JPH08134103A - Siloxane-containing pullulan and method for producing the same - Google Patents
Siloxane-containing pullulan and method for producing the sameInfo
- Publication number
- JPH08134103A JPH08134103A JP27378594A JP27378594A JPH08134103A JP H08134103 A JPH08134103 A JP H08134103A JP 27378594 A JP27378594 A JP 27378594A JP 27378594 A JP27378594 A JP 27378594A JP H08134103 A JPH08134103 A JP H08134103A
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- Prior art keywords
- pullulan
- group
- monovalent organic
- carbon atoms
- siloxane
- Prior art date
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
(57)【要約】 （修正有）
【目的】 プルランとシリコーン化合物の両方の性質を
兼備した安定なシロキサン含有プルランを提供する。
【構成】 一般式
で示される分子量が50,000〜10,000,000の置換シリルア
ルキルカルバミド酸プルラン、及び
（Ｉ）プルランの水酸基と
（II）一般式
で示されるイソシアネート基含有オルガノポリシロキサ
ンとを反応させることを特徴とする置換シリルアルキル
カルバミド酸プルランの製造方法。(57) [Summary] (Modified) [Objective] To provide a stable siloxane-containing pullulan having both properties of pullulan and a silicone compound. [Structure] General formula A substituted silylalkylcarbamic acid pullulan having a molecular weight of 50,000 to 10,000,000, and (I) a hydroxyl group of pullulan and (II) a general formula A method for producing a substituted silylalkylcarbamic acid pullulan, which comprises reacting with an isocyanate group-containing organopolysiloxane represented by
Description
【０００１】[0001]
【産業上の利用分野】本発明はシロキサン含有プルラ
ン、特にはプルランとシリコーンの両方の性質を兼備し
た新規で安定なシロキサン含有プルラン及びその製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a siloxane-containing pullulan, and more particularly to a novel and stable siloxane-containing pullulan having both properties of pullulan and silicone and a method for producing the same.
【０００２】[0002]
【従来の技術】プルランに有機ケイ素化合物を反応させ
て、その両者の特徴を生かした組成物を得るという試み
についての報告はいくつかなされているが、これには有
機ケイ素化合物の反応効率が悪く、また特開平５−1455
12号公報に開示されているトリメチルシリルプルランな
どのようにプルランに有機ケイ素化合物が含有されてい
るものは、水に対して不安定であるという問題点があ
り、さらに両者の特徴を生かした性能が発揮できないた
めに実用化に問題があった。2. Description of the Related Art There have been some reports on attempts to react pullulan with an organosilicon compound to obtain a composition that makes use of the characteristics of both, but the reaction efficiency of the organosilicon compound is poor. Japanese Patent Laid-Open No. 5-1455
Those containing an organosilicon compound in pullulan such as trimethylsilyl pullulan disclosed in Japanese Patent No. 12 have a problem that they are unstable to water, and further, the performance utilizing the characteristics of both is There was a problem in practical use because it could not be exhibited.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記の問題
点を解決するためになされたものであり、プルランとシ
リコーン化合物の両方の性質を兼備した安定なシロキサ
ン含有プルランを提供することを課題とする。The present invention has been made to solve the above problems, and it is an object of the present invention to provide a stable siloxane-containing pullulan having both properties of pullulan and a silicone compound. And
【０００４】[0004]
【課題を解決するための手段】本発明は、新規なシロキ
サン含有プルラン及びその製造方法に関するものであ
り、このシロキサン含有プルランは、一般式SUMMARY OF THE INVENTION The present invention relates to a novel siloxane-containing pullulan and a method for producing the same.
【化３】 ［ここにＰＬ−はプルランのグルコース残基、Ｒ1 は炭
素数１〜８の１価有機基、Ｒ2 、Ｒ3 、Ｒ4 は各々炭素
数１〜８の１価有機基または−ＯＳｉＲ5 Ｒ6 Ｒ7 で示
されるシロキシ基（Ｒ5 、Ｒ6 、Ｒ7 は各々炭素数１〜
８の１価有機基）、ｎは１〜10の整数、ａは０、１また
は２］で示される分子量が50,000〜10,000,000の置換シ
リルアルキルカルバミド酸プルランである。またこの化
合物の製造方法は（Ｉ）プルランの水酸基と（II）一般
式Embedded image [Where PL- is a glucose residue of pullulan, R 1 is a monovalent organic group having 1 to 8 carbon atoms, R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 8 carbon atoms or -OSiR 5 A siloxy group represented by R 6 R 7 (R 5 , R 6 , and R 7 are each a carbon number of 1 to
8 is a monovalent organic group), n is an integer of 1 to 10, and a is 0, 1 or 2] and is a substituted silylalkylcarbamic acid pullulan having a molecular weight of 50,000 to 10,000,000. Further, the production method of this compound is (I) a hydroxyl group of pullulan and (II) a general formula
【化４】 ［ここにＲ1 は炭素数１〜８の１価有機基、Ｒ2 、Ｒ
3 、Ｒ4 は各々炭素数１〜８の１価有機基または−ＯＳ
ｉＲ5 Ｒ6 Ｒ7 で示されるシロキシ基（Ｒ5 、Ｒ6、Ｒ7
は各々炭素数１〜８の１価有機基）、ｎは１〜10の整
数、ａは０、１または２］で示されるイソシアネート基
含有オルガノポリシロキサンとを反応させることを特徴
とするものである。[Chemical 4] [Here, R 1 is a monovalent organic group having 1 to 8 carbon atoms, R 2 and R
3 and R 4 are each a monovalent organic group having 1 to 8 carbon atoms or -OS
A siloxy group represented by iR 5 R 6 R 7 (R 5 , R 6 , R 7
Are each a monovalent organic group having 1 to 8 carbon atoms), n is an integer of 1 to 10 and a is 0, 1 or 2]. is there.
【０００５】すなわち本発明者らは、プルランとシリコ
ーン化合物の両方の性質を兼備したシロキサン含有プル
ランを開発すべく種々検討した結果、プルランの水酸基
と前記の一般式（化２）で示されるイソシアネート基含
有オルガノポリシロキサンとを反応させると、このイソ
シアネート基含有オルガノポリシロキサンのイソシアネ
ート基が反応性の高いものであるため、プルランの水酸
基と効果的に反応して前記一般式（化１）で示される置
換シリルアルキルカルバミド酸プルランが容易に得られ
ることを見いだした。また本発明者らはこのようにして
得られた置換シリルアルキルカルバミド酸プルランが、
新規なもので、プルランが有する造膜性、強靭性、有機
ケイ素化合物の有する弾性、ガス透過性などの特徴を合
わせ持ち、各種有機溶剤にも溶けるので、ガス分離膜、
化粧品材料、接着剤、繊維処理剤などの原料として有用
なことを確認して本発明を完成させた。That is, the inventors of the present invention have conducted various studies to develop a siloxane-containing pullulan having both the properties of pullulan and a silicone compound. As a result, the hydroxyl group of pullulan and the isocyanate group represented by the above general formula (Formula 2) When reacted with the containing organopolysiloxane, the isocyanate group of the isocyanate group-containing organopolysiloxane has a high reactivity, so that it effectively reacts with the hydroxyl group of pullulan and is represented by the general formula (Formula 1). It was found that a substituted silylalkylcarbamic acid pullulan can be easily obtained. Further, the present inventors have found that the substituted silylalkylcarbamic acid pullulan thus obtained is
It is a new one, and has the characteristics of pullulan's film-forming property, toughness, elasticity of organic silicon compounds, gas permeability, etc. It is soluble in various organic solvents, so it is a gas separation membrane,
The present invention has been completed by confirming that it is useful as a raw material for cosmetic materials, adhesives, fiber treatment agents and the like.
【０００６】本発明のシロキサン含有プルランは、
（Ｉ）プルランの水酸基と（II）一般式（化２）で示さ
れるイソシアネート基含有オルガノポリシロキサンを反
応させて得た置換シリルアルキルカルバミド酸プルラン
であるが、ここに使用するプルランとしては、分子量5
0,000〜10,000,000の範囲であればよく、目的とする用
途により適宜選ぶことが可能であるが、フィルム強度の
点からは、より高分子量のプルランを用いることが好ま
しい。このような高分子量プルランは、例えば、特開平
５−328988号公報に開示されているように、プルラン生
産菌であるオーレオバシディウム・プルランス（Ａureo
basidium pullulans ）を培養後、培養液を50〜75℃
で、0.3 〜３時間保持することにより得られる。The siloxane-containing pullulan of the present invention is
(I) A substituted silylalkylcarbamic acid pullulan obtained by reacting the hydroxyl group of pullulan with (II) the isocyanate group-containing organopolysiloxane represented by the general formula (Formula 2). The pullulan used here has a molecular weight of Five
It may be in the range of 0.00000 to 10,000,000 and can be appropriately selected depending on the intended use, but from the viewpoint of film strength, it is preferable to use pullulan having a higher molecular weight. Such a high molecular weight pullulan is disclosed in, for example, Japanese Patent Application Laid-Open No. 5-328988, which is a pullulan-producing bacterium, Aureobasidium pullulans (Aureo).
basidium pullulans) after culturing, culture medium at 50-75 ℃
At 0.3 to 3 hours.
【０００７】また、ここに使用されるイソシアネート基
含有オルガノポリシロキサンは、前記一般式（化２）で
示されるものである。このＲ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ
5 、Ｒ6 、Ｒ7 で示される炭素数１〜８の１価の有機基
としては、メチル基、エチル基、プロピル基、ブチル基
等のアルキル基；シクロペンチル基、シクロヘキシル基
などのシクロアルキル基；フェニル基などのアリール
基；ベンジル基などのアラルキル基；ビニル基、アリル
基などのアルケニル基；クロロメチル基、３，３，３−
トリフルオロプロピル基などの置換炭化水素基などが例
示され、このＲ1、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｒ6 、Ｒ7
はそれぞれ同じでも異なってもよいが、いずれもメチ
ル基であることが好ましい。また、このＲ2 、Ｒ3 、Ｒ
4 は各々−ＯＳｉＲ5 Ｒ6 Ｒ7 で示されるシロキシ基で
あってもよいが、このシロキシ基としてはトリメチルシ
ロキシ基、エチルジメチルシロキシ基、フェニルジメチ
ルシロキシ基、ビニルジメチルシロキシ基、クロロメチ
ルジメチルシロキシ基、３，３，３−トリフルオロプロ
ピルジメチルシロキシ基などが例示される。The isocyanate group-containing organopolysiloxane used here is represented by the above general formula (Formula 2). This R 1 , R 2 , R 3 , R 4 , R
Examples of the monovalent organic group having 1 to 8 carbon atoms represented by 5 , R 6 and R 7 include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group. An aryl group such as a phenyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group or an allyl group; a chloromethyl group, 3,3,3-
Substituted hydrocarbon groups such as trifluoropropyl group are exemplified, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are exemplified.
May be the same or different, but are preferably methyl groups. In addition, this R 2 , R 3 , R
Each 4 may be a siloxy group represented by -OSiR 5 R 6 R 7 , and the siloxy group may be a trimethylsiloxy group, an ethyldimethylsiloxy group, a phenyldimethylsiloxy group, a vinyldimethylsiloxy group, a chloromethyldimethylsiloxy group. Group, 3,3,3-trifluoropropyldimethylsiloxy group and the like.
【０００８】本発明のシロキサン含有プルランの製造方
法はプルランの水酸基とイソシアネート基含有オルガノ
ポリシロキサンとのウレタン結合生成反応によるもので
あるために、特別な反応条件や反応装置を用いる必要は
ないが、プルランとイソシアネート基含有オルガノポリ
シロキサンとの混合、反応効率、反応制御のためには溶
媒を使用することが好ましい。この溶媒としては酢酸メ
チル、酢酸エチル、酢酸ブチル、酢酸イソブチルなどの
エステル類；アセトン、メチルエチルケトン、メチルイ
ソブチルケトン、ジイソブチルケトン、シクロヘキサノ
ン等のケトン類；ベンゼン、トルエン、キシレンなどの
芳香族炭化水素類；ジエチルエーテル、ジブチルエーテ
ル、テトラヒドロフラン、ジオキサンなどのエーテル
類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリ
ドン等のアミド類などが例示されるが、これらは単独で
も２種以上を混合して用いてもよい。Since the method for producing the siloxane-containing pullulan of the present invention is based on the urethane bond-forming reaction between the hydroxyl group of pullulan and the isocyanate group-containing organopolysiloxane, it is not necessary to use special reaction conditions or reaction equipment. It is preferable to use a solvent for mixing pullulan and the isocyanate group-containing organopolysiloxane, reaction efficiency, and reaction control. Examples of the solvent include esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N-methylpyrrolidone. These may be used alone or in combination of two or more. Good.
【０００９】また、この反応はここに使用する溶媒の種
類によって異なるが、通常は20〜 150℃で１〜10時間と
すれば良く、この場合には触媒としてトリエチルアミ
ン、トリエチレンジアミン、Ｎ−メチルモルホリン等の
アミン類、ジラウリン酸ジ−ｎ−ブチル錫、オレイン酸
第一錫等の有機金属化合物のようなウレタン結合形成に
際して用いられる公知の触媒を添加してもよい。反応終
了後は洗浄、乾燥すれば目的とするシロキサン含有プル
ランを得ることが出来る。本発明によるシロキサン含有
プルランの製造は上記のようにプルランの水酸基とイソ
シアネート基含有オルガノポリシロキサンとの反応によ
り行われるが、このイソシアネート基含有オルガノポリ
シロキサンとしては特にトリストリメチルシロキシシリ
ルプロピルイソシアネート（以下ＴＭＳＩと略記する）
を用いることが好ましく、プルランとＴＭＳＩを反応さ
せればトリストリメチルシロキシシリルプロピルカルバ
ミド酸プルランを得ることができるが、これは式The reaction may be carried out at 20 to 150 ° C. for 1 to 10 hours, though it depends on the type of solvent used here. In this case, triethylamine, triethylenediamine, N-methylmorpholine is used as a catalyst. Known catalysts used in the formation of urethane bonds, such as amines such as ## STR1 ## and organic metal compounds such as di-n-butyltin dilaurate and stannous oleate, may be added. After completion of the reaction, the desired siloxane-containing pullulan can be obtained by washing and drying. The siloxane-containing pullulan according to the present invention is produced by the reaction between the hydroxyl group of pullulan and the isocyanate group-containing organopolysiloxane as described above. This isocyanate group-containing organopolysiloxane is particularly tristrimethylsiloxysilylpropyl isocyanate (hereinafter TMSI). Abbreviated as)
Is preferred, and pullulan can be reacted with TMSI to give tristrimethylsiloxysilylpropylcarbamate pullulan, which has the formula
【化５】 で示される。Embedded image Indicated by.
【００１０】なお、この場合に使用するＴＭＳＩの量は
プルランに含まれるグルコース単位当たりの３個の水酸
基への導入量によって変わるが、ＴＭＳＩがこの水酸基
の２等量より多いとＴＭＳＩが無駄になるだけでなく、
生成するシロキサン含有プルランの生成が難しくなるの
で、プルランのグルコース単位当たりの水酸基の２当量
以下で、グルコース単位当たり 0.1モル以上とすること
がよい。The amount of TMSI used in this case depends on the amount introduced into the three hydroxyl groups per glucose unit contained in pullulan, but if the TMSI is more than 2 equivalents of these hydroxyl groups, the TMSI will be wasted. not only,
Since it is difficult to form the siloxane-containing pullulan that is formed, it is preferable that the amount of hydroxyl group is 2 equivalents or less per glucose unit of pullulan and 0.1 mol or more per glucose unit.
【００１１】[0011]
【実施例】次に本発明の実施例をあげる。 実施例 プルラン［林原商事（株）製商品名ＰＦ−20］を 105℃
で２時間乾燥させたもの 10gとジラウリン酸ジ−ｎ−ブ
チル錫1.2gを 300mlのＮ−メチルピロリドン中に 100℃
で溶解し、この温度で撹拌しながらＴＭＳＩ 70.5gを滴
下し、 100〜 110℃で２時間撹拌反応させて反応を完結
させ、反応液を水 1,000ml中に撹拌しながら注ぎ、生じ
た析出物をろ別し、繰り返し水洗した後更にメタノール
による洗浄を繰り返し、乾燥したところ、生成物 58gが
得られた。この生成物のＳｉ含有量は24.4重量％であっ
た。ついで、この生成物を元素分析、ＩＲ定性分析する
と共に13Ｃ−ＮＭＲによる物質同定を行ったところ、図
１及び表１に示したとおりの結果が得られ、これはトリ
ストリメチルシロキシシリルプロピルカルバミド酸プル
ランであることが確認された。次にこれをトルエンに溶
解し、キャスティング法で厚さ50μｍのフィルムを作製
したところ、強靭で弾性に富んだフィルムが得られ、こ
のものの酸素透過係数が 1.4×10-8cm3(STP)・cm/cm2・se
c・cmHgであり、ガス分離膜として有用であることが判明
した。Next, examples of the present invention will be described. Example Pullulan [trade name PF-20 manufactured by Hayashibara Shoji Co., Ltd.] was heated to 105 ° C.
10g dried for 2 hours at room temperature and 1.2g di-n-butyltin dilaurate in 300ml N-methylpyrrolidone at 100 ° C.
Then, TMSI (70.5 g) was added dropwise with stirring at this temperature, the reaction was completed by stirring at 100-110 ° C for 2 hours, and the reaction mixture was poured into water (1,000 ml) with stirring. Was filtered off, washed with water repeatedly, and then washed with methanol repeatedly, and dried to obtain 58 g of a product. The Si content of this product was 24.4% by weight. Then, the product was subjected to elemental analysis, IR qualitative analysis and substance identification by 13 C-NMR, and the results as shown in FIG. 1 and Table 1 were obtained. This was tristrimethylsiloxysilylpropylcarbamic acid. It was confirmed to be pullulan. Next, this was dissolved in toluene, and a film with a thickness of 50 μm was made by the casting method. A film that was tough and elastic was obtained, and the oxygen permeability coefficient of this film was 1.4 × 10 -8 cm 3 (STP) ・cm / cm 2 · se
It was c · cmHg and was found to be useful as a gas separation membrane.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】本発明のシロキサン含有プルランは新規
物質で、これらはいずれもプルランとシリコーンの両方
の性質を兼備した安定なもので、ガス分離膜、化粧品材
料、接着剤、塗料などとして有用なものであり、前記の
製造方法によればこれに使用するイソシアネート基含有
オルガノポリシロキサンのイソシアネート基が反応性の
高いものであるため、プルランの水酸基と反応して目的
とするシロキサン含有プルランを容易にかつ効率よく得
ることができる。INDUSTRIAL APPLICABILITY The siloxane-containing pullulan of the present invention is a novel substance, both of which are stable and have the properties of both pullulan and silicone, and are useful as gas separation membranes, cosmetic materials, adhesives, paints, etc. According to the above-mentioned production method, the isocyanate group of the isocyanate group-containing organopolysiloxane used for this is highly reactive, so that the desired siloxane-containing pullulan can be easily reacted by reacting with the hydroxyl group of pullulan. And it can be obtained efficiently.
【図１】本発明の実施例で得られたトリストリメチルシ
ロキシシリルプロピルカルバミド酸プルランのＩＲスペ
クトルを示したものである。1 is an IR spectrum of pullulan tristrimethylsiloxysilylpropylcarbamate obtained in an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 福井 育生 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 遠藤 幹夫 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 梅沢 宏 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 (72)発明者 名倉 茂広 新潟県中頸城郡頸城村大字西福島28番地の １ 信越化学工業株式会社合成技術研究所 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Ikuo Fukui, inventor Ikuo Fukui, 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture, Shinsei Chemical Industry Co., Ltd. (72) Inventor, Mikio Endo Naka-kubiki-gun, Niigata Prefecture 1 at 28, Nishifukushima, Kubiki-mura, Shin-Etsu Chemical Co., Ltd., Research Institute for Synthetic Technology (72) Inventor, Hiroshi Umezawa, 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata (72) Inventor Shigehiro Nagura 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd.
Claims (4)
素数１〜８の１価有機基、Ｒ2 、Ｒ3 、Ｒ4 は各々炭素
数１〜８の１価有機基または−ＯＳｉＲ5 Ｒ6 Ｒ7 で示
されるシロキシ基（Ｒ5 、Ｒ6 、Ｒ7 は各々炭素数１〜
８の１価有機基）、ｎは１〜10の整数、ａは０、１また
は２］で示される分子量が50,000〜10,000,000の置換シ
リルアルキルカルバミド酸プルラン。1. A compound of the general formula [Where PL- is a glucose residue of pullulan, R 1 is a monovalent organic group having 1 to 8 carbon atoms, R 2 , R 3 and R 4 are each a monovalent organic group having 1 to 8 carbon atoms or -OSiR 5 A siloxy group represented by R 6 R 7 (R 5 , R 6 , and R 7 are each a carbon number of 1 to
8 is a monovalent organic group, n is an integer of 1 to 10, and a is 0, 1 or 2] and is a substituted silylalkylcarbamic acid pullulan having a molecular weight of 50,000 to 10,000,000.
ａ＝０である請求項１記載の置換シリルアルキルカルバ
ミド酸プルラン。2. The substituted silylalkylcarbamic acid pullulan according to claim 1, wherein n is 3, R 2 , R 3 and R 4 are methyl groups and a = 0.
3 、Ｒ4 は各々炭素数１〜８の１価有機基または−ＯＳ
ｉＲ5 Ｒ6 Ｒ7 で示されるシロキシ基（Ｒ5 、Ｒ6、Ｒ7
は各々炭素数１〜８の１価有機基）、ｎは１〜10の整
数、ａは０、１または２］で示されるイソシアネート基
含有オルガノポリシロキサンとを反応させることを特徴
とする置換シリルアルキルカルバミド酸プルランの製造
方法。3. A hydroxyl group of pullulan (I) and a general formula (II): [Here, R 1 is a monovalent organic group having 1 to 8 carbon atoms, R 2 and R
3 and R 4 are each a monovalent organic group having 1 to 8 carbon atoms or -OS
A siloxy group represented by iR 5 R 6 R 7 (R 5 , R 6 , R 7
Is a monovalent organic group each having 1 to 8 carbon atoms, n is an integer of 1 to 10, and a is 0, 1 or 2]. Method for producing pullulan alkylcarbamate.
キサンがトリストリメチルシロキシシリルプロピルイソ
シアネートである請求項３記載の置換シリルアルキルカ
ルバミド酸プルランの製造方法。4. The method for producing a substituted silylalkylcarbamic acid pullulan according to claim 3, wherein the isocyanate group-containing organopolysiloxane is tristrimethylsiloxysilylpropyl isocyanate.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6273785A JP3009090B2 (en) | 1994-11-08 | 1994-11-08 | Siloxane-containing pullulan and method for producing the same |
| FR9513091A FR2726564B1 (en) | 1994-11-08 | 1995-11-06 | PULULAN CONTAINING SILOXANE AND A PROCESS FOR THE PREPARATION THEREOF |
| US08/551,807 US5583244A (en) | 1994-11-08 | 1995-11-07 | Siloxane-containing pullulan and method for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6273785A JP3009090B2 (en) | 1994-11-08 | 1994-11-08 | Siloxane-containing pullulan and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08134103A true JPH08134103A (en) | 1996-05-28 |
| JP3009090B2 JP3009090B2 (en) | 2000-02-14 |
Family
ID=17532555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6273785A Expired - Lifetime JP3009090B2 (en) | 1994-11-08 | 1994-11-08 | Siloxane-containing pullulan and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3009090B2 (en) |
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