JPH04351602A - Cyclodextrin derivative - Google Patents
Cyclodextrin derivativeInfo
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- JPH04351602A JPH04351602A JP15406691A JP15406691A JPH04351602A JP H04351602 A JPH04351602 A JP H04351602A JP 15406691 A JP15406691 A JP 15406691A JP 15406691 A JP15406691 A JP 15406691A JP H04351602 A JPH04351602 A JP H04351602A
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- cyclodextrin
- dmf
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- water
- precipitate
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Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はシクロデキストリンの誘
導体に関し、更に詳しくは高い水溶性を有するシクロデ
キストリン誘導体に関する。FIELD OF THE INVENTION The present invention relates to cyclodextrin derivatives, and more particularly to cyclodextrin derivatives having high water solubility.
【０００２】0002
【従来の技術】一般に医薬、農薬等の薬品類等は用途上
、水溶性を有することが求められる。近年、これらの水
溶性を向上させる手段の一つとして、上記薬品類等をシ
クロデキストリンに包接させることによって水溶性を向
上させる方法が提案されている。BACKGROUND OF THE INVENTION In general, drugs such as medicines and agricultural chemicals are required to be water-soluble due to their use. In recent years, as one means for improving the water solubility of these substances, a method has been proposed in which the above-mentioned chemicals and the like are included in cyclodextrin to improve the water solubility.
【０００３】0003
【発明が解決しようとする課題】しかしながら、このよ
うなシクロデキストリン包接化合物においても、シクロ
デキストリン自体の水への溶解度に限度があるため、そ
の水溶性は実用上未だ不十分であった。このため、シク
ロデキストリンの水に対する溶解度を向上させるため、
シクロデキストリンをメチル化、ヒドロキシエチル化、
ヒドロキシプロピル化するか、あるいはエピクロルヒド
リンを用いて架橋させたポリマーを合成する等の方法が
行なわれているが、未だ十分な効果は得られていなかっ
た。[Problems to be Solved by the Invention] However, even in such cyclodextrin clathrate compounds, the solubility in water of cyclodextrin itself is limited, so that its water solubility is still insufficient for practical use. Therefore, to improve the solubility of cyclodextrin in water,
Methylation, hydroxyethylation of cyclodextrin,
Methods such as hydroxypropylation or synthesis of crosslinked polymers using epichlorohydrin have been used, but sufficient effects have not yet been obtained.
【０００４】従って、本発明の目的は、水に対して高い
溶解性を有するシクロデキストリン誘導体を提供するこ
とにある。[0004] Accordingly, an object of the present invention is to provide a cyclodextrin derivative having high solubility in water.
【０００５】[0005]
【課題を解決するための手段】本発明者は前記課題に鑑
みて鋭意研究の結果、本発明の上記目的は、少なくとも
一つのカルボキシル基又は少なくとも一つのカルボン酸
塩基を有するシクロデキストリン誘導体を提供すること
により達成されることを見出した。[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have made extensive research and found that the above-mentioned object of the present invention is to provide a cyclodextrin derivative having at least one carboxyl group or at least one carboxylic acid group. We found that this can be achieved by
【０００６】以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
【０００７】本発明は、カルボキシル基（−ＣＯＯＨ）
又はカルボン酸塩基（−ＣＯＯＭ）をシクロデキストリ
ン（以下、ＣＤと略記する）分子に確実に導入すること
により水に対する溶解度を大幅に向上させるものである
が、この結果得られる本発明のＣＤ誘導体としては、具
体的には、モノカルボン酸β−ＣＤ、ジカルボン酸β−
ＣＤ、ヘプタカルボン酸β−ＣＤ等が挙げられる。[0007] The present invention provides carboxyl group (-COOH)
Alternatively, the solubility in water is greatly improved by surely introducing a carboxylic acid group (-COOM) into a cyclodextrin (hereinafter abbreviated as CD) molecule, and as a result of this, the CD derivative of the present invention Specifically, monocarboxylic acid β-CD, dicarboxylic acid β-
CD, heptacarboxylic acid β-CD, and the like.
【０００８】また、本発明に用いられるＣＤとしてはα
−ＣＤ、β−ＣＤ、γ−ＣＤ等のいずれも用いることが
できる。[0008] Also, the CD used in the present invention is α
-CD, β-CD, γ-CD, etc. can be used.
【０００９】少なくとも１つのカルボキシル基又は少な
くとも一つのカルボン酸塩基を有するＣＤ誘導体の合成
例を以下に示す。Examples of the synthesis of CD derivatives having at least one carboxyl group or at least one carboxylic acid group are shown below.
【００１０】0010
【化１】[Chemical formula 1]
【００１１】[0011]
【化２】[Case 2]
【００１２】0012
【化３】 上記反応について、具体的合成例について以下に示す。[Chemical formula 3] Concerning the above reaction, specific synthesis examples are shown below.
【００１３】（Ａ）モノカルボン酸β−ＣＤの合成β−
ＣＤを脱水ピリジンに室温で溶解し、その系に２０℃以
下でピリジンに溶解したｐ−トルエンスルホニルクロラ
イドを滴下する。滴下終了後、室温でさらに一昼夜攪拌
する。反応終了後、ピリジンを減圧下４０℃以下で留去
し残渣を大量のアセトンより再沈殿を行ない、沈殿物を
集めて水より再結晶を３度行なう。（収率：約２５％）
(A) Synthesis of monocarboxylic acid β-CD β-
CD is dissolved in dehydrated pyridine at room temperature, and p-toluenesulfonyl chloride dissolved in pyridine is added dropwise to the system at 20° C. or below. After completion of the dropwise addition, the mixture was further stirred at room temperature overnight. After the reaction is completed, pyridine is distilled off under reduced pressure at 40° C. or lower, the residue is reprecipitated from a large amount of acetone, and the precipitate is collected and recrystallized from water three times. (Yield: approx. 25%)
【００１４】得られたβ−ＣＤモノトシレートをＤＭＦ
に溶解し、ＫＩと７０〜８０℃の温度下一昼夜反応させ
る。
反応終了後、ＤＭＦを減圧下で留去、残渣を大量のアセ
トンより再沈殿を行ない、沈殿物は集めてｎ−ブタノー
ル／エタノール／水系より再結晶を行なった。（収率：
約６０％）[0014] The obtained β-CD monotosylate was diluted with DMF.
and react with KI at a temperature of 70 to 80°C overnight. After the reaction was completed, DMF was distilled off under reduced pressure, the residue was reprecipitated from a large amount of acetone, and the precipitate was collected and recrystallized from an n-butanol/ethanol/water system. (yield:
approximately 60%)
【００１５】次にＤＭＦ中でグリコール酸（ｎ＝１）と
ＮａＨを室温、窒素気流下で反応させ、１時間後系を３
０〜４０℃の温度に上げ、そこにＤＭＦに溶解したβ−
ＣＤモノアイオダイドを滴下し、滴下終了後９０〜１０
０℃で一昼夜反応させる。反応終了後ＤＭＦを減圧下留
去し残渣を大量のアセトンより再沈殿させ、沈殿物は熱
メタノールに溶解させ、濾過後、再度大量のアセトンよ
り再沈殿させる。沈殿物は集めて水に溶解させ、強酸性
イオン交換樹脂で処理することで目的物を得る。（収率
：約３５％）Next, glycolic acid (n=1) and NaH were reacted in DMF at room temperature under a nitrogen stream, and after 1 hour, the system was
β- dissolved in DMF was raised to a temperature of 0-40 °C.
Drop CD monoiodide, 90 to 10 after finishing dropping.
React overnight at 0°C. After completion of the reaction, DMF is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of acetone. The precipitate is dissolved in hot methanol, filtered, and reprecipitated again from a large amount of acetone. The precipitate is collected, dissolved in water, and treated with a strongly acidic ion exchange resin to obtain the desired product. (Yield: approx. 35%)
【００１６】（Ｂ）ジカルボン酸β−ＣＤの合成β−Ｃ
Ｄを室温下ピリジンに溶解し、これにピリジンに溶解し
たジフェニルメタンｐ，ｐ′−ジスルホニルクロライド
を５℃にて滴下した。滴下終了後２０℃以下にて１昼夜
攪拌した。反応終了後ピリジンを４０℃以下で減圧留去
し、残渣を大量のアセトンより再沈殿を行なう。沈殿物
を集め、水より再結晶を繰り返し精製し、化合物（１）
を得る。（収率：約１５％）(B) Synthesis of dicarboxylic acid β-CD β-C
D was dissolved in pyridine at room temperature, and diphenylmethane p,p'-disulfonyl chloride dissolved in pyridine was added dropwise thereto at 5°C. After the dropwise addition was completed, the mixture was stirred at 20° C. or lower for one day and night. After the reaction is completed, pyridine is distilled off under reduced pressure at a temperature below 40°C, and the residue is reprecipitated from a large amount of acetone. The precipitate was collected and purified by repeated recrystallization from water to obtain compound (1).
get. (Yield: about 15%)
【００１７】得られた化合物（１）を、ＤＭＦ中でＫＩ
と７０〜８０℃の温度下１昼夜反応させ、終了後ＤＭＦ
を減圧下留去し、残渣を大量のアセトンより再沈殿させ
る。
沈殿物は集めてｎ−ブタノール／エタノール／水系より
再結晶し精製し、化合物（２）を得る。（収率：約５５
％）The obtained compound (1) was treated with KI in DMF.
The reaction was carried out for one day and night at a temperature of 70 to 80°C, and after completion of the reaction, DMF
is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of acetone. The precipitate is collected and purified by recrystallization from n-butanol/ethanol/water system to obtain compound (2). (Yield: approx. 55
%)
【００１８】次に、ＤＭＦ中でグリコール酸（ｎ＝１）
とＮａＨを室温、窒素気流下反応させ、１時間後、系を
３０〜４０℃に上げ、そこにＤＭＦに溶解した化合物（
２）を滴下し、滴下終了後９０〜１００℃の温度で一昼
夜反応させる。反応終了後ＤＭＦを減圧下留去し残渣を
大量のアセトンより再沈殿させ、沈殿物は熱エタノール
に溶解させ、濾過後、再度大量のアセトンより再沈殿さ
せ、化合物（３）を得る。沈殿物は集めて水に溶解させ
、強酸性イオン交換樹脂で処理することで目的物（４）
を得た。
（収率：約２０％）Next, glycolic acid (n=1) in DMF
and NaH were reacted at room temperature under a nitrogen stream, and after 1 hour, the system was raised to 30-40°C, and the compound dissolved in DMF (
2) was added dropwise, and after the completion of the dropwise addition, the mixture was allowed to react overnight at a temperature of 90 to 100°C. After completion of the reaction, DMF is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of acetone. The precipitate is dissolved in hot ethanol, filtered, and reprecipitated again from a large amount of acetone to obtain compound (3). The precipitate is collected, dissolved in water, and treated with a strongly acidic ion exchange resin to obtain the desired product (4).
I got it. (Yield: approx. 20%)
【００１９】（Ｃ）ヘプタカルボン酸β−ＣＤの合成Ｄ
ＭＦ中に室温でβ−ＣＤを溶解し、メタンスルホニルブ
ロマイドを加え添加後６０〜７０℃の温度で２４時間攪
拌した。反応終了後ＤＭＦを減圧下留去し、残渣を大量
のメタノールより再沈殿した。そして中和後氷冷水に加
え濾過し、沈殿物を氷冷水でよく洗浄し、乾燥すること
でβ−ＣＤヘプタブロマイドを得た。（収率：約８０％
）(C) Synthesis D of heptacarboxylic acid β-CD
β-CD was dissolved in MF at room temperature, methanesulfonyl bromide was added, and after the addition, the mixture was stirred at a temperature of 60 to 70°C for 24 hours. After the reaction was completed, DMF was distilled off under reduced pressure, and the residue was reprecipitated from a large amount of methanol. After neutralization, it was added to ice-cold water and filtered, and the precipitate was thoroughly washed with ice-cold water and dried to obtain β-CD heptabromide. (Yield: about 80%
)
【００２０】次にＤＭＦ中でグリコール酸（ｎ＝１）
とＮａＨを室温、窒素気流下反応させ、１時間後、系を
３０〜４０℃の温度に上げ、そこにＤＭＦに溶解したβ
−ＣＤヘプタブロマイドを滴下し、滴下終了後９０〜１
００℃の温度で一昼夜反応させる。反応終了後、ＤＭＦ
を減圧下留去し、残渣を大量のジエチルエーテルより再
沈殿させ、沈殿物は熱エタノールに溶解し、濾過後、再
度大量のジエチルエーテルより再沈殿させる。沈殿物は
集めて水に溶解させ、強酸性イオン交換樹脂で処理する
ことで目的物を得る。（収率：約１０％）Next, glycolic acid (n=1) in DMF
and NaH were reacted at room temperature under a nitrogen stream, and after 1 hour, the system was raised to a temperature of 30-40°C, and β dissolved in DMF was added thereto.
-Drop CD heptabromide, 90 to 1 after completion of dripping
React overnight at a temperature of 00°C. After the reaction is complete, DMF
is distilled off under reduced pressure, the residue is reprecipitated from a large amount of diethyl ether, the precipitate is dissolved in hot ethanol, filtered, and reprecipitated again from a large amount of diethyl ether. The precipitate is collected, dissolved in water, and treated with a strongly acidic ion exchange resin to obtain the desired product. (Yield: about 10%)
【００２１】（Ｄ） β−ＣＤを脱水ＤＭＦに溶解し
、窒素気流下ＮａＨと反応させる。室温で１時間攪拌後
、その系を６０〜７０℃に加温する。その温度にてβ−
プロピオラクトン（ｎ＝１）のＤＭＦ溶液をゆっくりと
滴下する。滴下終了後、系を１００℃に上げ、その温度
で１２時間反応させる。反応終了後、ＤＭＦを減圧下留
去させ、残渣を大量のアセトンより再沈殿させる。沈殿
物は熱メタノールに溶解させ、濾過後、再度大量のアセ
トンより再沈殿させる。沈殿物は集めて水に溶解させ、
強酸性イオン交換樹脂で処理することで目的物を得る。
（収率：７５％）(D) β-CD is dissolved in dehydrated DMF and reacted with NaH under a nitrogen stream. After stirring for 1 hour at room temperature, the system is warmed to 60-70°C. At that temperature β-
A DMF solution of propiolactone (n=1) is slowly added dropwise. After the dropwise addition is completed, the system is raised to 100°C and reacted at that temperature for 12 hours. After the reaction is completed, DMF is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of acetone. The precipitate is dissolved in hot methanol, filtered, and reprecipitated again from a large amount of acetone. The precipitate is collected and dissolved in water,
The desired product is obtained by treatment with a strongly acidic ion exchange resin. (Yield: 75%)
【００２２】（Ｅ）ビスカルボン酸β−ＣＤの合成β−
ＣＤを脱水ＤＭＦに溶解し、窒素気流下ＮａＨと反応さ
せる。室温で１時間攪拌後、その系を６０〜７０℃に加
温する。その温度にて２−ブロモエチルマロン酸ジエチ
ルのＤＭＦ溶液をゆっくりと滴下する。滴下終了後、系
を１００℃に上げ、その温度で１２時間反応させる。反
応終了後、ＤＭＦを減圧下留去させ残渣を大量のアセト
ンより再沈殿させる。沈殿物を濾別し、乾燥後メタノー
ルに溶解させ、その系にナトリウムアルコラートのメタ
ノール溶液を滴下し、室温で２４時間反応させる。終了
後沈殿物を濾別し、濾液に強酸性イオン交換樹脂を加え
、１時間攪拌する。メタノールを濃縮後、残渣を大量の
アセトンより再沈殿させる。沈殿物を濾過し、乾燥する
ことで目的物を得る。（収率：約６０％）(E) Synthesis of biscarboxylic acid β-CD β-
CD is dissolved in dehydrated DMF and reacted with NaH under a nitrogen stream. After stirring for 1 hour at room temperature, the system is warmed to 60-70°C. At that temperature, a DMF solution of diethyl 2-bromoethylmalonate is slowly added dropwise. After the dropwise addition is completed, the system is raised to 100°C and reacted at that temperature for 12 hours. After the reaction is complete, DMF is distilled off under reduced pressure and the residue is reprecipitated from a large amount of acetone. The precipitate is filtered, dried, and dissolved in methanol. A methanol solution of sodium alcoholate is added dropwise to the system, and the mixture is allowed to react at room temperature for 24 hours. After the completion of the reaction, the precipitate is filtered off, a strongly acidic ion exchange resin is added to the filtrate, and the mixture is stirred for 1 hour. After concentrating the methanol, the residue is reprecipitated from a large amount of acetone. The desired product is obtained by filtering the precipitate and drying it. (Yield: about 60%)
【００２３】次にカルボン酸塩基を有するＣＤ誘導体の
合成について説明する。Next, the synthesis of a CD derivative having a carboxylic acid group will be explained.
【００２４】前記（Ａ）〜（Ｄ）に対応するモノ、ジ、
ヘプタカルボン酸塩β−ＣＤおよびカルボン酸塩β−Ｃ
Ｄ（Ｄ）のそれぞれの合成は、前記（Ａ）〜（Ｄ）に示
した反応の最終工程における強酸性のイオン交換樹脂に
よる処理を行なわないことにより目的物が得られる。Mono, di, corresponding to the above (A) to (D)
heptacarboxylate β-CD and carboxylate β-C
In each synthesis of D (D), the desired product can be obtained by omitting the treatment with a strongly acidic ion exchange resin in the final step of the reactions shown in (A) to (D) above.
【００２５】また、（Ｆ）テトラデカカルボン酸塩β−
ＣＤの合成は以下のように行なうことができる。[0025] Also, (F) tetradecacarboxylate β-
CD synthesis can be performed as follows.
【００２６】（Ｆ）テトラデカカルボン酸塩β−ＣＤの
合成
β−ＣＤとイミダゾールを室温下ＤＭＦに溶解し、これ
にＤＭＦに溶解したｔ−ブチルジメチルシリルクロライ
ドを滴下する。滴下終了後６時間室温にて撹拌し、反応
終了後ＤＭＦを減圧下留去して残渣をシリカゲルカラム
クロマトグラフィーにより分離、精製する。得られた化
合物をエタノールより再結晶し化合物（１）を精製した
。（収率：約７０％）(F) Synthesis of tetradecacarboxylate β-CD β-CD and imidazole are dissolved in DMF at room temperature, and t-butyldimethylsilyl chloride dissolved in DMF is added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours, and after the reaction was completed, DMF was distilled off under reduced pressure and the residue was separated and purified by silica gel column chromatography. The obtained compound was recrystallized from ethanol to purify compound (1). (Yield: about 70%)
【００２７】
化合物（１）をＤＭＦ中に溶解し、室温下窒素雰囲気で
ＮａＨと反応させる。そしてＤＭＦに溶解したクロロ酢
酸ナトリウム（ｎ＝１）をゆっくり滴下し、滴下終了後
６０〜７０℃で１２時間反応させる。反応終了後ＤＭＦ
を減圧下で留去し、残渣を大量のエチルエーテルより再
沈殿させる。沈殿物は集めて乾燥し、化合物（２）をシ
リカゲルカラムクロマトグラフィーにより分離、精製す
る。
（収率：約３５％）Compound (1) is dissolved in DMF and reacted with NaH in a nitrogen atmosphere at room temperature. Then, sodium chloroacetate (n=1) dissolved in DMF was slowly added dropwise, and after the dropwise addition was completed, the mixture was allowed to react at 60 to 70°C for 12 hours. DMF after the reaction
is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of ethyl ether. The precipitate is collected and dried, and compound (2) is separated and purified by silica gel column chromatography. (Yield: approx. 35%)
【００２８】
化合物（１）をＤＭＦ中に溶解し、室温下窒素雰囲気で
ＮａＨと反応させる。そしてＤＭＦに溶解したβ−プロ
ピオラクトン（ｘ＝１）をゆっくり滴下し、滴下終了後
９０〜１００℃で２４時間反応させる。反応終了後ＤＭ
Ｆを減圧下で留去し、残渣を大量のエチルエーテルより
再沈殿させる。沈殿物は集めて乾燥し、化合物（３）を
シリカゲルカラムクロマトグラフィーにより分離、精製
する。
（収率：約４０％）Compound (1) is dissolved in DMF and reacted with NaH in a nitrogen atmosphere at room temperature. Then, β-propiolactone (x=1) dissolved in DMF is slowly added dropwise, and after the dropwise addition is completed, the mixture is reacted at 90 to 100° C. for 24 hours. DM after reaction
F is distilled off under reduced pressure, and the residue is reprecipitated from a large amount of ethyl ether. The precipitate is collected and dried, and compound (3) is separated and purified by silica gel column chromatography. (Yield: about 40%)
【００２９】化合物（２）及び（３）をそれぞれＴＨＦ
に溶解し、室温下ＴＨＦに溶解したテトラブチルアンモ
ニウムフルオライドを滴下する。滴下終了後、還流下５
時間反応させ、その後沈殿物を濾別し、アセトンで繰り
返し洗浄することで化合物（４）を得る。Compounds (2) and (3) were each treated with THF.
Tetrabutylammonium fluoride dissolved in THF at room temperature is added dropwise. After dropping, reflux 5
After reacting for a period of time, the precipitate is filtered and washed repeatedly with acetone to obtain compound (4).
【００３１】なお目的物の確認はＮＭＲスペクトル、マ
ススペクトル、元素分析などの方法を用いて行なった。The target product was confirmed using methods such as NMR spectrum, mass spectrum, and elemental analysis.
【００３２】その他のＣＤ誘導体についても上記方法に
準じて同様に合成することができる。Other CD derivatives can also be synthesized in the same manner as described above.
【００３３】上記の如く得られるＣＤ誘導体の水に対す
る溶解度を調べた結果を以下に示す。The results of examining the water solubility of the CD derivative obtained as described above are shown below.
【００３４】[0034]
【表１】[Table 1]
【００３５】本発明の高い水溶性を有するＣＤ誘導体は
、例えば医薬、農薬等の薬品、芳香剤、化粧品、洗剤、
塗料、染料、食料品の食品添加物等に用いることができ
る。The highly water-soluble CD derivative of the present invention can be used, for example, in pharmaceuticals, chemicals such as agricultural chemicals, fragrances, cosmetics, detergents,
It can be used in paints, dyes, food additives, etc.
【００３６】以上詳細に述べたように、本発明によりカ
ルボキシル基又はカルボン酸塩基をＣＤに確実に導入す
ることにより、ＣＤの水に対する溶解度を大幅に向上さ
せることができ、この結果水溶性の高いＣＤ包接化合物
を得ることができる。As described in detail above, by reliably introducing a carboxyl group or a carboxylic acid group into CD according to the present invention, the solubility of CD in water can be greatly improved, resulting in highly water-soluble A CD clathrate can be obtained.
Claims (1)
少なくとも一つのカルボン酸塩基を有するシクロデキス
トリン誘導体。1. A cyclodextrin derivative having at least one carboxyl group or at least one carboxylic acid group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15406691A JPH04351602A (en) | 1991-05-29 | 1991-05-29 | Cyclodextrin derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15406691A JPH04351602A (en) | 1991-05-29 | 1991-05-29 | Cyclodextrin derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04351602A true JPH04351602A (en) | 1992-12-07 |
Family
ID=15576153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15406691A Pending JPH04351602A (en) | 1991-05-29 | 1991-05-29 | Cyclodextrin derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04351602A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100761761B1 (en) * | 2006-09-14 | 2007-10-04 | 삼성전자주식회사 | Molecular resin, photoresist composition comprising same and pattern forming method using same |
| KR100761759B1 (en) * | 2006-09-14 | 2007-10-04 | 삼성전자주식회사 | Molecular resin, photoresist composition comprising same and pattern forming method using same |
| JP2009061429A (en) * | 2007-09-07 | 2009-03-26 | Kanagawa Prefecture | Method for separating hydrophobic substance using polyvalent anionic cyclodextrin compound, and selective adsorbent for hydrophobic substance |
-
1991
- 1991-05-29 JP JP15406691A patent/JPH04351602A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100761761B1 (en) * | 2006-09-14 | 2007-10-04 | 삼성전자주식회사 | Molecular resin, photoresist composition comprising same and pattern forming method using same |
| KR100761759B1 (en) * | 2006-09-14 | 2007-10-04 | 삼성전자주식회사 | Molecular resin, photoresist composition comprising same and pattern forming method using same |
| JP2009061429A (en) * | 2007-09-07 | 2009-03-26 | Kanagawa Prefecture | Method for separating hydrophobic substance using polyvalent anionic cyclodextrin compound, and selective adsorbent for hydrophobic substance |
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