ
／ｌ，溶媒の使用量１０ｍｌとして溶媒を下記の表４に
記載のように変更して合成を行った。結果を表４に示
す。Example 23 Triphenylamine was used as a raw material amine, and anhydrous iron (III) chloride was used as an oxidizing agent.
Was used at a charge equivalent of 4.0. The reaction conditions were as follows: reaction time 1 hour, reaction temperature 40 ° C., amine concentration 2.5 mmol
The synthesis was carried out by changing the solvent as shown in Table 4 below, with the solvent used being 10 ml / l and the used amount of the solvent being 10 ml. Table 4 shows the results.
【００２５】[0025]
【表４】 [Table 4]
【００２６】〔実施例２４〕原料アミンとしてｐ−トリ
ルジフェニルアミンを使用し、実施例２３と同様の条件
で合成を行った。結果を表５に示す。Example 24 Synthesis was performed under the same conditions as in Example 23, except that p-tolyldiphenylamine was used as the starting amine. Table 5 shows the results.
【００２７】[0027]
【表５】 [Table 5]
【００２８】〔実施例２５〕原料アミンとしてｍ−トリ
ルジフェニルアミンを使用し、実施例２３と同様の条件
で合成を行った。結果を表６に示す。Example 25 Synthesis was carried out under the same conditions as in Example 23, except that m-tolyldiphenylamine was used as the starting amine. Table 6 shows the results.
【００２９】[0029]
【表６】 [Table 6]
【００３０】[0030]
【発明の効果】本発明の方法は、高温を必要とせず、電
子写真の感光体や電界発光素子などの電荷輸送性物質と
して広く用いられるトリアリールアミンの重合物を選択
性良く、高収率で簡便に製造できるものである。特に、
反応条件を適宜選択することにより、トリアリールアミ
ンの２量体を高収率で得ることが出来、また、反応条件
の変更によって、３量体以上の重合度の高い重合物の生
成割合を高くすることも可能であり、このような高重合
物は長い共役系を有するので、新しい用途に利用するこ
とが考えられる。The method of the present invention does not require a high temperature, and has good selectivity and high yield to a polymer of triarylamine widely used as a charge transporting substance for an electrophotographic photosensitive member or an electroluminescent device. And can be easily manufactured. In particular,
By appropriately selecting the reaction conditions, a triarylamine dimer can be obtained in a high yield, and by changing the reaction conditions, the production ratio of a trimer or higher polymer having a high degree of polymerization can be increased. Since such a high polymer has a long conjugated system, it may be used for a new use.
【図１】実施例１で得られた化合物のＨ−１核磁気共鳴
スペクトルである。FIG. 1 is an H-1 nuclear magnetic resonance spectrum of the compound obtained in Example 1.
【図２】実施例１で得られた化合物のＣ−１３各磁気共
鳴スペクトルである。FIG. 2 shows C-13 magnetic resonance spectra of the compound obtained in Example 1.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA06 BB08A BB08B BC66A BC66B BD12A BD12B CB07 CB46 DA02 4H006 AA02 AC12 BA19 BA37 BC10 BC19 BC34 4H039 CA41 CD10 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA06 BB08A BB08B BC66A BC66B BD12A BD12B CB07 CB46 DA02 4H006 AA02 AC12 BA19 BA37 BC10 BC19 BC34 4H039 CA41 CD10
Claims (2)
ルキル基を示す。）で表される３級アリールアミンを塩
化鉄の存在下で酸化重合させて、一般式 【化２】 （式中、Ｒは前記の一般式（１）におけるＲと同一であ
り、ｎは０以上の整数であって、ｎの異なる化合物の混
合物も含む）で表される３級アリールアミン重合物を製
造する方法。1. A compound of the general formula (Wherein, R represents a substituted or unsubstituted aryl group or lower alkyl group). Oxidative polymerization of a tertiary arylamine represented by the following formula: (Wherein, R is the same as R in the above general formula (1), n is an integer of 0 or more, and also includes a mixture of compounds having different n). How to make.
約１：４〜１：６とし、溶媒の存在下に反応温度０〜４
０℃、反応時間３０分から２時間で反応を行い、一般式
（１）で表される３級アリールアミンから一般式（２）
で表される重合物のうち、２量体を主とする３級アリー
ルアミン重合物を製造することを特徴とする請求項１に
記載の方法。2. A tertiary arylamine and iron chloride having a molar ratio of about 1: 4 to 1: 6 and a reaction temperature of 0 to 4 in the presence of a solvent.
The reaction is carried out at 0 ° C. for a reaction time of 30 minutes to 2 hours, and the tertiary arylamine represented by the general formula (1) is converted to the general formula (2)
The method according to claim 1, wherein a tertiary arylamine polymer mainly composed of a dimer is produced from the polymer represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10240167A JP2000072722A (en) | 1998-08-26 | 1998-08-26 | Manufacture of tertiary aryl amine polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10240167A JP2000072722A (en) | 1998-08-26 | 1998-08-26 | Manufacture of tertiary aryl amine polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000072722A true JP2000072722A (en) | 2000-03-07 |
Family
ID=17055498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10240167A Pending JP2000072722A (en) | 1998-08-26 | 1998-08-26 | Manufacture of tertiary aryl amine polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000072722A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6998181B2 (en) | 2000-09-26 | 2006-02-14 | Cambridge Display Technology Limited | Polymer and uses thereof |
| JP2010202638A (en) * | 2009-02-05 | 2010-09-16 | Hodogaya Chem Co Ltd | Method for producing n,n,n',n'-tetraarylbenzidine derivative |
| WO2010149259A2 (en) | 2009-06-22 | 2010-12-29 | Merck Patent Gmbh | Conducting formulation |
| WO2011076324A1 (en) | 2009-12-23 | 2011-06-30 | Merck Patent Gmbh | Compositions comprising organic semiconducting compounds |
| WO2011128035A1 (en) | 2010-04-12 | 2011-10-20 | Merck Patent Gmbh | Composition and method for preparation of organic electronic devices |
| WO2011147523A1 (en) | 2010-05-27 | 2011-12-01 | Merck Patent Gmbh | Formulation and method for preparation of organic electronic devices |
| JP2017064680A (en) * | 2015-10-02 | 2017-04-06 | トヨタ自動車株式会社 | Catalyst for purifying exhaust gas, and method for manufacturing the same |
-
1998
- 1998-08-26 JP JP10240167A patent/JP2000072722A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6998181B2 (en) | 2000-09-26 | 2006-02-14 | Cambridge Display Technology Limited | Polymer and uses thereof |
| JP2010202638A (en) * | 2009-02-05 | 2010-09-16 | Hodogaya Chem Co Ltd | Method for producing n,n,n',n'-tetraarylbenzidine derivative |
| WO2010149259A2 (en) | 2009-06-22 | 2010-12-29 | Merck Patent Gmbh | Conducting formulation |
| WO2011076324A1 (en) | 2009-12-23 | 2011-06-30 | Merck Patent Gmbh | Compositions comprising organic semiconducting compounds |
| WO2011128035A1 (en) | 2010-04-12 | 2011-10-20 | Merck Patent Gmbh | Composition and method for preparation of organic electronic devices |
| WO2011147523A1 (en) | 2010-05-27 | 2011-12-01 | Merck Patent Gmbh | Formulation and method for preparation of organic electronic devices |
| JP2017064680A (en) * | 2015-10-02 | 2017-04-06 | トヨタ自動車株式会社 | Catalyst for purifying exhaust gas, and method for manufacturing the same |
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