JPH0525201A - Production of highly cyanoethylated pullulan - Google Patents
Production of highly cyanoethylated pullulanInfo
- Publication number
- JPH0525201A JPH0525201A JP3186553A JP18655391A JPH0525201A JP H0525201 A JPH0525201 A JP H0525201A JP 3186553 A JP3186553 A JP 3186553A JP 18655391 A JP18655391 A JP 18655391A JP H0525201 A JPH0525201 A JP H0525201A
- Authority
- JP
- Japan
- Prior art keywords
- cyanoethylated
- pullulan
- cyanoethylated pullulan
- highly
- cyanoethylation
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はシアノエチル化置換率95
〜 100％の高シアノエチル化プルランの製造方法に関す
る。This invention relates to a cyanoethylation substitution rate of 95.
~ 100% high cyanoethylated pullulan production method.
【０００２】[0002]
【従来技術】分散型エレクトロルミネッセンス（ＥＬ）
素子は、一般にアルミニウム箔などを背面電極とし、こ
の背面電極上に酸化チタンやチタン酸バリウム等の無機
高誘電体粉末を有機高誘電体バインダーに分散させた反
射絶縁体層を形成し、さらにその上に硫化亜鉛などの蛍
光体粉末を有機高誘電体バインダーに分散させた発光層
を形成し、最後にＩＴＯ（酸化インジウムと酸化スズの
混合物）等の透明電極を対電極として設置した構造を有
し、両電極間に交流電極を印加することにより蛍光体が
発光するものである。2. Description of the Related Art Dispersed electroluminescence (EL)
The element generally has an aluminum foil or the like as a back electrode, and a reflective insulating layer in which an inorganic high dielectric powder such as titanium oxide or barium titanate is dispersed in an organic high dielectric binder is formed on the back electrode. It has a structure in which a light-emitting layer is formed by dispersing phosphor powder such as zinc sulfide in an organic high-k dielectric binder, and finally a transparent electrode such as ITO (a mixture of indium oxide and tin oxide) is installed as a counter electrode. However, the phosphor emits light by applying an AC electrode between both electrodes.
【０００３】尚、背面電極と透明電極の間に発光層のみ
を挟み込んだ形態の分散型ＥＬ素子も用いられる。A dispersion type EL element in which only a light emitting layer is sandwiched between a back electrode and a transparent electrode is also used.
【０００４】このようなＥＬ素子に使用される蛍光体層
や絶縁体層用のバインダーは高い誘電率をもつことが要
求される。従来ＥＬ素子用バインダーとしてはシアノエ
チル化セルロース、シアノエチル化ポバール、シアノエ
チル化ヒドロキシエチルセルロース、シアノエチル化プ
ルラン、シアノエチル化スターチなどのシアノエチル化
高分子誘電体が用いられている。この内、シアノエチル
化プルランは耐熱性が高いので特に好ましく用いられ
る。これらのシアノエチル化高分子の製造方法としては
米国特許 3,161,539号、同第 3,637,656号公報などに記
載されているような水酸基をアルカリ存在下でアクリロ
ニトリルと反応させる方法が一般的であり、またプルラ
ンのシアノエチル化方法としては特開昭56-8601 号公報
にプルランを水の存在下アルカリ触媒でアクリロニトリ
ルと反応させる方法が開示されている。Binders for phosphor layers and insulator layers used in such EL devices are required to have a high dielectric constant. Conventionally, cyanoethylated polymer dielectrics such as cyanoethylated cellulose, cyanoethylated poval, cyanoethylated hydroxyethyl cellulose, cyanoethylated pullulan, and cyanoethylated starch have been used as binders for EL devices. Of these, cyanoethylated pullulan is particularly preferably used because it has high heat resistance. As a method for producing these cyanoethylated polymers, a method of reacting a hydroxyl group with acrylonitrile in the presence of an alkali is generally used as described in U.S. Pat.Nos. 3,161,539 and 3,637,656, and cyanoethyl of pullulan is also used. As a method of conversion, JP-A-56-8601 discloses a method of reacting pullulan with acrylonitrile in the presence of water with an alkali catalyst.
【０００５】しかし、これらの方法で具体的に開示され
るシアノエチル化プルランはシアノエチル化置換率が最
高でも90％程度であるため、誘電率が余り高くならず、
高い輝度を要するＥＬ素子のバインダーとしては不満足
の場合があった。また残存水酸基が存在するため耐湿性
が悪く、ＥＬ素子の寿命が短くなるという不利益もあっ
た。However, the cyanoethylated pullulan specifically disclosed by these methods has a cyanoethylated substitution ratio of about 90% at the maximum, so that the dielectric constant does not become so high.
In some cases, it was unsatisfactory as a binder for EL devices that require high brightness. Further, since residual hydroxyl groups are present, the moisture resistance is poor and there is a disadvantage that the life of the EL element is shortened.
【０００６】このためシアノエチル化プルランのシアノ
エチル化置換率を上げようとする試みがなされている
が、アルカリ水溶液を用いるシアノエチル化では副反応
としてシアノエチル基の加水分解（シアノエチル基がカ
ルボン酸もしくはカルボン酸アミドに加水分解する）が
進行し、 100％シアノエチル化を達成することが出来な
かった。For this reason, attempts have been made to increase the cyanoethylation substitution rate of cyanoethylated pullulan. However, in the cyanoethylation using an alkaline aqueous solution, hydrolysis of the cyanoethyl group (wherein the cyanoethyl group is a carboxylic acid or a carboxylic acid amide) is a side reaction. However, 100% cyanoethylation could not be achieved.
【０００７】[0007]
【発明が解決しようとする課題】本発明者等はＥＬ素子
のバインダーとして使用する時、高い輝度を有し、寿命
の長いＥＬ素子を得ることのできる誘電率が高く、残存
水酸基が極めて少ない高シアノエチル化プルランを製造
すべく鋭意検討を行った。The inventors of the present invention can obtain an EL device having high brightness and long life when used as a binder for an EL device. The dielectric constant is high and the residual hydroxyl group is extremely small. An intensive study was carried out to produce cyanoethylated pullulan.
【０００８】[0008]
【課題を解決するための手段】本発明の高シアノエチル
化プルランの製造方法は、シアノエチル化置換率50〜90
％のシアノエチル化プルランを非水溶媒中で塩基触媒の
存在下、残存水酸基をシアノエチル化することを特徴と
するシアノエチル化置換率9５〜 100％の高シアノエチ
ル化プルランを得る方法である。The method for producing highly cyanoethylated pullulan of the present invention comprises a cyanoethylated substitution ratio of 50 to 90.
% Cyanoethylated pullulan in a non-aqueous solvent in the presence of a base catalyst to cyanoethylate residual hydroxyl groups, which is a method for obtaining highly cyanoethylated pullulan having a cyanoethylated substitution rate of 95 to 100%.
【０００９】本発明の特色は非水溶媒中で塩基触媒の存
在下でシアノエチル化を行うことであり、非水溶媒中で
はシアノエチル基の加水分解のおそれがないため、長時
間反応を行うことができ、このためシアノエチル化置換
率が向上するものと考えられる。A feature of the present invention is that cyanoethylation is carried out in a non-aqueous solvent in the presence of a base catalyst. Since there is no fear of hydrolysis of the cyanoethyl group in the non-aqueous solvent, it is possible to carry out the reaction for a long time. Therefore, it is considered that the cyanoethylation substitution rate is improved.
【００１０】本発明ではシアノエチル化置換率が50〜90
％のシアノエチル化プルランを原料として用いる。置換
率が50％未満では反応が余りに長時間になりすぎて工業
的に不利となる。原料のシアノエチル化プルランのシア
ノエチル化置換率はなるべく高い方が好ましいが90％以
上のシアノエチル化プルランは従来の提案されている方
法では入手が困難である。このようなシアノエチル化プ
ルランは市販のものを用いても良いし、又通常の水溶媒
中でプルランをアルカリ触媒の存在下シアノエチル化す
ることにより製造される。例えば前記米国特許 3,161,5
39号、 3,637,656号、特開昭 56-8601号公報の方法等が
利用される。In the present invention, the cyanoethylation substitution ratio is 50 to 90.
% Cyanoethylated pullulan is used as a raw material. If the substitution rate is less than 50%, the reaction takes too long, which is industrially disadvantageous. The cyanoethylated pullulan of the raw material is preferably as high as possible in the cyanoethylated substitution rate, but cyanoethylated pullulan having a cyanoethylated pullulan of 90% or more is difficult to obtain by the conventionally proposed method. Such cyanoethylated pullulan may be a commercially available product, or may be produced by cyanoethylating pullulan in an ordinary water solvent in the presence of an alkali catalyst. For example, U.S. Pat.
The methods disclosed in JP-A No. 39, 3,637,656 and JP-A-56-8601 are used.
【００１１】非水溶媒としては、ジメチルホルムアミ
ド、アセトン、ジクロロメタン、アセトニトリル等が用
いられるが、アクリロニトリルを溶媒として兼用するこ
ともできる。塩基触媒としては有機塩基である１，８−
ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢ
Ｕ）、１，４−ジアザビシクロ［２，２，２］−オクタ
ン（ＤＢＯ）、１，５−ジアザビシクロ［４，３，０］
−ノン−５エン（ＤＢＮ）、炭酸カリウム、炭酸ナトリ
ウム、炭酸水素ナトリウム等が用いられるが特にＤＢＵ
が好ましい。有機塩基は溶媒に溶解するので反応し易く
好ましく用いられるが無機塩基も使用することができ
る。As the non-aqueous solvent, dimethylformamide, acetone, dichloromethane, acetonitrile and the like are used, but acrylonitrile can also be used as the solvent. 1,8- which is an organic base as a base catalyst
Diazabicyclo [5,4,0] -7-undecene (DB
U), 1,4-diazabicyclo [2,2,2] -octane (DBO), 1,5-diazabicyclo [4,3,0]
-Non-5ene (DBN), potassium carbonate, sodium carbonate, sodium hydrogen carbonate, etc. are used, but especially DBU
Is preferred. Since an organic base dissolves in a solvent and easily reacts, it is preferably used, but an inorganic base can also be used.
【００１２】本発明のシアノエチル化プルランの製造方
法は上述の低シアノエチル化プルランを非水溶媒中に溶
解もしくは分散させ、この溶媒中に有機塩基の存在下、
アクリロニトリルを加え、好ましくは20〜80℃で１日〜
10日間反応せしめる。非水溶媒はシアノエチル化プルラ
ン１重量部に対し好ましくは５〜20重量部使用される。
またシアノエチル化プルラン１重量部に対しアクリロニ
トリル５〜20重量部、有機塩基0.01〜 0.5当量使用する
ことが好ましい。反応が終了した後、反応液を適当な酸
を用いて中和した後、溶媒を濃縮し、濃縮物をアセトン
で溶解、水−メタノール混合液（水：メタノール＝１：
１）で晶析することを３回以上繰返した後、得られた晶
出物を真空乾燥する。The method for producing cyanoethylated pullulan of the present invention comprises dissolving or dispersing the above-mentioned low cyanoethylated pullulan in a non-aqueous solvent, and in the presence of an organic base in the solvent,
Add acrylonitrile, preferably at 20-80 ° C for 1 day-
Let react for 10 days. The non-aqueous solvent is preferably used in an amount of 5 to 20 parts by weight based on 1 part by weight of cyanoethylated pullulan.
Further, it is preferable to use 5 to 20 parts by weight of acrylonitrile and 0.01 to 0.5 equivalents of an organic base with respect to 1 part by weight of cyanoethylated pullulan. After the reaction was completed, the reaction solution was neutralized with a suitable acid, the solvent was concentrated, the concentrate was dissolved in acetone, and a water-methanol mixed solution (water: methanol = 1: 2) was added.
After repeating the crystallization in 1) three times or more, the obtained crystallized product is vacuum dried.
【００１３】このようにしてシアノエチル化置換率が95
〜100 ％好ましくは98〜100 ％、更に好ましくは99〜10
0 ％の極めてシアノエチル化の高いシアノエチル化プル
ランを容易に得ることができる。シアノエチル化置換率
はキェルダー法により窒素含量を測定し、この値から換
算して求めた。Thus, the cyanoethylation substitution rate is 95
-100%, preferably 98-100%, more preferably 99-10
A cyanoethylated pullulan having a very high cyanoethylation of 0% can be easily obtained. The cyanoethylation substitution rate was determined by measuring the nitrogen content by the Kjelder method and converting from this value.
【００１４】一般に誘電率はシアノエチル化プルランの
シアノエチル化率が高くなるに従い高くなるため、本発
明によって得られた高シアノエチル化プルランは誘電率
が24〜26と高く、ＥＬ素子蛍光体層用バインダーや絶縁
体層用バインダーとして好適に用いられる。Generally, the higher the cyanoethylation rate of cyanoethylated pullulan, the higher the cyanoethylated pullulan. Therefore, the high cyanoethylated pullulan obtained according to the present invention has a high dielectric constant of 24 to 26. It is preferably used as a binder for an insulating layer.
【００１５】以下、実施例により本発明を具体的に説明
するが、本発明はこれら実施例に限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
【００１６】[0016]
【実施例】実施例１
低シアノエチル化プルラン（ＣＲ−Ｓ、信越化学製、シ
アノエチル化置換率85％）１重量部をアクリロニトリル
7.5重量部に溶解し、ＤＢＵ0.06重量部(0.3当量）を加
えた。室温（約20℃）にて約10日間放置したのち、酢酸
で中和しアクリロニトリルを濃縮した。残渣を少量のア
セトンに溶かし、（水：メタノール１：１）混合液で晶
出することを３回くり返した。晶出物を真空乾燥し、目
的物0.98重量部（収率 90.7％）を得た。 Example 1 1 part by weight of low cyanoethylated pullulan (CR-S, manufactured by Shin-Etsu Chemical, cyanoethylated substitution rate 85%) was added to acrylonitrile.
It was dissolved in 7.5 parts by weight, and 0.06 parts by weight (0.3 equivalent) of DBU was added. After leaving it at room temperature (about 20 ° C.) for about 10 days, it was neutralized with acetic acid to concentrate acrylonitrile. The residue was dissolved in a small amount of acetone and crystallized with a (water: methanol 1: 1) mixture, which was repeated 3 times. The crystallized product was vacuum dried to obtain 0.98 part by weight of the desired product (yield 90.7%).
【００１７】得られた高シアノエチル化プルランの赤外
吸収スペクトルを図１に示す。2150cm-1にニトリル基の
ピークがみられ、3600cm-1付近の水酸基の吸収と加水分
解によるアミド、もしくはカルボン酸（カルボニル基）
のピーク1600〜1650cm-1はみられない。The infrared absorption spectrum of the obtained highly cyanoethylated pullulan is shown in FIG. 2150 cm -1 peak of the nitrile groups found in the amide by absorption and hydrolysis of the hydroxyl group in the vicinity of 3600 cm -1 or carboxylic acid, (carbonyl group)
The peak of 1600 to 1650 cm -1 is not seen.
【００１８】
Ｎ％ 13.08 （シアノエチル化率 100％）
残存水酸基 未検出（アセチル化法による）比較例１
プルラン（ＰＦ−20 林原研究所製）１重量部及び５％
水酸化ナトリウム水溶液10重量部から成る溶液にアクリ
ロニトリル 7.5重量部とアセトン 7.5重量部の混合物を
加え、室温（15〜20℃）で24時間反応させた。次にこの
反応液に氷酢酸0.75重量部を加えて中和後、水中に撹拌
しながら注ぎ、シアノエチル化プルランを析出させた。
これをアセトンに溶解させて水中で晶出により精製し
た。この操作をさらにもう一度くりかえし、白色のシア
ノエチル化プルラン15重量部が得られた。N% 13.08 (Cyanoethylation rate 100%) Residual hydroxyl group undetected (by acetylation method) Comparative Example 1 Pullulan (PF-20 manufactured by Hayashibara Laboratory) 1 part by weight and 5%
A mixture of 7.5 parts by weight of acrylonitrile and 7.5 parts by weight of acetone was added to a solution consisting of 10 parts by weight of an aqueous sodium hydroxide solution, and the mixture was reacted at room temperature (15 to 20 ° C.) for 24 hours. Next, 0.75 parts by weight of glacial acetic acid was added to the reaction solution to neutralize it, and the mixture was poured into water with stirring to precipitate cyanoethylated pullulan.
This was dissolved in acetone and purified by crystallization in water. This operation was repeated once more to obtain 15 parts by weight of white cyanoethylated pullulan.
【００１９】
Ｎ％ 12.0（シアノエチル化置換率85％）
残存水酸基 0.45 個／分子（アセチル化法による）比較例２
比較例１と同じ方法により反応時間をさらに延長し、２
日間反応を行った。比較例１と同様に反応液を中和後水
中に撹拌しながら水中に注いだ。折出物はアセトンに不
溶で大量の水に可溶であった。折出物を少量の水で２回
洗浄し、乾燥すると、無色の固体が得られた。このもの
の赤外線吸収スペクトル分析から1680cm-1付近にカルボ
ニル基のピークが見られた。長時間の反応により、シア
ノ基が加水分解して、アミドもしくはカルボン酸が生成
したものと考えられる。この赤外線吸収スペクトルを図
２に示す。N% 12.0 (Cyanoethylation substitution rate 85%) 0.45 residual hydroxyl groups / molecule (by acetylation method) Comparative Example 2 By the same method as Comparative Example 1, the reaction time was further extended to 2
The reaction was carried out for a day. As in Comparative Example 1, the reaction solution was neutralized and then poured into water while stirring. The exudate was insoluble in acetone and soluble in a large amount of water. The exudate was washed twice with a small amount of water and dried to give a colorless solid. Infrared absorption spectrum analysis of this product showed a peak of carbonyl group at around 1680 cm -1 . It is considered that the cyano group was hydrolyzed by the reaction for a long time to generate an amide or a carboxylic acid. This infrared absorption spectrum is shown in FIG.
【００２０】Ｎ％ 12.0％
このように水溶液の反応では長時間反応してもシアノエ
チル化は行われ難く、逆にシアノエチル基が加水分解す
るため、却って誘電率が低下する。N% 12.0% As described above, in the reaction of the aqueous solution, cyanoethylation is difficult to be performed even if the reaction is carried out for a long time, and conversely, the cyanoethyl group is hydrolyzed, so that the dielectric constant is rather lowered.
【００２１】実施例１及び比較例１で得られたシアノエ
チル化プルランの誘電率（25℃，１KHz)及び誘電正接(t
anδ）を第１表に示す。The dielectric constant (25 ° C., 1 KHz) and dielectric loss tangent (t) of the cyanoethylated pullulan obtained in Example 1 and Comparative Example 1
an δ) is shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】分散型ＥＬの製造
実施例１及び比較例１の各シアノエチル化プルランの30
％ＤＭＦ溶液 100ｇに無機高誘電体としてのチタン酸バ
リウム（富士チタン社製ＢＴ−１００Ｍ）の粉末 139.2
ｇを混練分散させ均一スラリーとし高誘電体ペーストを
作製しアルミニウム板に塗布して乾燥膜厚30μm の反射
絶縁体層を形成した。Preparation of Dispersion Type EL 30 of each cyanoethylated pullulan of Example 1 and Comparative Example 1
Powder of barium titanate (BT-100M manufactured by Fuji Titanium Co., Ltd.) as an inorganic high dielectric substance in 100 g of a 100% DMF solution 139.2
g was kneaded and dispersed to form a uniform slurry, and a high dielectric paste was prepared and applied to an aluminum plate to form a reflective insulating layer having a dry film thickness of 30 μm.
【００２４】一方上記バインダー溶液 100ｇに蛍光体と
して硫化亜鉛（ＧＴＥプロダクツ社製シルバニア７２
３）の粉末98.4ｇと混練させ均一スラリーとして蛍光体
ペーストを作製し反射絶縁体層上に塗布して乾燥膜厚42
μm の発光層を形成した。On the other hand, zinc sulfide (Silvania 72 manufactured by GTE Products Co., Ltd.) was used as a phosphor in 100 g of the binder solution.
3) The powder of 9) was mixed with 98.4 g of powder to prepare a phosphor paste as a uniform slurry, which was applied on the reflective insulator layer to obtain a dry film thickness of 42
A luminescent layer of μm was formed.
【００２５】以上の一連の工程によって作製された積層
物は10cm×10cmの大きさに裁断され、リード端子を取付
けた後、乾燥させた。The laminate produced by the above series of steps was cut into a size of 10 cm × 10 cm, attached with lead terminals, and then dried.
【００２６】一方、ポリエチレンテレフタレートの片面
にＩＴＯ膜を形成した透明導電性フイルムを同じく10cm
×10cmの大きさに切り、リード端子を取り付けた後に前
述の積層物の発光層と透明導電性フイルムのＩＴＯ面と
を加熱、ラミネートした。その後背面電極の表面及び前
面電極の表面に対し、それぞれナイロンフイルムが積層
され、更にポリ三フッ化塩化エチレンフイルムで全周が
囲まれ、封止された。On the other hand, a transparent conductive film having an ITO film formed on one side of polyethylene terephthalate is also 10 cm.
After cutting into a size of 10 cm and attaching a lead terminal, the light emitting layer of the above-mentioned laminate and the ITO surface of the transparent conductive film were heated and laminated. Then, a nylon film was laminated on each of the surface of the back electrode and the surface of the front electrode, and the entire circumference was surrounded by a polytrifluoroethylene chloride film and sealed.
【００２７】得られたＥＬ素子の両電極間に 100Ｖ−40
0Hz の交流電場を印加した時の輝度及び20℃−70％ＲＨ
の環境条件下で点灯し続けた時輝度が半減する迄の時間
（輝度半減時間）を第２表に示した。Between the electrodes of the obtained EL device, 100 V-40
Luminance and 0 ℃ -70% RH when an AC electric field of 0Hz is applied
Table 2 shows the time until the luminance is reduced to half (Brightness half time) when the lamp is continuously lit under the above environmental conditions.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】本発明の製造方法によって得られた高シ
アノエチル化プルランは誘電率が高いため、ＥＬ素子の
発光層形成用蛍光体ペースト及び絶縁体層形成用高誘電
体ペーストのバインダーとして使用する時、ＥＬ素子に
高い輝度を与えることができ、また残存水酸基が極めて
少ないため耐湿性に富み、ＥＬ素子の寿命を長くするこ
とができる。Since the high cyanoethylated pullulan obtained by the production method of the present invention has a high dielectric constant, it is used as a binder for a phosphor paste for forming a light emitting layer of an EL device and a high dielectric paste for forming an insulator layer. At this time, high brightness can be given to the EL element, and since the residual hydroxyl groups are extremely small, the EL element is rich in moisture resistance and the life of the EL element can be extended.
【図１】実施例１のシアノエチル化プルランの赤外吸収
スペクトルFIG. 1 is an infrared absorption spectrum of cyanoethylated pullulan of Example 1.
【図２】比較例２のシアノエチル化プルランの赤外吸収
スペクトルFIG. 2 Infrared absorption spectrum of cyanoethylated pullulan of Comparative Example 2.
Claims (2)
エチル化プルランを非水溶媒中で塩基触媒の存在下、そ
の残存水酸基をシアノエチル化することを特徴とするシ
アノエチル化置換率95〜 100％の高シアノエチル化プル
ランの製造方法。1. A cyanoethylated pullulan having a cyanoethylated substitution ratio of 50 to 90% is cyanoethylated at the residual hydroxyl group in the presence of a base catalyst in a non-aqueous solvent. Method for producing high cyanoethylated pullulan.
が１，８−ジアザビシクロ［５，４，０］−７−ウンデ
センである請求項１記載の高シアノエチル化プルランの
製造方法。2. The method for producing a highly cyanoethylated pullulan according to claim 1, wherein the non-aqueous solvent is acrylonitrile and the base catalyst is 1,8-diazabicyclo [5,4,0] -7-undecene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3186553A JP2512352B2 (en) | 1991-07-25 | 1991-07-25 | Method for producing highly cyanoethylated pullulan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3186553A JP2512352B2 (en) | 1991-07-25 | 1991-07-25 | Method for producing highly cyanoethylated pullulan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0525201A true JPH0525201A (en) | 1993-02-02 |
| JP2512352B2 JP2512352B2 (en) | 1996-07-03 |
Family
ID=16190535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3186553A Expired - Lifetime JP2512352B2 (en) | 1991-07-25 | 1991-07-25 | Method for producing highly cyanoethylated pullulan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2512352B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0934925A1 (en) * | 1998-01-30 | 1999-08-11 | Basf Aktiengesellschaft | Process for the preparation of beta-alkoxy nitriles |
| EP2378526A1 (en) * | 2010-04-07 | 2011-10-19 | Samsung Electronics Co., Ltd. | Dielectric paste composition, method of forming dielectric layer, dielectric layer, and device including the dielectric layer |
| US10568839B2 (en) | 2011-01-11 | 2020-02-25 | Capsugel Belgium Nv | Hard capsules |
| US11319566B2 (en) | 2017-04-14 | 2022-05-03 | Capsugel Belgium Nv | Process for making pullulan |
| US11576870B2 (en) | 2017-04-14 | 2023-02-14 | Capsugel Belgium Nv | Pullulan capsules |
-
1991
- 1991-07-25 JP JP3186553A patent/JP2512352B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0934925A1 (en) * | 1998-01-30 | 1999-08-11 | Basf Aktiengesellschaft | Process for the preparation of beta-alkoxy nitriles |
| US6794530B1 (en) | 1998-01-30 | 2004-09-21 | Basf Aktiengesellschaft | Process for making γ-alkoxyamines |
| EP2378526A1 (en) * | 2010-04-07 | 2011-10-19 | Samsung Electronics Co., Ltd. | Dielectric paste composition, method of forming dielectric layer, dielectric layer, and device including the dielectric layer |
| US8586660B2 (en) | 2010-04-07 | 2013-11-19 | Samsung Electronics Co., Ltd. | Dielectric paste composition, method of forming dielectric layer, dielectric layer, and device including the dielectric layer |
| US10568839B2 (en) | 2011-01-11 | 2020-02-25 | Capsugel Belgium Nv | Hard capsules |
| US11319566B2 (en) | 2017-04-14 | 2022-05-03 | Capsugel Belgium Nv | Process for making pullulan |
| US11576870B2 (en) | 2017-04-14 | 2023-02-14 | Capsugel Belgium Nv | Pullulan capsules |
| US11878079B2 (en) | 2017-04-14 | 2024-01-23 | Capsugel Belgium Nv | Pullulan capsules |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2512352B2 (en) | 1996-07-03 |
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