JPH0415232A - Film of calixarene and/or its derivative, and production thereof - Google Patents
Film of calixarene and/or its derivative, and production thereofInfo
- Publication number
- JPH0415232A JPH0415232A JP12031090A JP12031090A JPH0415232A JP H0415232 A JPH0415232 A JP H0415232A JP 12031090 A JP12031090 A JP 12031090A JP 12031090 A JP12031090 A JP 12031090A JP H0415232 A JPH0415232 A JP H0415232A
- Authority
- JP
- Japan
- Prior art keywords
- film
- calixarene
- derivative
- substrate
- derivatives
- 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.)
- Granted
Links
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound 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 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 2
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- -1 N=NAr Chemical compound 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 2
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 abstract 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野ン
本発明は、カリックスアレーンおよびｌまたはカノック
スアレーン誘導体のフィルムに関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to films of calixarene and l or canoxarene derivatives.
（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・アレーンの特徴は、高融点、溶液に対する難溶性、
および包接化合物を形成することであり、特にその包接
能による海水中のウラニルイオンや排水中の重金属イオ
ンの吸着剤として期待されており、近年、そのための誘
導体の合成法や物性が活発に研究されている化合物であ
る。(Prior Art) Calixarene is a cyclic oligomer produced by condensation of phenol and formaldehyde. The characteristics of calix arene are high melting point, low solubility in solutions,
It is expected to be used as an adsorbent for uranyl ions in seawater and heavy metal ions in wastewater due to its clathration ability, and in recent years, synthetic methods and physical properties of derivatives for this purpose have been actively researched. It is a compound that is being studied.
特に、水に対する溶解度を向上させることを目的とした
誘導体の合成が試みられている。In particular, attempts have been made to synthesize derivatives aimed at improving solubility in water.
（発明が解決しようとする課題）
しかしながら、カリソクスアレーンおよび／またはカリ
ックスアレーン誘導体は有機溶剤には難溶であるため、
カリックスアレーンを高分子中に練りこむ例は見受けら
れるが、カリックスアレーンおよびｌまたはカリックス
アレーン誘導体そのものをフィルムとすることはこれま
でなされていない。したがって、本発明の目的は第一に
カリックスアレーンおよび／またはカリックスアレーン
誘導体のフィルムを提供することにあり、第二にその製
造法を提供することにある。(Problems to be Solved by the Invention) However, since calixarene and/or calixarene derivatives are poorly soluble in organic solvents,
Although there have been examples of kneading calixarene into polymers, it has not been attempted to form a film from calixarene and l or a calixarene derivative itself. Therefore, the object of the present invention is firstly to provide a film of calixarene and/or calixarene derivative, and secondly to provide a method for producing the same.
（課題を解決するための手段）
本発明者は、上記目的を達成するため実験研究を行った
結果、カリックスアレーンおよびｌまたはカリックスア
レーン誘導体をフィルム化する事が可能である事を見い
だして本発明を完成するに至った。(Means for Solving the Problems) As a result of conducting experimental research to achieve the above object, the present inventor found that it is possible to form a film from calixarene and l or calixarene derivatives, and the present invention has been made. I was able to complete it.
すなわち、本発明は、１００Å以上の厚さをもつカリッ
クスアレーンおよびｌまたはカリツクスアレーン誘導体
のフィルムである。また、本発明の製造方法はカリック
スアレーンおよびｌまたはカリックスアレーン誘導体を
含む溶液をスピンコート法で基板上にフィルムとして形
成し、４００℃以下の温度で焼成して残留溶媒を除去す
る工程よりなる。That is, the present invention is a film of calixarene and l or calixarene derivatives having a thickness of 100 Å or more. Further, the manufacturing method of the present invention comprises a step of forming a film on a substrate by spin coating a solution containing calixarene and l or a calixarene derivative, and removing residual solvent by baking at a temperature of 400° C. or lower.
本発明において用いられるカリックスレーンおよびｌま
たはカリックスアレーン誘導体とは、フェノールとホル
ムアルデヒドの縮合により生成する環状オリゴマーおよ
びその誘導体であって、つぎの−数式で示される構造を
有する。The calixarene and l or calixarene derivatives used in the present invention are cyclic oligomers and derivatives thereof produced by condensation of phenol and formaldehyde, and have a structure represented by the following formula.
Ｒ′
ｎは、４．５．６．７．８のものが既知であり、特にｎ
＝４．６および８のものは、−段階で収率よく合成でき
る。R′ n is known to be 4.5.6.7.8, especially n
Those with =4.6 and 8 can be synthesized in -step with good yield.
Ｒは−Ｈ，−ＣＨ３，−ＣＯＣＨ３，（ＣＨ２）ｎＣＨ
３，−ＣＨ２Ａｒ。R is -H, -CH3, -COCH3, (CH2)nCH
3,-CH2Ar.
−〇Ｈ２ＣＨＣＨ２，−３ｉＣＨ３，−ＣＨ２ＣＯＯＨ
等Ｒ′は−Ｈ，−ｔ−Ｃ４Ｈｇ、−Ｂｒ、−８Ｏ３Ｎａ
、 −ＣＨ２ＮＨ２゜−Ｎ＝ＮＡｒ、 −ＣＨ２Ｃ１，
−ＣＯＡｒ、 ＮＯ２゜−Ｃ５Ｈ５ＣＯＣＨ＝ＣＨ２等
シクロデキストリンと異なりベンゼン環よりなるカリッ
クスアレーン類は、芳香族置換反応を利用して種々の誘
導体が合成できる。-〇H2CHCH2, -3iCH3, -CH2COOH
R' is -H, -t-C4Hg, -Br, -8O3Na
, -CH2NH2゜-N=NAr, -CH2C1,
-COAr, NO2°-C5H5COCH=CH2, etc. Unlike cyclodextrins, calixarenes consisting of benzene rings can be synthesized into various derivatives using aromatic substitution reactions.
これら、カリックスアレーンおよび／またはカリックス
アレーン誘導体は、シクロデキストリン類クラウンエー
テル類と同様に包接機能を有する事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
中の包摂が報告されている。しかしながら、機能性材料
として用いるには、これをフィルム化する事がきわめて
有用である。これらカリックスアレーンおよび／または
カリックスアレーン誘導体は、有機溶剤には難溶である
が、希薄な溶液からでも１００Å以上の厚みを有するフ
ィルムを製造できることを見い出した。溶剤は高めの沸
点を有し、塗布する基板となじみの良いものが好ましい
。例えば、ピリジンは溶解度の点では好ましいが、ガラ
ス、石英、シリコン基板等に塗布するための溶剤として
は好ましくなかった。一方、シクロヘキサノン、ジオキ
サンは好ましい溶剤の例である。極端に薄いフィルムは
欠陥等の面で好ましくないが、１００Å以上はフィルム
として機能する。また本発明の製造方法では基板上にス
ピンコートしたあと４００℃以下の温度で焼成している
が、これはカリックスアレーンあるいはその誘導体が４
００’Ｃ程度までであれば安定であるためである。得ら
れたフィルムは、高い耐熱性を有し、また、一般の高分
子膜と比べると、きわめて高い硬度を有する。It has recently been revealed that these calixarene and/or calixarene derivatives have an inclusion function similar to cyclodextrin crown ethers, and the synthesis of water-soluble calixarene has been studied and inclusion in aqueous solutions has been reported. ing. However, in order to use it as a functional material, it is extremely useful to form it into a film. Although these calixarene and/or calixarene derivatives are poorly soluble in organic solvents, it has been found that a film having a thickness of 100 Å or more can be produced even from a dilute solution. The solvent preferably has a high boiling point and is compatible with the substrate to which it is applied. For example, pyridine is preferable in terms of solubility, but is not preferable as a solvent for coating glass, quartz, silicon substrates, etc. On the other hand, cyclohexanone and dioxane are examples of preferred solvents. Although an extremely thin film is unfavorable in terms of defects, etc., an extremely thin film of 100 Å or more functions as a film. In addition, in the manufacturing method of the present invention, calixarene or its derivatives are spin-coated onto a substrate and then baked at a temperature of 400°C or less.
This is because it is stable up to about 00'C. The obtained film has high heat resistance and extremely high hardness compared to general polymer films.
このようなフィルムを得ることにより、粉末状または溶
液として扱われていたカリックスアレーンおよび／また
はカリックスアレーン誘導体をフィルム状で扱え、しか
も、このフィルムは、カリックスアレーンの特徴である
種々の機能を発揮させるための基材である。By obtaining such a film, calixarene and/or calixarene derivatives, which have been treated as powder or solution, can be treated in film form, and this film can exhibit various functions characteristic of calixarene. It is a base material for
（実施例）
合成例１；ｔ−ブチルーカリックス［４１アレーンｐ−
ｔｅｒｔ−ブチルフェノール１０ｇを、３７％ホルムア
ルデヒド水溶液９．７ｇに溶かし、３Ｎの水酸化ナトリ
ウム水溶液１０ｍ１加えた。これを５０〜５５℃で４５
時間、さらに１１０−１２０℃で２時間加熱した。そし
て、ＩＮの塩酸１００ｍ１を加え１時間撹拌後、不溶物
をろ過し真空１１０℃で１時間乾燥した。それを、ジフ
ェニルエーテル７０ｇに溶かし２２０℃で２時間加熱し
、酢酸エチルで抽出し、粗結晶を得た。クロロホルム−
メタノールで再結晶させ、ｔ−プチルカリックス［８］
アレーンを３．２ｇ得た。融点は３４４〜３４６℃であ
った。確まごは、ＩＲ，ＮＭＲ，およびマススペクトル
により行った。以下、同様である。(Example) Synthesis Example 1; t-butyl calix [41 arene p-
10 g of tert-butylphenol was dissolved in 9.7 g of a 37% formaldehyde aqueous solution, and 10 ml of a 3N aqueous sodium hydroxide solution was added. This was heated to 50-55℃ for 45 minutes.
The mixture was further heated at 110-120° C. for 2 hours. Then, 100 ml of IN hydrochloric acid was added, and after stirring for 1 hour, insoluble matter was filtered and dried in vacuum at 110° C. for 1 hour. It was dissolved in 70 g of diphenyl ether, heated at 220°C for 2 hours, and extracted with ethyl acetate to obtain crude crystals. Chloroform-
Recrystallize with methanol to obtain t-butylcalix [8]
3.2g of arene was obtained. The melting point was 344-346°C. The identification was conducted by IR, NMR, and mass spectrometry. The same applies hereafter.
合成例２；ｔ−プチルーカリックス［８］アレーンｐ−
ｔｅｒｔ−ブチルフェノール２７．８ｇをキシレン１５
０ｍ１に溶かしパラホルムアルデヒド９ｇを加え、さら
に１ＯＮの水酸化カリウム水溶液０．４ｍｌ加えた。こ
れを、４時間加熱還流し、析出物をろ過し、トルエン、
エーテル、アセトン、水の順で洗浄し粗結晶を得た。こ
れをクロロホルムで再結晶させ、ｔ、ブチルー力ワック
ス［８］アレーンを１５．５ｇ得た。融点は４１１から
４１２℃であった。Synthesis example 2; t-butylucaryx [8] arene p-
27.8 g of tert-butylphenol was added to 15 g of xylene.
9 g of paraformaldehyde was added to the solution, and 0.4 ml of 1ON potassium hydroxide aqueous solution was added thereto. This was heated under reflux for 4 hours, the precipitate was filtered, and toluene,
Crude crystals were obtained by washing with ether, acetone, and water in that order. This was recrystallized from chloroform to obtain 15.5 g of butylene wax [8]arene. The melting point was 411-412°C.
合成例３；ｔ−オクチルーカリソクス［８］アレーンｐ
−ｔｅｒｔ−オクチルフェノール３７．１４ｇを、キシ
レン１５０ｍ１に溶かし、パラホルムアルデヒド９ｇを
溶かし、ＩＯＮの水酸化カリウム水溶液０．４ｍｌ加え
た。これを４時間加熱還流した。その後クロロホルムで
抽出し粗結晶を得た。クロロホルム−メタノールで再結
晶し、ｔ−オクチル、カリソクス［８］アレーンを７．
１ｇ得た。融点は３３８〜３４０℃であった。Synthesis Example 3; t-octylukalysox[8]arene p
37.14 g of -tert-octylphenol was dissolved in 150 ml of xylene, 9 g of paraformaldehyde was dissolved, and 0.4 ml of an aqueous potassium hydroxide solution of ION was added. This was heated under reflux for 4 hours. Thereafter, it was extracted with chloroform to obtain crude crystals. Recrystallize from chloroform-methanol to obtain t-octyl, calisox[8]arene in 7.
I got 1g. The melting point was 338-340°C.
合成例４；カリソクス［６］アレーン
ｔ−プチルー力すツクス［６１アレ一ン１０ｇとフェノ
ール６．０ｇをトルエンに溶かし、塩化アルミニウム１
２．４ｇを加え、室温で１時間撹拌した。さらに、冷水
１００ｍ１を加え、有機層をエバボレートした。アセト
ンやメタノールなどで洗浄し、カワックス［６］アレー
ンを３．９ｇ得た。融点は３８０〜３８１℃であった。Synthesis Example 4: Calisox[6]arene t-butyl-butysox[61] Dissolve 10g of arene and 6.0g of phenol in toluene, and dissolve 1 gram of aluminum chloride.
2.4 g was added and stirred at room temperature for 1 hour. Furthermore, 100 ml of cold water was added and the organic layer was evaporated. After washing with acetone, methanol, etc., 3.9 g of Kawax[6]arene was obtained. The melting point was 380-381°C.
合成例５；Ｌ−プチルー力リックス［８コアレーン、ア
セテート
七−プチルー力すックス［８１アレ一ン２ｇをピリジン
１００ｍ１に溶かし、無水酢酸０．２ｍｌ加え、３０分
撹拌した。反応溶液を水にあけ、不溶物をろ過し粗結晶
を得た。これをクロロホルムで再結晶させ、ｔ４ブチル
ー力トリソクス［８］アレーン・アセテート２．１ｇ−
を得た。Synthesis Example 5: L-butylene chloride [8 corerene, acetate 7-butylene chloride 2 g [81] were dissolved in 100 ml of pyridine, 0.2 ml of acetic anhydride was added, and the mixture was stirred for 30 minutes. The reaction solution was poured into water, and insoluble matter was filtered to obtain crude crystals. This was recrystallized from chloroform, and 2.1 g of t4butyl trisox[8]arene acetate was obtained.
I got it.
実施例１
合成例２で示したｔ−プチルー力すックス［８１アレー
ンの０．２５ｗｔ％・ｔ−ブチルーカリンクス［８］ア
レーンシクロキサノン溶液を調整し、それを０．２１１
ｍ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Ｕ数３
００ｒｐｍで１０秒、ひきつづき、８００ｒｐｍで６０
秒行った。これを１５０℃で３０分ベーキングをおこな
いフィルムを得た。得られたフィルムの膜厚は、６００
Ａであった。微小硬度計により表面のヴイッカース硬度
は１００以上であった。Example 1 A solution of 0.25 wt% t-butyl-calcinx [8]arene cycloxanone shown in Synthesis Example 2 was prepared, and it was added to 0.211
After passing through an M filter, it was formed into a film on a silicon substrate by spin coating. Spin coat 3 times
00 rpm for 10 seconds, then 800 rpm for 60 seconds.
Seconds went. This was baked at 150° C. for 30 minutes to obtain a film. The thickness of the obtained film was 600
It was A. The Vickers hardness of the surface was determined to be 100 or more using a microhardness meter.
実施例２
合成例１．３．４．５の生成物を実施例１と同様な方法
によりスピンコートシ、そのフィルムを得た。Example 2 The product of Synthesis Example 1.3.4.5 was spin-coated in the same manner as in Example 1 to obtain a film.
実施例３
合成例２，４の生成物を混合し、それを実施例と同様な
方法によりスピンコートし、そのフィルムを得た。Example 3 The products of Synthesis Examples 2 and 4 were mixed and spin coated in the same manner as in Example to obtain a film.
（発明の効果）
以上の説明から明らかなように、カリックスアレーンお
よび／またはカリックスアレーン誘導体のフィルムが得
られ、また、このフィルムを得たことにより高耐熱性、
高硬度のコーティングが行えるだけでなく、カリックス
アレーンを機能性材料として利用するための有効な手段
を得た。(Effect of the invention) As is clear from the above explanation, a film of calixarene and/or a calixarene derivative can be obtained, and by obtaining this film, high heat resistance,
In addition to being able to form coatings with high hardness, we have found an effective means to utilize calixarene as a functional material.
Claims (1)
び／またはカリックスアレーン誘導体のフィルム。 ２、フィルムは基板上に形成されたものである事を特徴
とする請求項１に記載のフィルム。 ３、カリックスアレーンおよび／またはカリックスアレ
ーン誘導体を含む溶液をスピンコート法で基板上にフィ
ルムとして形成し、４００℃以下の温度で焼成して残留
溶剤を除去する工程よりなるカリックスアレーンおよび
／またはカリックスアレーン誘導体のフィルムの製造法
。 ４、溶剤はシクロヘキサノンである請求項３に記載の製
造法。[Claims] 1. A film of calixarene and/or calixarene derivatives having a thickness of 100 Å or more. 2. The film according to claim 1, wherein the film is formed on a substrate. 3. Calixarene and/or calixarene consisting of a step of forming a film on a substrate by spin coating a solution containing calixarene and/or a calixarene derivative, and removing residual solvent by baking at a temperature of 400°C or less. Method for manufacturing derivative films. 4. The manufacturing method according to claim 3, wherein the solvent is cyclohexanone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2120310A JPH0653819B2 (en) | 1990-05-10 | 1990-05-10 | Film of calixarene and / or calixarene derivative and method for producing the same |
| 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 |
|---|---|---|---|
| JP2120310A JPH0653819B2 (en) | 1990-05-10 | 1990-05-10 | Film of calixarene and / or calixarene derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0415232A true JPH0415232A (en) | 1992-01-20 |
| JPH0653819B2 JPH0653819B2 (en) | 1994-07-20 |
Family
ID=14783076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2120310A Expired - Lifetime JPH0653819B2 (en) | 1990-05-10 | 1990-05-10 | Film of calixarene and / or calixarene derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653819B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0578327A1 (en) * | 1992-07-10 | 1994-01-12 | Akzo Nobel N.V. | Non-linear optical waveguiding material comprising a dopant having multiple donor-pi-acceptor systems |
| JPH09236919A (en) * | 1996-02-28 | 1997-09-09 | Nec Corp | Superfine pattern forming method and superfine etching method |
| JP2005336135A (en) * | 2004-05-28 | 2005-12-08 | Sumitomo Bakelite Co Ltd | Bisaminophenol compound |
| JP2008046206A (en) * | 2006-08-11 | 2008-02-28 | Shin Etsu Chem Co Ltd | Resist protective film material and pattern forming method |
| US7514197B2 (en) * | 2002-09-09 | 2009-04-07 | Nec Corporation | Resist and method of forming resist pattern |
| WO2010134639A1 (en) * | 2009-05-21 | 2010-11-25 | 株式会社トクヤマ | Method for formation of resist pattern, and developing solution |
| US20120164575A1 (en) * | 2009-08-31 | 2012-06-28 | Mitsubishi Gas Chemical Company, Inc. | Cyclic compound, manufacturing method therefor, radiation-sensitive composition, and method for forming a resist pattern |
| JP2013173839A (en) * | 2012-02-24 | 2013-09-05 | Dic Corp | Cyanic ester resin, curable resin composition, cured matter thereof, semiconductor sealing material, prepreg, circuit board and build-up film |
| JP2013181164A (en) * | 2012-03-05 | 2013-09-12 | Dic Corp | Active ester resin, curable resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and build-up film |
| CN113663529A (en) * | 2021-08-24 | 2021-11-19 | 北京工业大学 | Novel macrocyclic aromatic hydrocarbon composite nanofiltration membrane and preparation method thereof |
-
1990
- 1990-05-10 JP JP2120310A patent/JPH0653819B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| J.AM.CHEM.SOC=1989US * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0578327A1 (en) * | 1992-07-10 | 1994-01-12 | Akzo Nobel N.V. | Non-linear optical waveguiding material comprising a dopant having multiple donor-pi-acceptor systems |
| US5434208A (en) * | 1992-07-10 | 1995-07-18 | Akzo Nobel N.V. | Optically non-linear active waveguiding material comprising a dopant having multiple donor-n-acceptor systems |
| JPH09236919A (en) * | 1996-02-28 | 1997-09-09 | Nec Corp | Superfine pattern forming method and superfine etching method |
| US7514197B2 (en) * | 2002-09-09 | 2009-04-07 | Nec Corporation | Resist and method of forming resist pattern |
| JP2005336135A (en) * | 2004-05-28 | 2005-12-08 | Sumitomo Bakelite Co Ltd | Bisaminophenol compound |
| JP2008046206A (en) * | 2006-08-11 | 2008-02-28 | Shin Etsu Chem Co Ltd | Resist protective film material and pattern forming method |
| WO2010134639A1 (en) * | 2009-05-21 | 2010-11-25 | 株式会社トクヤマ | Method for formation of resist pattern, and developing solution |
| JP5442008B2 (en) * | 2009-05-21 | 2014-03-12 | 株式会社トクヤマ | Resist pattern forming method and developer |
| US8703402B2 (en) | 2009-05-21 | 2014-04-22 | Tokuyama Corporation | Resist pattern forming method and developer |
| US20120164575A1 (en) * | 2009-08-31 | 2012-06-28 | Mitsubishi Gas Chemical Company, Inc. | Cyclic compound, manufacturing method therefor, radiation-sensitive composition, and method for forming a resist pattern |
| US8883937B2 (en) * | 2009-08-31 | 2014-11-11 | Mitsubishi Gas Chemical Company, Inc. | Cyclic compound, manufacturing method therefor, radiation-sensitive composition, and method for forming a resist pattern |
| JP2013173839A (en) * | 2012-02-24 | 2013-09-05 | Dic Corp | Cyanic ester resin, curable resin composition, cured matter thereof, semiconductor sealing material, prepreg, circuit board and build-up film |
| JP2013181164A (en) * | 2012-03-05 | 2013-09-12 | Dic Corp | Active ester resin, curable resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and build-up film |
| CN113663529A (en) * | 2021-08-24 | 2021-11-19 | 北京工业大学 | Novel macrocyclic aromatic hydrocarbon composite nanofiltration membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653819B2 (en) | 1994-07-20 |
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