JP2704200B2 - Fluorine-containing pyromellitic anhydride and method for producing the same - Google Patents
Fluorine-containing pyromellitic anhydride and method for producing the sameInfo
- Publication number
- JP2704200B2 JP2704200B2 JP63165056A JP16505688A JP2704200B2 JP 2704200 B2 JP2704200 B2 JP 2704200B2 JP 63165056 A JP63165056 A JP 63165056A JP 16505688 A JP16505688 A JP 16505688A JP 2704200 B2 JP2704200 B2 JP 2704200B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- pyromellitic anhydride
- anhydride
- producing
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はポリイミドのモノマーとなりうる新規な含フ
ツ素ピロメリツト酸無水物及びその製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a novel fluorine-containing pyromellitic anhydride which can be a monomer of polyimide and a method for producing the same.
（従来の技術） ポリイミドは種々の有機ポリマーの中で耐熱性に優れ
ているため、宇宙、航空分野から電子通信分野まで幅広
く使われ始めている。特に最近では、単に耐熱性に優れ
ているだけでなく、用途に応じて種々の性能を合わせ持
つことが期待されている。例えばプリント板や、LSI用
の層間絶縁膜などでは、熱膨張計数、誘電率が小さいこ
とが期待され、光通信分野では屈折率が小さいことが期
待されている。しかしながら、これらの性能に充分満足
のいくポリイミドは得られていない。これらのポリイミ
ドを得るためには、ポリイミドの主鎖をできる限り剛直
構造にし低熱膨張性を発現させ、さらにモノマーである
テトラカルボン酸二無水物又はジアミンに低誘電率性、
低屈折率性を発現する置換基を導入する方法が考えられ
る。例えばエポキシ樹脂においては、ジャーナル オブ
ポリマー サイエンス（Journal of Polymer Scienc
e）のパート（Part）Ｃ、ポリマー レターズ（Polymer
Letters）、第24巻、第249頁（1986）に示されている
ようにエポキシ樹脂の硬化剤に多フツ素置換基を導入す
ることにより、これまでのエポキシ樹脂の中でもつとも
低い誘電率を達成している。(Prior Art) Polyimide is excellent in heat resistance among various organic polymers, and thus has begun to be widely used in the fields of space and aviation to the field of electronic communication. In particular, recently, it is expected that not only excellent heat resistance but also various performances may be obtained depending on applications. For example, printed circuit boards and interlayer insulating films for LSIs are expected to have low thermal expansion coefficients and low dielectric constants, and are expected to have low refractive indexes in the optical communication field. However, polyimides which are sufficiently satisfactory in these properties have not been obtained. In order to obtain these polyimides, the main chain of the polyimide has a rigid structure as much as possible to exhibit low thermal expansion, and furthermore, a low dielectric constant of tetracarboxylic dianhydride or diamine as a monomer,
A method of introducing a substituent exhibiting a low refractive index can be considered. For example, in the case of epoxy resins, the Journal of Polymer Scienc
e) Part C, Polymer Letters
Letters), Vol. 24, p. 249 (1986), by introducing a polyfluorinated substituent into the epoxy resin curing agent, it is possible to reduce the dielectric constant of all epoxy resins to date. Have achieved.
また特開昭61−44969号公報で示されているように、
屈折率においても多フツ素置換基を導入することによ
り、これまでのエポキシ樹脂の中で最も低い屈折率を達
成している。このようにフツ素置換基を導入することに
より、誘電率、屈折率の低減が期待できる。Also, as shown in JP-A-61-44969,
The introduction of a polyfluorine substituent also achieves the lowest refractive index among epoxy resins so far. By introducing a fluorine substituent in this way, a reduction in the dielectric constant and the refractive index can be expected.
（発明が解決しようとする課題） しかしながら、これまでにポリイミドにフツ素置換基
を導入して、低熱膨張係数、低誘電率、低屈折率を達成
したという報告はない。また、フツ素化ポリイミド用含
フツ素酸無水物、含フツ素ジアミンの合成例は少なく、
今後多くのフツ素化ポリイミド用モノマーの出現が期待
されている。(Problems to be Solved by the Invention) However, there is no report to date that a fluorine substituent is introduced into polyimide to achieve a low coefficient of thermal expansion, a low dielectric constant, and a low refractive index. Also, there are few synthesis examples of fluorinated anhydrides for fluorinated polyimides and fluorinated diamines,
It is expected that many fluorinated polyimide monomers will appear in the future.
本発明は目的は従来のポリイミドでは有していなかつ
た低熱膨張係数、低誘電率、低屈折率を有するポリイミ
ドを合成するのに必要な含フツ素ピロメリツト酸無水物
及びその製造方法を提供することにある。An object of the present invention is to provide a fluorine-containing pyromellitic anhydride which is necessary for synthesizing a polyimide having a low coefficient of thermal expansion, a low dielectric constant, and a low refractive index, which is not possessed by a conventional polyimide, and a method for producing the same. It is in.
（課題を解決するための手段） 本発明を概説すれば、本発明の第１の発明は含フツ素
ピロメリツト酸無水物に関する発明であつて、下記一般
式I: （式中Ｙは水素又はCnF2n+1基、ｎは２〜10の数を示
す）で表されることを特徴とする。(Means for Solving the Problems) To summarize the present invention, the first invention of the present invention relates to a fluorine-containing pyromellitic anhydride, and has the following general formula I: (Wherein Y represents hydrogen or a C n F 2n + 1 group, and n represents a number of 2 to 10).
そして、本発明の第２の発明は第１の発明の含フツ素
ピロメリツト酸無水物の製造方法に関する発明であつ
て、下記一般式II: （式中Ｙ及びｎはＩ式と同義である）で表される含フツ
素デユレンを酸化、脱水することを特徴とする。The second invention of the present invention relates to the process for producing a fluorine-containing pyromellitic anhydride according to the first invention, and comprises the following general formula II: (Where Y and n have the same meanings as in the formula I).
本発明者らは、テトラカルボン酸二無水物について分
子設計した結果、脂肪族ではポリイミド主鎖が剛直性と
はならず低熱膨張性を損なうため、剛直な芳香族からな
るピロメリツト酸無水物が好適であること、フツ素基の
導入位置としては芳香族環の1,4の位置に導入すること
とし、Ｉ式に示す含フツ素ピロメリツト酸無水物を合成
することとした。The present inventors have made a molecular design of tetracarboxylic dianhydride, and as a result, the polyimide main chain does not become rigid in aliphatic, and impairs low thermal expansion property.Therefore, pyromellitic anhydride composed of rigid aromatic is preferable. Thus, the fluorine group was introduced at the 1,4 position of the aromatic ring, and the fluorine-containing pyromellitic anhydride shown in Formula I was synthesized.
Ｉ式の含フツ素ピロメリツト酸無水物はII式の含フツ
素デユレンの酸化、脱水により合成するが、II式の含フ
ツ素デユレンは例えば下記III式に示す反応式に従つて
合成することができる。The fluorine-containing pyromellitic anhydride of the formula I is synthesized by oxidizing and dehydrating the fluorine-containing duranium of the formula II. it can.
含フツ素ヨウ化物は例えば、ペンタフルオロエチルア
イオダイド、ヘプタフルオロプロピルアイオダイド、パ
ーフルオロ−ｎ−ブチルアイオダイド、パーフルオロ−
ｎ−ペンチルアイオダイド、パーフルオロ−ｎ−ヘキシ
ルアイオダイド、１−ヨードパーフルオロヘプタン、１
−ヨードパーフルオロオクタン、１−ヨードパーフルオ
ロデカンなどがある。本反応の溶媒は、ジメチルホルム
アミド、ピリジンなどの極性溶媒が好適であり、触媒と
して活性銅粉を加える。反応条件は、オートクレーブ中
150℃〜250℃、20〜300気圧で10時間〜150時間であり、
III式中含フツ素ヨウ化物のｎの数が大きくなるほど高
温、高圧、長時間を要する。 Fluorine-containing iodides include, for example, pentafluoroethyl iodide, heptafluoropropyl iodide, perfluoro-n-butyl iodide, perfluoro-
n-pentyl iodide, perfluoro-n-hexyl iodide, 1-iodoperfluoroheptane, 1
-Iodoperfluorooctane, 1-iodoperfluorodecane and the like. The solvent for this reaction is preferably a polar solvent such as dimethylformamide or pyridine, and an active copper powder is added as a catalyst. Reaction conditions are in autoclave
150-250 ° C, 10-150 hours at 20-300 atm,
The higher the number of n of the fluorine-containing iodide in the formula III, the higher the temperature, the higher the pressure and the longer the time.
次にII式の含フツ素デユレンからＩ式の含フツ素ピロ
メリツト酸無水物への酸化、脱水反応であるが、これは
通常の酸化、脱水閉環手法が利用できる。Next, the oxidation and dehydration reaction of the fluorine-containing duren of the formula II to the fluorine-containing pyromellitic anhydride of the formula I can be carried out by a conventional oxidation and dehydration ring closure method.
例えば過マンガン酸カリウム法、硝酸法等によるメチ
ル基の酸化及び無水酢酸法、加熱脱水法等による酸無水
物化法が利用できる。又は、五酸化バナジウムを触媒と
して空気酸化により直接酸無水物化する方法が利用でき
る。For example, oxidation of a methyl group by a potassium permanganate method, a nitric acid method, or the like, and an acid anhydride method by an acetic anhydride method, a heating dehydration method, or the like can be used. Alternatively, a method of directly converting into an acid anhydride by air oxidation using vanadium pentoxide as a catalyst can be used.
（実施例） 以下実施例により本発明の含フツ素ピロメリツト酸無
水物及びその製造方法について詳細に説明するが、本発
明はこれら実施例に限定されない。(Examples) Hereinafter, the fluorine-containing pyromellitic anhydride and the production method thereof of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
実施例１ （含フツ素デユレンの合成） 500mlオートクレーブにジヨウ化デユレン38.6g（100
ミリモル）、ヘプタフルオロプロピルアイオダイド118g
（400ミリモル）、活性化銅粉38.6g（600ミリモル）及
び乾燥ジメチルホルムアミド200mlを入れ、オートクレ
ーブ中160℃、200気圧で120時間加熱かくはんした。冷
却後反応混合物から銅粉及び固体をろ別乾燥し、昇華精
製して1,4−ジヘプタフルオロプロピルデユレン28.6gを
得た。融点、66℃。Example 1 (Synthesis of fluorine-containing duranium) In a 500 ml autoclave, 38.6 g (100 g
Mmol), 118 g of heptafluoropropyl iodide
(400 mmol), activated copper powder (38.6 g, 600 mmol) and dry dimethylformamide (200 ml) were placed in an autoclave and heated and stirred at 160 ° C. and 200 atm for 120 hours. After cooling, the copper powder and the solid were separated from the reaction mixture by filtration, dried and purified by sublimation to obtain 28.6 g of 1,4-diheptafluoropropyldurene. Melting point, 66 [deg.] C.
元素分析、計算値;C,40.86;H,2.57 測定値;C,40.89;H,2.61 赤外吸収スペクトル、NMRスペクトル及びマススペク
トルは予想構造式と一致した。Elemental analysis, calculated; C, 40.86; H, 2.57 Measured; C, 40.89; H, 2.61 The infrared absorption spectrum, NMR spectrum, and mass spectrum were consistent with the expected structural formula.
（含フツ素ピロメリツト酸無水物の合成） 三口フラスコに1,4−ジヘプタフルオロプロピルデユ
レン28.6g（61ミリモル）、ピリジン300ml、水150mlを
加え100℃まで上げた後、過マンガン酸カリウム48.2g
（305ミリモル）をゆっくり加え３時間かくはんした。
反応混合物をろ過し、ろ液中の溶媒をエバポレータで除
去し、生成物を６％水酸化ナトリウム400ml中に加え100
℃まで上げた後、過マンガン酸カリウム60.7g（384ミリ
モル）をゆっくり加えた。1.5時間かくはんした後、エ
タノールを加え余分の過マンガン酸カリウムを分解させ
ろ過した。ろ液を冷却後、塩酸水溶液を加え酸性にする
と沈殿物が析出した。この沈殿物を水で再結晶し、1,4
−ジヘプタフルオロピロピルピロメリツト酸を得た。(Synthesis of fluorine-containing pyromellitic anhydride) 28.6 g (61 mmol) of 1,4-diheptafluoropropyldeurene, 300 ml of pyridine and 150 ml of water were added to a three-necked flask, and the mixture was heated to 100 ° C. g
(305 mmol) was added slowly and stirred for 3 hours.
The reaction mixture was filtered, the solvent in the filtrate was removed by an evaporator, and the product was added to 400 ml of 6% sodium hydroxide.
After the temperature was raised to 6 ° C., 60.7 g (384 mmol) of potassium permanganate was slowly added. After stirring for 1.5 hours, excess potassium permanganate was decomposed by adding ethanol and filtered. After cooling the filtrate, an aqueous solution of hydrochloric acid was added to make the solution acidic, and a precipitate was deposited. The precipitate was recrystallized from water to give 1,4
-Diheptafluoropyrrolpyrromelitic acid was obtained.
この1,4−ジヘプタフルオロプロピルピロメリツト酸
を真空中150℃、２時間加熱した後、昇華精製して1,4−
ジヘプタフルオロピルピロメリツト酸無水物11.8gを得
た。このものは、赤外吸収スペクトル図で1800cm-1及び
1870cm-1に酸無水物特有の二つの吸収、1200cm-1にＣ−
Ｆ基に基づく吸収が現れたこと、NMRスペクトルにおい
てプロトンの吸収が全く現れないこと、そして下記に示
すように元素分析において測定値と計算値がほぼ一致し
ていることから、目的化合物であることを確認した。The 1,4-diheptafluoropropyl pyromellitic acid was heated in vacuum at 150 ° C. for 2 hours, and then purified by sublimation to obtain 1,4-diheptafluoropropyl pyromellitic acid.
11.8 g of diheptafluoropyrropomerittic anhydride was obtained. It has an infrared absorption spectrum of 1800 cm -1 and
1870Cm -1 acid anhydride unique two absorption, the 1200 cm -1 C-
The target compound because the absorption based on the F group appeared, the proton absorption did not appear at all in the NMR spectrum, and the measured and calculated values almost coincided in elemental analysis as shown below. It was confirmed.
元素分析、計算値;C,34.68 測定値;C,34.68 実施例２ １−ヨウ化デユレンを出発原料として、実施例１と同
様の方法によつて１−ヘプタフルオロプロピルデユレン
を経て１−ヘプタフルオロプロピルピロメリツト酸無水
物を合成した。Elemental analysis, calculated value; C, 34.68 Measured value; C, 34.68 Fluoropropyl pyromellitic anhydride was synthesized.
このものは、実施例１と同様に赤外吸収スペクトル図
で1800cm-1及び1870cm-1に酸無水物特有の二つの吸収、
1200cm-1にＣ−Ｆ基に基づく吸収が現れたこと、NMRス
ペクトルにおいてプロトンのシングルピークが一本現れ
たこと、そして下記に示すように元素分析において測定
値と計算値がほぼ一致していることから、目的化合物で
あることを確認した。This compound, in the same manner as in Example 1 Infrared absorption spectrum Two absorption at 1800 cm -1 and 1870cm -1 of anhydride specific, the
The absorption based on the C-F group appeared at 1200 cm -1 , a single proton peak appeared in the NMR spectrum, and the measured and calculated values in elemental analysis almost matched as shown below. Thus, it was confirmed that the compound was the target compound.
元素分析、計算値;C,40.34;H,0.27 測定値;C,40.38;H,0.28 実施例３ ジヨウ化デユレンを出発原料として、実施例１と同様
の方法によつて、1,4−ジパーフルオロデシルデユレン
を経て1,4−ジパーフルオロデシルピロメリツト酸無水
物を合成した。Elemental analysis, calculated values; C, 40.34; H, 0.27 Measured values; C, 40.38; H, 0.28 Example 3 Starting from duurene diiodide as a starting material, 1,4-diene was obtained in the same manner as in Example 1. 1,4-Diperfluorodecyl pyromellitic anhydride was synthesized via perfluorodecyldurene.
このものは、実施例１と同様に赤外吸収スペクトル図
で1800cm-1及び1870cm-1に酸無水物特有の二つの吸収、
1200cm-1にＣ−Ｆ基に基づく吸収が現れたこと、NMRス
ペクトルにおいてプロトンの吸収が全く現れないこと、
そして下記に示すように元素分析において測定値と計算
値がほぼ一致していることから、目的化合物であること
を確認した。This compound, in the same manner as in Example 1 Infrared absorption spectrum Two absorption at 1800 cm -1 and 1870cm -1 of anhydride specific, the
That absorption based on C-F group appeared at 1200 cm -1 , no absorption of proton appeared in NMR spectrum,
Then, as shown below, the measured value and the calculated value in the elemental analysis were almost the same, and thus it was confirmed that the compound was the target compound.
元素分析、計算値;C,28.73 測定値;C,28.75 実施例４ １−ヨウ化デユレンを出発原料として、実施例１と同
様の方法によつて１−パーフルオロデシルデユレンを経
て１−パーフルオロデシルピロメリツト酸無水物を合成
した。Elemental analysis, calculated value; C, 28.73 measured value; C, 28.75 Example 4 Starting from 1-durylene iodide as a starting material, 1-perfluorodecyldeulene was used in the same manner as in Example 1 to give 1-part. Fluorodecyl pyromellitic anhydride was synthesized.
このものは、実施例１と同様に赤外吸収スペクトル図
で1800cm-1及び1870cm-1に酸無水物特有の二つの吸収、
1200cm-1にＣ−Ｆ基に基づく吸収が現れたこと、NMRス
ペクトルにおいてプロトンのシングルピークが一本現れ
たこと、そして下記に示すように元素分析において測定
値と計算値がほぼ一致していることから、目的化合物で
あることを確認した。This compound, in the same manner as in Example 1 Infrared absorption spectrum Two absorption at 1800 cm -1 and 1870cm -1 of anhydride specific, the
The absorption based on the C-F group appeared at 1200 cm -1 , a single proton peak appeared in the NMR spectrum, and the measured and calculated values in elemental analysis almost matched as shown below. Thus, it was confirmed that the compound was the target compound.
元素分析、計算値;C,32.63;H,0.13 測定値;C,32.61;H,0.15 実施例５ （含フツ素ポリイミドの合成） 三角フラスコに1,4−ジヘプタフルオロプロピルピロ
メリツト酸無水物19.92g、ｏ−トリジン7.63g、Ｎ−メ
チル−２−ピロリドン（NMR）156gを加えた。この混合
物を窒素雰囲気下、室温で３日間かくはんし、ポリアミ
ド酸のNMP溶液（η:55ポアズ）を得た。このものをアル
ミ板上に流し、ドクターブレードで平坦にした後、100
℃で１時間、200℃で１時間、350℃で１時間加熱キユア
することにより強じんなポリイミドフイルムが得られ
た。Elemental analysis, calculated values; C, 32.63; H, 0.13 measured values; C, 32.61; H, 0.15 Example 5 (Synthesis of Fluorine-Containing Polyimide) 1,4-Diheptafluoropropylpyromellitic anhydride in an Erlenmeyer flask 19.92 g, o-tolidine 7.63 g, and N-methyl-2-pyrrolidone (NMR) 156 g were added. This mixture was stirred under a nitrogen atmosphere at room temperature for 3 days to obtain an NMP solution of polyamic acid (η: 55 poise). This is poured on an aluminum plate and flattened with a doctor blade.
A tough polyimide film was obtained by heating at 200C for 1 hour, 200C for 1 hour, and 350C for 1 hour.
（発明の効果） 以上説明したように、本発明の含フツ素ピロメリツト
酸無水物は、通常のピロメリツト酸無水物と同様にジア
ミンと反応させポリイミドを得ることができ、新たなフ
ツ素化ポリイミドを合成可能となる利点がある。(Effect of the Invention) As described above, the fluorine-containing pyromellitic anhydride of the present invention can be reacted with a diamine similarly to ordinary pyromellitic anhydride to obtain a polyimide, and a new fluorine-containing polyimide can be obtained. There is an advantage that it can be synthesized.
Claims (2)
す）で表されることを特徴とする含フツ素ピロメリツト
酸無水物。(1) The following general formula (I): (Wherein Y represents hydrogen or a C n F 2n + 1 group, and n represents a number of 2 to 10).
す）で表される含フツ素デユレンを酸化、脱水すること
を特徴とする請求項１記載の含フツ素ピロメリツト酸無
水物の製造方法。2. A compound represented by the following general formula II: (Wherein Y is hydrogen or C n F 2n + 1 group, n is a number of 2 to 10) fluorine-according to claim 1, wherein a fluorine-containing Deyuren represented by oxidation, dehydration A method for producing elementary pyromellitic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165056A JP2704200B2 (en) | 1988-07-04 | 1988-07-04 | Fluorine-containing pyromellitic anhydride and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165056A JP2704200B2 (en) | 1988-07-04 | 1988-07-04 | Fluorine-containing pyromellitic anhydride and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0215084A JPH0215084A (en) | 1990-01-18 |
| JP2704200B2 true JP2704200B2 (en) | 1998-01-26 |
Family
ID=15805006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63165056A Expired - Lifetime JP2704200B2 (en) | 1988-07-04 | 1988-07-04 | Fluorine-containing pyromellitic anhydride and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2704200B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8168327B2 (en) | 2006-01-11 | 2012-05-01 | Idemitsu Kosan Co., Ltd. | Imide derivative, material for organic electroluminescent device and organic electroluminescent device using the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2052368C (en) * | 1990-09-28 | 1998-09-15 | Shinji Ando | Perfluorinated polyimide, perfluorinated poly(amic acid), starting compounds therefor, and methods for preparing them |
| KR100362913B1 (en) * | 2000-10-10 | 2002-12-05 | 학교법인 포항공과대학교 | 9,10-dialkyloxy-1,2,3,4,5,6,7,8-octahydro-2,3,6,7-anthracenetetracarboxylic- 2,3:6,7-dianhydrides and process for their manufacture |
| KR100376287B1 (en) * | 2001-01-26 | 2003-03-17 | 광주과학기술원 | 3,6-di(3',5'-bis(trifluoromethyl)benzene)pyromellitic dianhydride, and process for preparing them |
| KR100431166B1 (en) * | 2001-11-06 | 2004-05-12 | 삼성종합화학주식회사 | 3,6-dialkyloxypyromellitic dianhydrides, its preparation method, and polyimides prepared from the same |
| KR100469080B1 (en) * | 2002-10-31 | 2005-02-02 | 광주과학기술원 | 1-(3',5'-bis(fluoroalkyl)benzene)pyromellitic dianhydride and preparation method thereof |
| JP6407645B2 (en) * | 2013-09-27 | 2018-10-17 | 国立大学法人 東京大学 | Perfluoroalkylation of aromatic compounds |
-
1988
- 1988-07-04 JP JP63165056A patent/JP2704200B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8168327B2 (en) | 2006-01-11 | 2012-05-01 | Idemitsu Kosan Co., Ltd. | Imide derivative, material for organic electroluminescent device and organic electroluminescent device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0215084A (en) | 1990-01-18 |
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