JPH05339225A - 1-(1'-cyanoethenyl)adamantan and resist material - Google Patents
1-(1'-cyanoethenyl)adamantan and resist materialInfo
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- JPH05339225A JPH05339225A JP4150645A JP15064592A JPH05339225A JP H05339225 A JPH05339225 A JP H05339225A JP 4150645 A JP4150645 A JP 4150645A JP 15064592 A JP15064592 A JP 15064592A JP H05339225 A JPH05339225 A JP H05339225A
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- Prior art keywords
- cyanoethenyl
- adamantane
- formula
- compound
- adamantan
- Prior art date
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Abstract
Description
【0001】本発明は、新規なアダマンタン化合物であ
る1−(1′−シアノエテニル)アダマンタンに関す
る。この新規化合物は重合性を有し、電子材料、光学材
料、医薬、農薬等の有機合成の原料、あるいは機能性高
分子材料等の原料として有用である。The present invention relates to a novel adamantane compound, 1- (1'-cyanoethenyl) adamantane. This novel compound has polymerizability, and is useful as a raw material for organic synthesis such as electronic materials, optical materials, pharmaceuticals and agricultural chemicals, or a raw material for functional polymer materials.
【0002】[0002]
【従来の技術】アダマンタン骨格を有する化合物は数多
く知られているが、本発明のアダマンタン化合物はこれ
まで知られていなかった。この新規化合物に類似の化合
物としては、1−ビニルアダマンタン、1−イソプロペ
ニルアダマンタンが知られている。Many compounds having an adamantane skeleton are known, but the adamantane compound of the present invention has not been known so far. As compounds similar to this novel compound, 1-vinyl adamantane and 1-isopropenyl adamantane are known.
【0003】[0003]
【発明が解決しようとする課題】現在までに知られてい
る1−ビニルアダマンタンや1−イソプロペニルアダマ
ンタンでは、重合性が乏しいため、所望の重合体を思い
通りに得ることが必ずしもできるとは限らなかった。例
えば、1−ビニルアダマンタンや1−イソプロペニルア
ダマンタンではカチオン触媒によってそれらの単一重合
体が得られているが、カチオン触媒によってアクリレー
ト系モノマーやメタクリレート系モノマーとの共重合体
を得ることはできなかった。また、ラジカル開始剤ある
いはアニオン開始剤を用いて、これらの化合物とアクリ
レート系モノマーやメタクリレート系モノマーとの共重
合体を得ることもできなかった。The 1-vinyl adamantane and 1-isopropenyl adamantane known to date have poor polymerizability, so that the desired polymer cannot always be obtained as desired. It was For example, 1-vinyl adamantane and 1-isopropenyl adamantane have obtained their homopolymers by a cation catalyst, but it has been impossible to obtain a copolymer with an acrylate monomer or a methacrylate monomer by a cation catalyst. .. Further, it was not possible to obtain a copolymer of these compounds with an acrylate-based monomer or a methacrylate-based monomer by using a radical initiator or an anion initiator.
【0004】本発明の目的は、高分子材料、医薬、農薬
等の有機合成の原料として実用性が高い、アダマンタン
骨格を備えた高重合性の化合物を提供することである。An object of the present invention is to provide a highly polymerizable compound having an adamantane skeleton, which is highly practical as a raw material for organic synthesis of polymer materials, pharmaceuticals, agricultural chemicals and the like.
【0005】[0005]
【課題を解決するための手段】本発明の新規化合物の1
−(1′−シアノエテニル)アダマンタンは、下記構造
式で示される。One of the novel compounds of the present invention
-(1'-Cyanoethenyl) adamantane is represented by the following structural formula.
【0006】[0006]
【化2】 [Chemical 2]
【0007】この化合物は、アクリレート誘導体やメタ
クリレート誘導体といったような他のモノマーと容易に
共重合させることができ、側鎖としてアダマンチル基が
主鎖に直接結合した新規な共重合体を提供することがで
きる。This compound can be easily copolymerized with other monomers such as an acrylate derivative or a methacrylate derivative to provide a novel copolymer having an adamantyl group as a side chain directly bonded to the main chain. it can.
【0008】本発明の1−(1′−シアノエテニル)ア
ダマンタンは、知られている様々な方法を応用して製造
することが可能である。例えば、この新しいアダマンタ
ン化合物は、アダマンチルメチルケトンを出発原料とし
て、次の三段階の反応からたやすく製造することができ
る。The 1- (1'-cyanoethenyl) adamantane of the present invention can be produced by applying various known methods. For example, this new adamantane compound can be easily produced from the following three-step reaction using adamantyl methyl ketone as a starting material.
【0009】(1)アダマンチルメチルケトンへのシア
ノトリメチルシランの付加反応(1) Addition reaction of cyanotrimethylsilane to adamantyl methyl ketone
【0010】[0010]
【化3】 [Chemical 3]
【0011】このシアノトリメチルシリル化反応は、例
えば、窒素雰囲気下に乾燥塩化メチレンを溶媒とし、ヨ
ウ化亜鉛の存在下でシアノトリメチルシランをアダマン
チルメチルケトンに作用させることにより容易に行わせ
ることができ、当該付加体(トリメチルシリルエーテ
ル)を高収率で得ることができる。反応終了後、溶媒を
除去し、残留物を精製して高純度の付加体が得られる。The cyanotrimethylsilylation reaction can be easily carried out, for example, by using dry methylene chloride as a solvent in a nitrogen atmosphere and reacting cyanotrimethylsilane with adamantyl methyl ketone in the presence of zinc iodide, The adduct (trimethylsilyl ether) can be obtained in high yield. After completion of the reaction, the solvent is removed and the residue is purified to obtain a highly pure adduct.
【0012】(2)トリメチルシリルエーテルの加水分
解反応(2) Hydrolysis reaction of trimethylsilyl ether
【0013】[0013]
【化4】 [Chemical 4]
【0014】トリメチルシリルエーテルの加水分解反応
は、例えば、テトラヒドロフラン(THF)中で塩酸を
用い、加熱して行わせることができる。反応終了後、反
応溶液をアルカリ水溶液で中和し、反応生成物をエーテ
ル等の有機溶媒で水層から抽出して水分を除去し、更に
有機溶媒を除去することによって、対応するヒドロキシ
ル体を容易に且つ高収率で得ることができる。The hydrolysis reaction of trimethylsilyl ether can be carried out, for example, by using hydrochloric acid in tetrahydrofuran (THF) and heating. After completion of the reaction, the reaction solution is neutralized with an alkaline aqueous solution, the reaction product is extracted from the aqueous layer with an organic solvent such as ether to remove water, and the organic solvent is further removed to easily prepare the corresponding hydroxyl compound. And can be obtained in high yield.
【0015】(3)ヒドロキシル体の脱水反応(3) Dehydration reaction of hydroxyl group
【0016】[0016]
【化5】 [Chemical 5]
【0017】ヒドロキシル体をピリジンに溶解させ、還
流下に過剰量のオキシ塩化リンを作用させる。反応終了
後、反応溶液をエーテルで希釈し、氷を加えて冷却しな
がら過剰のオキシ塩化リンを加水分解し、水層からエー
テル等で抽出した後の抽出液をもとの油層と一緒にし、
これを希アルカリ水溶液で洗い、水分を除去し、更に有
機溶媒を除去してから残留物を精製して、1−(1′−
シアノエテニル)アダマンタンが得られる。The hydroxyl form is dissolved in pyridine and an excess amount of phosphorus oxychloride is allowed to act under reflux. After completion of the reaction, the reaction solution was diluted with ether, excess phosphorus oxychloride was hydrolyzed while adding ice and cooling, and the extract after extraction from the aqueous layer with ether etc. was combined with the original oil layer,
This is washed with a dilute aqueous alkaline solution to remove water and further remove an organic solvent, and then the residue is purified to give 1- (1'-
Cyanoethenyl) adamantane is obtained.
【0018】本発明の1−(1′−シアノエテニル)ア
ダマンタンは上に例示したような方法によって容易に製
造することができるが、この新しいアダマンタン化合物
の製造方法はこれだけに限定されるものではなく、この
ほかに知られている種々の方法を利用して適宜製造する
ことが可能であることは言うまでもない。従って、どの
ような製造方法で調製されたものでも上記構造式で表さ
れるものである限り、全て本発明の範囲内に含まれる。The 1- (1'-cyanoethenyl) adamantane of the present invention can be easily produced by the method as exemplified above, but the production method of the new adamantane compound is not limited thereto. Needless to say, it is possible to appropriately manufacture by using various known methods. Therefore, as long as it is prepared by any manufacturing method as long as it is represented by the above structural formula, it is included in the scope of the present invention.
【0019】[0019]
【作用】本発明の1−(1′−シアノエテニル)アダマ
ンタンは、その分子中にシアノエテニル基を有する。こ
のシアノエテニル基は、従来のアダマンタン化合物であ
る1−ビニルアダマンタンや1−イソプロペニルアダマ
ンタンにおけるビニル基やイソプロペニル基と異なり、
重合活性が高く、そのため本発明のアダマンタン化合物
を他の共重合性モノマーと容易に重合して共重合体を得
ることができるものにする。これらの重合体は、側鎖と
してアダマンチル基が主鎖に直接結合した新規の重合体
となる。The 1- (1'-cyanoethenyl) adamantane of the present invention has a cyanoethenyl group in its molecule. This cyanoethenyl group is different from the vinyl group and isopropenyl group in 1-vinyladamantane and 1-isopropenyladamantane, which are conventional adamantane compounds,
The polymerization activity is high, and therefore, the adamantane compound of the present invention can be easily polymerized with another copolymerizable monomer to obtain a copolymer. These polymers are novel polymers in which an adamantyl group as a side chain is directly bonded to the main chain.
【0020】更に、本発明の1−(1′−シアノエテニ
ル)アダマンタンでは、アダマンチル基の水素原子を他
の原子又は原子団で置換する反応や、シアノ基の位置で
の様々な反応等も期待できることから、この化合物は高
分子材料、医薬、農薬等の有機合成の原料としての広い
用途を提供する。Further, in the 1- (1'-cyanoethenyl) adamantane of the present invention, a reaction of substituting a hydrogen atom of an adamantyl group with another atom or an atomic group, various reactions at the position of a cyano group, etc. can be expected. Therefore, this compound provides a wide range of uses as a raw material for organic synthesis of polymer materials, pharmaceuticals, agricultural chemicals and the like.
【0021】[0021]
【実施例】本発明の1−(1′−シアノエテニル)アダ
マンタンの製造を、以下の実施例でもって更に詳しく説
明する。EXAMPLES The preparation of 1- (1'-cyanoethenyl) adamantane of the present invention will be described in more detail by the following examples.
【0022】(1)1−(1′−シアノ−1′−トリメ
チルシロキシエチル)アダマンタンの調製 十分に乾燥させた100mlの三つ口フラスコに、ラバー
セプタム、塩化カルシウム管及びジムロート冷却器を取
付け、ポリテトラフルオロエチレン(PTFE)でコー
ティングされたスターラーバーを入れ、そしてアダマン
チルメチルケトン17.115g(96mmol)、ヨウ化
亜鉛500mg及び無水塩化メチレン20mlを入れて、窒
素雰囲気下に10℃で攪拌した。この混合溶液へ、PT
FEチューブのキャヌラーを使ってシアノトリメチルシ
ラン10g(100.8mmol)をゆっくりと滴下導入し
た。1時間後、反応溶液を室温に戻し、更に4時間攪拌
した。薄層クロマトグラフィーで反応終了を確認した
後、減圧下で溶媒を除去し、そして残留物をシリカゲル
カラムクロマトグラフィーで精製して、2/98〜4/
96の酢酸エチル/ヘキサンで溶出されたフラクション
を集めた。(1) Preparation of 1- (1'-cyano-1'-trimethylsiloxyethyl) adamantane A fully dried 100 ml three-necked flask was equipped with a rubber septum, a calcium chloride tube and a Dimroth condenser, A stirrer bar coated with polytetrafluoroethylene (PTFE) was added, and 17.115 g (96 mmol) of adamantyl methyl ketone, 500 mg of zinc iodide and 20 ml of anhydrous methylene chloride were added, and the mixture was stirred at 10 ° C. under a nitrogen atmosphere. To this mixed solution, PT
10 g (100.8 mmol) of cyanotrimethylsilane was slowly added dropwise using a can of an FE tube. After 1 hour, the reaction solution was returned to room temperature and further stirred for 4 hours. After confirming the completion of the reaction by thin layer chromatography, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to give 2 / 98-4 /
Fractions eluted with 96 ethyl acetate / hexanes were collected.
【0023】得られた1−(1′−シアノ−1′−トリ
メチルシロキシエチル)アダマンタンは白色結晶であ
り、その収量は26.4g(定量的)であった。また、
この化合物の赤外分光分析の結果(KBr、ディスク、
cm-1)は次に示すとおりであった。2905,2659
(vw),2227(vw),1449,1252,112
7,1002,866,843,764,627The 1- (1'-cyano-1'-trimethylsiloxyethyl) adamantane obtained was white crystals and the yield was 26.4 g (quantitative). Also,
Results of infrared spectroscopy analysis of this compound (KBr, disk,
cm -1 ) was as shown below. 2905, 2659
(Vw), 2227 (vw), 1449, 1252, 112
7,1002,866,843,764,627
【0024】(2)1−(1′−シアノ−1′−ヒドロ
キシエチル)アダマンタンの調製 200mlのナス型フラスコに、PTFEコーティングさ
れたスターラーバーを入れ、9.11g(32.9mmo
l)の1−(1′−シアノ−1′−トリメチルシロキシ
エチル)アダマンタン、15mlのテトラヒドロフラン及
び15mlの2規定塩酸水溶液を入れ、そしてジムロート
冷却器を取付けて80℃で激しく攪拌した。10時間
後、薄層クロマトグラフィーで原料の消失していること
を確認してから、反応溶液を0℃に冷却し、激しく攪拌
しながら炭酸水素カリウム水溶液をゆっくり加えて中和
した。(2) Preparation of 1- (1'-cyano-1'-hydroxyethyl) adamantane In a 200 ml eggplant-shaped flask, a PTFE-coated stirrer bar was placed, and 9.11 g (32.9 mmo).
1) 1- (1'-cyano-1'-trimethylsiloxyethyl) adamantane, 15 ml of tetrahydrofuran and 15 ml of 2N aqueous hydrochloric acid solution were added, and a Dimroth condenser was attached, and the mixture was vigorously stirred at 80 ° C. After 10 hours, it was confirmed by thin layer chromatography that the raw materials had disappeared, and then the reaction solution was cooled to 0 ° C., and an aqueous potassium hydrogencarbonate solution was slowly added to neutralize the solution while vigorously stirring.
【0025】次いで、分液ロートで油層を分離し、水層
をジエチルエーテルで3回抽出してから得られた抽出液
をもとの油層と合わせ、その結果得られた溶液を飽和食
塩水で洗い、再び油層と水層とを分離して、油層溶液を
無水硫酸ナトリウムで乾燥させた。硫酸ナトリウムをろ
別後、減圧下で溶媒を除去して、粗生成物の1−(1′
−シアノ−1′−ヒドロキシエチル)アダマンタンを白
色結晶として得た。Then, the oil layer was separated with a separating funnel, the aqueous layer was extracted three times with diethyl ether, and the extract obtained was combined with the original oil layer, and the resulting solution was saturated with brine. After washing, the oil layer and the aqueous layer were separated again, and the oil layer solution was dried over anhydrous sodium sulfate. After the sodium sulfate was filtered off, the solvent was removed under reduced pressure to give the crude product 1- (1 '
-Cyano-1'-hydroxyethyl) adamantane was obtained as white crystals.
【0026】このアダマンタン化合物の収量は6.71
g(定量的)であった。赤外分光分析の結果(KBr、
ディスク、cm-1)は次に示すとおりであった。350
6,2909,2678(vw),2226(w),14
51,1355,1134,919,819The yield of this adamantane compound is 6.71.
g (quantitative). Results of infrared spectroscopy (KBr,
Discs, cm -1 ) were as shown below. 350
6,2909,2678 (vw), 2226 (w), 14
51, 1355, 1134, 919, 819
【0027】複生成物は認められなかったので、調製し
た化合物を未精製のまま次の反応のために使用した。Since no double product was observed, the prepared compound was used for the next reaction without purification.
【0028】(3)1−(1′−シアノエテニル)アダ
マンタンの製造 PTFEでコーティングされたスターラーバーを入れた
200mlのナス型フラスコに、8.80g(42.9mm
ol)の1−(1′−シアノ−1′−ヒドロキシエチル)
アダマンタンを入れ、窒素雰囲気下に無水ピリジン60
ml、オキシ塩化リン11.7ml(129mmol)を加え、
攪拌しながら還流させた。10時間後、薄層クロマトグ
ラフィーで原料の消失を確認してから室温に放冷した。
この反応溶液をジエチルエーテルで希釈し、この希釈反
応溶液を、4規定塩酸200mlと氷を入れて0℃で攪拌
している1リットルの三角フラスコにゆっくりと注い
だ。溶液の温度が上がらないように適時氷を加え、希釈
反応溶液を全て注ぎ終わったらそのまま1時間攪拌を続
けた。(3) Preparation of 1- (1'-cyanoethenyl) adamantane In a 200 ml eggplant-shaped flask containing a stirrer bar coated with PTFE, 8.80 g (42.9 mm)
1- (1'-cyano-1'-hydroxyethyl) of ol)
Add adamantane and add anhydrous pyridine 60 under nitrogen atmosphere.
ml, 11.7 ml (129 mmol) of phosphorus oxychloride,
Refluxed with stirring. After 10 hours, disappearance of the raw materials was confirmed by thin layer chromatography, and then the mixture was allowed to cool to room temperature.
The reaction solution was diluted with diethyl ether, and the diluted reaction solution was slowly poured into a 1 liter Erlenmeyer flask containing 200 ml of 4N hydrochloric acid and ice and stirring at 0 ° C. Ice was added at appropriate times so that the temperature of the solution did not rise, and after all the diluted reaction solution had been poured, stirring was continued for 1 hour.
【0029】次いで、三角フラスコの内容液を分液ロー
トにあけて油層を分離し、水層をジエチルエーテルで3
回抽出してから得られた抽出液をもとの油層と一緒に
し、この混合溶液を希炭酸水素カリウム溶液で、次いで
飽和食塩水で洗った。油層と水層とを分離後、油層溶液
を無水硫酸ナトリウムで乾燥させた。次に、硫酸ナトリ
ウムをろ別し、減圧下で溶媒を除去し、そして残留物を
シリカゲルカラムクロマトグラフィーで精製して、4/
96のジエチルエーテル/ヘキサンで溶出されたフラク
ションを集めた。Then, the content liquid of the Erlenmeyer flask was poured into a separating funnel to separate an oil layer, and the aqueous layer was washed with diethyl ether.
The extract obtained after the second extraction was combined with the original oil layer, and this mixed solution was washed with a dilute potassium hydrogen carbonate solution and then with a saturated saline solution. After separating the oil layer and the aqueous layer, the oil layer solution was dried over anhydrous sodium sulfate. Then the sodium sulphate is filtered off, the solvent is removed under reduced pressure and the residue is purified by silica gel column chromatography, 4 /
Fractions eluted with 96 diethyl ether / hexane were collected.
【0030】得られた1−(1′−シアノエテニル)ア
ダマンタンは無色透明の液体で、その収量は7.62g
(94.8%)であった。また、この化合物の赤外分光
分析(IR)の結果(KBr、ニート、cm-1)、 1H
NMR及び13C NMR分析の結果(CDCl3 ,δ、
内部標準TMS)は、次に示すとおりであった。The obtained 1- (1'-cyanoethenyl) adamantane was a colorless transparent liquid, and the yield was 7.62 g.
(94.8%). Also, the results of infrared spectroscopic analysis (IR) of this compound (KBr, neat, cm −1 ), 1 H
Results of NMR and 13 C NMR analyzes (CDCl 3 , δ,
The internal standard TMS) was as shown below.
【0031】IR:2906,2680,2220
(m),1614,1452,931,6271 H NMR:5.81(1H、一重線)、5.63
(1H、一重線)、2.08(3H、一重線)、1.7
7〜1.63(12H、多重線)13 C NMR:134.1(s),126.1(t),
117.8(s),40.5(t),36.8(s),
36.3(t),28.1(d)IR: 2906, 2680, 2220
(M), 1614, 1452, 931, 627 1 H NMR: 5.81 (1H, singlet), 5.63.
(1H, singlet), 2.08 (3H, singlet), 1.7
7 to 1.63 (12H, multiplet) 13 C NMR: 134.1 (s), 126.1 (t),
117.8 (s), 40.5 (t), 36.8 (s),
36.3 (t), 28.1 (d)
【0032】IRデータのうち、2220cm-1のピーク
はα, β不飽和ニトリルに由来し、1614cm-1のピー
クは共役二重結合に由来する。 1H NMRデータのう
ち、5.81,5.63ppm のピークはシアノエテニル
基のメチレンプロトンに由来し、2.08ppm のピーク
はアダマンタン環のメチレンプロトンに由来する。13C
NMRデータのうち、117.8ppm のピークはシア
ノ基の炭素に由来する。In the IR data, the peak at 2220 cm -1 is derived from α, β unsaturated nitrile, and the peak at 1614 cm -1 is derived from conjugated double bond. In the 1 H NMR data, the peaks at 5.81 and 5.63 ppm are derived from the methylene proton of the cyanoethenyl group, and the peak at 2.08 ppm is derived from the methylene proton of the adamantane ring. 13 C
In the NMR data, the peak at 117.8 ppm is derived from the carbon of the cyano group.
【0033】こうして得られた本発明のアダマンタン化
合物をエッチング耐性に優れたメタクリレート系などの
他の重合性モノマーと共重合させて作られた共重合体を
ベースポリマーとしてレジスト材料を製造すれば、エッ
チング耐性の強いレジスト材料を提供することができ
る。When a resist material is produced using a copolymer prepared by copolymerizing the adamantane compound of the present invention thus obtained with another polymerizable monomer such as a methacrylate having excellent etching resistance, as a base polymer, etching is performed. A resist material having high resistance can be provided.
【0034】[0034]
【発明の効果】本発明の1−(1′−シアノエテニル)
アダマンタンは、重合活性のあるシアノエテニル基を分
子中に有し、更にアダマンチル基の水素原子を他の原子
又は原子団で置換する反応やシアノ基の位置での反応等
も期待できるため、高分子材料、医薬、農薬等の有機合
成の原料として実用性が高い。1- (1'-cyanoethenyl) of the present invention
Adamantane has a cyanoethenyl group having a polymerization activity in the molecule, and since a reaction of substituting the hydrogen atom of the adamantyl group with another atom or atomic group, a reaction at the position of the cyano group, etc. can be expected, the polymer material It is highly practical as a raw material for organic synthesis such as pharmaceuticals and agricultural chemicals.
【0035】最も実用性が高いのは、その重合活性を利
用した重合性モノマーとしての用途であり、機能性高分
子材料の合成原料として有利に用いることができる。す
なわち、本発明の1−(1′−シアノエテニル)アダマ
ンタンは、例えば金属アルコキシド、金属アルキル、グ
リニヤール試薬等のアニオン触媒、あるいはアゾ系ラジ
カル発生剤等の存在下で、共重合性モノマーと重合して
共重合体を与えることができる。また、用途や目的に応
じて相手の共重合性モノマーを選択することによって、
物性のより改善された共重合体を得ることができる。The most practical use is as a polymerizable monomer utilizing its polymerization activity, and it can be advantageously used as a raw material for synthesizing a functional polymer material. That is, 1- (1'-cyanoethenyl) adamantane of the present invention is polymerized with a copolymerizable monomer in the presence of an anion catalyst such as a metal alkoxide, a metal alkyl, a Grignard reagent, or an azo radical generator. A copolymer can be provided. Also, by selecting the other copolymerizable monomer according to the application or purpose,
A copolymer having improved physical properties can be obtained.
【0036】更に、現在までに知られている1−ビニル
アダマンタンや1−イソプロペニルアダマンタンではカ
チオン触媒によって単一重合体が得られてはいるが、カ
チオン触媒でもってこれらの化合物のモノマーとアクリ
レート系あるいはメタクリレート系モノマーとの共重合
体を得ることはできず、重合体の改質を図ることが難し
いため、汎用性が低かったのとは違って、本発明の1−
(1′−シアノエテニル)アダマンタンを利用すること
によって重合体を用途や目的に合わせて設計することが
可能になり、汎用性を高めることができる。Further, although 1-vinyl adamantane and 1-isopropenyl adamantane which have been known so far have been obtained as a homopolymer by a cation catalyst, a monomer and an acrylate type compound of these compounds can be obtained by the cation catalyst. Since a copolymer with a methacrylate-based monomer cannot be obtained and it is difficult to modify the polymer, the versatility was low, and
By using (1'-cyanoethenyl) adamantane, the polymer can be designed according to the intended use and purpose, and the versatility can be enhanced.
【0037】また、重合体の主鎖に直接アダマンチル基
が側鎖として結合した新規の重合体が得られるため、新
材料への適用が期待できる。Further, since a new polymer in which an adamantyl group is directly bonded to the main chain of the polymer as a side chain is obtained, application to a new material can be expected.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 G03F 7/027 511 7/038 H01L 21/027 Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI Technical display location G03F 7/027 511 7/038 H01L 21/027
Claims (2)
ノエテニル)アダマンタン。 【化1】 1. 1- (1′-cyanoethenyl) adamantane represented by the following structural formula: [Chemical 1]
ニル)アダマンタンと他の共重合性有機化合物との共重
合体をベースポリマーとするレジスト材料。2. A resist material containing a copolymer of 1- (1′-cyanoethenyl) adamantane according to claim 1 and another copolymerizable organic compound as a base polymer.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4150645A JP3069816B2 (en) | 1992-06-10 | 1992-06-10 | 1- (1'-cyanoethenyl) adamantane and resist material |
DE4319178A DE4319178C2 (en) | 1992-06-10 | 1993-06-09 | Resist composition containing a polymer material and an acid generator |
US08/275,360 US5399647A (en) | 1992-06-10 | 1994-07-15 | Photoresist composition of 1-(1'-cyanoethenyl)adamantane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4150645A JP3069816B2 (en) | 1992-06-10 | 1992-06-10 | 1- (1'-cyanoethenyl) adamantane and resist material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05339225A true JPH05339225A (en) | 1993-12-21 |
JP3069816B2 JP3069816B2 (en) | 2000-07-24 |
Family
ID=15501383
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4150645A Expired - Fee Related JP3069816B2 (en) | 1992-06-10 | 1992-06-10 | 1- (1'-cyanoethenyl) adamantane and resist material |
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JP (1) | JP3069816B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100412072C (en) * | 2003-10-16 | 2008-08-20 | 旭硝子株式会社 | Novel fluorine-containing dioxolane compound and novel fluorine-containing polymer |
JP2013028820A (en) * | 2004-03-09 | 2013-02-07 | Rohm & Haas Electronic Materials Llc | Cyanoadamantyl compound and polymer |
-
1992
- 1992-06-10 JP JP4150645A patent/JP3069816B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100412072C (en) * | 2003-10-16 | 2008-08-20 | 旭硝子株式会社 | Novel fluorine-containing dioxolane compound and novel fluorine-containing polymer |
JP2013028820A (en) * | 2004-03-09 | 2013-02-07 | Rohm & Haas Electronic Materials Llc | Cyanoadamantyl compound and polymer |
Also Published As
Publication number | Publication date |
---|---|
JP3069816B2 (en) | 2000-07-24 |
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