JPH0723340B2 - Calixarene derivative, film thereof, and pattern forming method thereof - Google Patents
Calixarene derivative, film thereof, and pattern forming method thereofInfo
- Publication number
- JPH0723340B2 JPH0723340B2 JP24915190A JP24915190A JPH0723340B2 JP H0723340 B2 JPH0723340 B2 JP H0723340B2 JP 24915190 A JP24915190 A JP 24915190A JP 24915190 A JP24915190 A JP 24915190A JP H0723340 B2 JPH0723340 B2 JP H0723340B2
- Authority
- JP
- Japan
- Prior art keywords
- calixarene
- film
- forming method
- pattern forming
- methyl
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title description 17
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 uranyl ions Chemical class 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、多種の有機溶剤に対し高溶解性を示すカリッ
クスアレーン誘導体に関するものである。TECHNICAL FIELD The present invention relates to a calixarene derivative having high solubility in various organic solvents.
（従来の技術） カリックスアレーンは、フェノール・ホルムアルデヒド
の縮合により生成する環状オリゴマーである。カリック
スアレーンおよびカリックスアレーン誘導体は、シクロ
デキストリンやクラウンエーテル類と同様に包接能を有
することが近年明らかにされ、水溶性カリックスアレー
ンの合成が研究され、水溶液中の包接が報告さており、
海水中ウラニルイオンの回収などを目的としたカリック
スアレーン誘導体の研究なども行われている。また、カ
リックスアレーンは、その特徴から優れた機能性材料と
なることが期待でき、本出願人は既にカリックスアレー
ンをフィルム化することを提案した。(Prior Art) Calixarene is a cyclic oligomer produced by condensation of phenol-formaldehyde. Recently, it was revealed that calixarene and calixarene derivatives have an inclusion ability similar to cyclodextrins and crown ethers, the synthesis of water-soluble calixarene was studied, and inclusion in an aqueous solution was reported.
Studies on calixarene derivatives for the purpose of recovering uranyl ions in seawater are also being conducted. Further, calixarene can be expected to be an excellent functional material because of its characteristics, and the applicant has already proposed to form calixarene into a film.
（発明が解決しようとする課題） しかしながら、機能性材料として用いるには、有機溶剤
に対し高溶解性を示すカリックスアレーン誘導体が必要
である。今までに知られているカリックスアレーンおよ
びカリックスアレーン誘導体は、非常に溶解性が低く
（0.1wt％以下）、これを機能性材料として用いた報告
（マルコヴィッツ，ヤヌート，カストナー，リーガン
（Michael A Markowitz,Vaclaw Janouut,David G.Gastn
er,and Steven L.Regen）ジャーナル オブ アメリカ
ン ケミカル ソサエテイ（J.Am.Chem.Soc.）1989,11
1,8192−8200）は500Å以下のフイルムについてのみで
あった。本発明者は有機溶剤に対する溶解度を向上させ
る手段として大きなアルキル基を有するカリックスアレ
ーン、例えば、オクチル−カリックスアレーン、ドデシ
ル−カリックスアレーンなどを合成し検討したが、溶解
性の向上はなかった。また、アセチル化も効果的と思わ
れたのでｔ−ブチル−カリックスアレーンをアセチル化
したが溶解性に大きな向上は見られなかった。(Problems to be Solved by the Invention) However, a calixarene derivative having high solubility in an organic solvent is required for use as a functional material. The known calixarene and calixarene derivatives have a very low solubility (0.1 wt% or less) and are reported to be used as a functional material (Markovitz, Janut, Kastner, Regan (Michael A Markowitz). , Vaclaw Janouut, David G. Gastn
er, and Steven L. Regen) Journal of American Chemical Society (J.Am.Chem.Soc.) 1989,11
1,8192-8200) was only for films under 500Å. The present inventor synthesized and studied calixarene having a large alkyl group, for example, octyl-calixarene and dodecyl-calixarene, as a means for improving the solubility in an organic solvent, but the solubility was not improved. Further, acetylation seemed to be effective, so t-butyl-calixarene was acetylated, but no significant improvement in solubility was observed.
本発明の目的は、有機溶剤に対して高溶解性を示すカリ
ックスアレーン誘導体を提供することにあり、また、そ
のフィルムおよびそのパターン形成方法を提供するもの
である。An object of the present invention is to provide a calixarene derivative having high solubility in an organic solvent, and also to provide a film thereof and a pattern forming method thereof.
（課題を解決するための手段） 本発明者は、新規な化合物としてメチル−カリックスア
レーンのアセチル化物の合成に成功し、この材料が多く
の溶剤（例；ピリジン、クロロホルム、ジクロロメタ
ン）などに対して高溶解性を示すのみでなく、その化合
物を有機溶剤（例；トルエン、モノクロロベンゼン、キ
シレン）に溶かし、スピンコート法により、膜厚のフィ
ルムを得ることが可能であること見だした。(Means for Solving the Problems) The present inventor has succeeded in synthesizing an acetylated product of methyl-calixarene as a novel compound, and this material can be used for many solvents (eg, pyridine, chloroform, dichloromethane) and the like. It was found that not only high solubility but also the compound can be dissolved in an organic solvent (eg, toluene, monochlorobenzene, xylene) and a film having a film thickness can be obtained by spin coating.
（実施例） 実施例１（合成） ｐ−クレーゾール18.7gをキシレン150mlに溶かしパラホ
ルムアルデヒド9gを加え、さらに、10Nの水酸化カリウ
ム水溶液0.4mlを加えた。これを、４時間加熱還流し、
析出物ろ過し、アセトン、エタノールで洗浄、乾燥し
た。さらに、エタノールと水の混合溶液で洗浄、乾燥
し、メチル−カリックスアレーンを10.3g得た。(Example) Example 1 (Synthesis) 18.7 g of p-cresol was dissolved in 150 ml of xylene, 9 g of paraformaldehyde was added, and 0.4 ml of 10N potassium hydroxide aqueous solution was further added. This is heated under reflux for 4 hours,
The precipitate was filtered, washed with acetone and ethanol, and dried. Further, it was washed with a mixed solution of ethanol and water and dried to obtain 10.3 g of methyl-calixarene.
得られたメチル−カリックスアレーン3.0gをピリジン30
mlに溶かし無水酢酸1mlを加え、室温で30分攪はんし
た。この反応溶液を300mlの水にあけ、析出物をろ過、
乾燥し、メチル−カリックスアレーンのアセチル化物3.
7gを得た。3.0 g of the obtained methyl-calixarene was added to pyridine 30
This was dissolved in ml, 1 ml of acetic anhydride was added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was poured into 300 ml of water, the precipitate was filtered,
Dried and acetylated methyl-calixarene 3.
I got 7g.
IR（第１図）、NMR（第２図）、マススペクトルデータ
（972）より、生成物はメチルカリックス［６］アレー
ン・アセチル化物と同定できた。From IR (Fig. 1), NMR (Fig. 2) and mass spectrum data (972), the product could be identified as methylcalix [6] arene acetylated product.
この生成物をアセトンに溶解させ強く攪はんすると、数
分後に析出物を得、これを濾過・乾燥して、メチル−カ
リックス［６］アレーンのアセチル化物の異性体を得
た。この異性体についてはIR,NMR,マススペクトルのデ
ータは同じである。This product was dissolved in acetone and stirred vigorously to obtain a precipitate after several minutes, which was filtered and dried to obtain an isomer of an acetylated product of methyl-calix [6] arene. The IR, NMR, and mass spectral data for this isomer are the same.
実施例２（フィルム） メチル−カリックスアレーンのアセチル化物の10wt％ト
ルンエン溶液を調整し、それを0.2μｍフィルターに通
した後に、スピンコート法によりシリコン基板上にフィ
ルム化した。スピンコートは回転数300rpmで５秒、ひき
つづき、1500rpmで60秒行った。これを、窒素中100℃で
30分ベーキングを行った。膜厚約0.45μｍの均一なフィ
ルムが得られた。Example 2 (Film) A 10 wt% torunene solution of an acetylated product of methyl-calixarene was prepared, passed through a 0.2 μm filter, and then formed into a film on a silicon substrate by spin coating. Spin coating was performed at 300 rpm for 5 seconds, followed by 1500 rpm for 60 seconds. This at 100 ℃ in nitrogen
I baked for 30 minutes. A uniform film having a film thickness of about 0.45 μm was obtained.
実施例３（パターン形成） 実施例２で得られたフィルムにイオンビームを選択的に
照射（日本電子JIBL−150集束イオンビーム描画装置、
イオン種;Be++、加速エネルギー;260KeV,ビーム電流;9.
6pA,ビーム径；約0.1μm,露光量;.4.0×1013ions/cm2）
して重合し、ついで、エタノールで30秒未照射部を溶解
除去させ、80℃で30分ポストベークを行うことによりパ
ターンを形成した。SEMでパターン形状を観察したとこ
ろ、角型性の良いパターンが0.1μｍ幅のパターンも正
確に形成された。また、300℃で30分加熱したが、形状
に変化はなかった。これは、電子線、Ｘ線でも同様であ
った。Example 3 (Pattern formation) The film obtained in Example 2 is selectively irradiated with an ion beam (JIBL-150 focused ion beam drawing device, JEOL,
Ion species; Be ++ , acceleration energy; 260 KeV, beam current; 9.
6pA, beam diameter; about 0.1 μm, exposure dose; .4.0 × 10 13 ions / cm 2 )
Then, the unirradiated portion was dissolved and removed with ethanol for 30 seconds and post-baked at 80 ° C. for 30 minutes to form a pattern. As a result of observing the pattern shape by SEM, a pattern having good squareness and a pattern having a width of 0.1 μm were accurately formed. In addition, there was no change in shape when heated at 300 ° C for 30 minutes. This was also the case with electron beams and X-rays.
以上の実施例は６量体について述べたが、４〜８量体
は、１ユニットずつ縮合させる逐次合成法によって任意
のｎ量体（ｎ＝４〜８）を合成することができる。Although the above examples have described the hexamers, the n-mers (n = 4 to 8) can be synthesized from the 4- to 8-mer by a sequential synthesis method in which one unit is condensed.
（発明の効果） 以上の説明から明らかなように、多種の有機溶剤に対し
高溶解性を示すカリックスアレーン誘導体であるメチル
−カリックスアレーンのアセチル化物を得、また、この
化合物により、厚いフィルムを得ることが可能となり、
また、それのパターン形成も可能となった。このよう
に、高溶解性カリックスアレーン誘導体を得たことによ
り、カリックスアレーンの機能性材料への応用の可能性
を広げた。(Effect of the Invention) As is clear from the above description, an acetylated product of methyl-calixarene, which is a calixarene derivative showing high solubility in various organic solvents, is obtained, and a thick film is obtained by this compound. Is possible,
Moreover, the pattern formation of it became possible. In this way, by obtaining a highly soluble calixarene derivative, the possibility of application of calixarene to a functional material was expanded.
【図面の簡単な説明】 第１図、第２図はそれぞれメチル−カリックスアレーン
のアセチル化物の赤外吸収スペクトルの図とプロトンNM
Rのスペクトルの図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 and FIG. 2 are the infrared absorption spectrum of the acetylated product of methyl-calixarene and proton NM, respectively.
It is a figure of the spectrum of R.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 61:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area C08L 61:06
Claims (3)
アレーンのアセチル化物。 1. An acetylated product of methyl-calixarene represented by the following structural formula.
物より形成されたフィルム。2. A film formed from an acetylated product of methyl-calixarene.
に、高エネルギー線を選択的に照射し、次いで溶剤によ
り未照射部を溶解除去するパターン形成方法。3. A pattern forming method in which the film of claim 2 formed on a substrate is selectively irradiated with high-energy rays, and then unexposed portions are dissolved and removed with a solvent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24915190A JPH0723340B2 (en) | 1990-09-19 | 1990-09-19 | Calixarene derivative, film thereof, and pattern forming method thereof |
| US07/694,491 US5143784A (en) | 1990-05-10 | 1991-05-02 | Soluble calixarene derivative and films thereof |
| EP91304191A EP0456497B1 (en) | 1990-05-10 | 1991-05-09 | Soluble calixarene derivative and films thereof |
| DE69110975T DE69110975T2 (en) | 1990-05-10 | 1991-05-09 | Soluble calixarene derivative and films thereof. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24915190A JPH0723340B2 (en) | 1990-09-19 | 1990-09-19 | Calixarene derivative, film thereof, and pattern forming method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04128253A JPH04128253A (en) | 1992-04-28 |
| JPH0723340B2 true JPH0723340B2 (en) | 1995-03-15 |
Family
ID=17188668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24915190A Expired - Fee Related JPH0723340B2 (en) | 1990-05-10 | 1990-09-19 | Calixarene derivative, film thereof, and pattern forming method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0723340B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2853626B2 (en) * | 1995-12-26 | 1999-02-03 | 日本電気株式会社 | Substrate surface flattening method |
| IT1282709B1 (en) * | 1996-02-28 | 1998-03-31 | Nec Corp | ULTRAFINE CONFIGURATION TRAINING PROCESS AND ULTRAFINE ENGRAVING PROCEDURE USING DERIVATIVE OF |
| US6511793B1 (en) * | 1999-03-24 | 2003-01-28 | Lg Electronics Inc. | Method of manufacturing microstructure using photosensitive glass substrate |
| JP6850079B2 (en) * | 2015-08-24 | 2021-03-31 | 学校法人 関西大学 | Polymer compounds, radiation-sensitive compositions and pattern-forming methods |
-
1990
- 1990-09-19 JP JP24915190A patent/JPH0723340B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04128253A (en) | 1992-04-28 |
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