JPH05262882A - Thermally reversible hydrogel material - Google Patents
Thermally reversible hydrogel materialInfo
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- JPH05262882A JPH05262882A JP1611492A JP1611492A JPH05262882A JP H05262882 A JPH05262882 A JP H05262882A JP 1611492 A JP1611492 A JP 1611492A JP 1611492 A JP1611492 A JP 1611492A JP H05262882 A JPH05262882 A JP H05262882A
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- temperature
- polymer compound
- water
- lcst
- hydrogel material
- Prior art date
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- Colloid Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、物質の分離や医薬品、
食品、農薬、化粧品などに利用されるハイドロゲル材料
に関する。さらに詳しくは、温度変化によって可逆的に
ゲル化する熱可逆性ハイドロゲル材料に関する。BACKGROUND OF THE INVENTION The present invention relates to the separation of substances and pharmaceuticals,
The present invention relates to a hydrogel material used for foods, agricultural chemicals, cosmetics and the like. More specifically, it relates to a thermoreversible hydrogel material that reversibly gels due to temperature changes.
【０００２】[0002]
【従来の技術】熱可逆性ハイドロゲルとしては、従来ゼ
ラチンゲルや寒天ゲルなどが知られている。これらのゲ
ル材料（ゼラチン、寒天）は、高温で水に溶解して水溶
液となり、冷却すると多量の水を保持したハイドロゲル
となる。このように、温度変化によって可逆的にゲル化
する性質を示すことから、物質の分離や医薬品、食品、
農薬、化粧品などに利用されている。しかし、従来知ら
れている熱可逆性ハイドロゲルはすべて、冷却によりゲ
ル化するものであるため、利用範囲が制限されてきた。2. Description of the Related Art Gelatin gel, agar gel and the like have been known as thermoreversible hydrogels. These gel materials (gelatin, agar) are dissolved in water at high temperature to form an aqueous solution, and when cooled, become a hydrogel that retains a large amount of water. In this way, since it exhibits the property of reversibly gelling due to temperature changes, it can be used to separate substances, drugs, foods,
It is used for agricultural chemicals and cosmetics. However, all of the conventionally known thermoreversible hydrogels are gelled by cooling, and thus their range of use has been limited.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、低温
では水に溶解し、高温では多量の水を保持したハイドロ
ゲルとなる熱可逆性ハイドロゲル材料を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoreversible hydrogel material which becomes a hydrogel which dissolves in water at low temperatures and retains a large amount of water at high temperatures.
【０００４】[0004]
【課題を解決するための手段】上記の目的は、本発明の
ＬＣＳＴを有する温度感応性高分子化合物と水溶性高分
子化合物が結合されてなる高分子化合物であって、該Ｌ
ＣＳＴを有する温度感応性高分子化合物部分が一分子内
に複数存在することを特徴とする熱可逆性ハイドロゲル
材料により達成される。The above-mentioned object is a polymer compound comprising a temperature-sensitive polymer compound having LCST of the present invention and a water-soluble polymer compound, which comprises:
This is achieved by a thermoreversible hydrogel material characterized in that a plurality of temperature-sensitive polymer compounds having CST are present in one molecule.
【０００５】本発明に用いられるＬＣＳＴを有する温度
感応性高分子化合物とは、水に対する溶解度温度係数が
負を示す高分子化合物であり、低温にて生成する高分子
化合物と水分子との水素結合に依存する水和物（オキソ
ニウムヒドロキシド）が高温で分解し、脱水和により高
分子化合物同士が凝集し沈殿する特徴を有する。ＬＣＳ
Ｔ（Lower Critical Solution Temperature）とは、こ
のような温度感応性高分子化合物の水和と脱水和の転移
温度をいう（例えば、ハスキンズ（M. Haskins）らの
J. Macromol, Sci.-Chem., A2 (8), 1441 (1986) 参
照）。すなわち、本発明の温度感応性高分子化合物はＬ
ＣＳＴ以下の温度では親水性で水に溶解するが、ＬＣＳ
Ｔ以上の温度では疎水性となって沈殿し、この変化は可
逆的である。本発明においては、上記温度感応性高分子
化合物のＬＣＳＴが０〜９０℃、さらには１０〜５０℃
であることが好ましい。The temperature-sensitive polymer compound having an LCST used in the present invention is a polymer compound having a negative solubility temperature coefficient in water, and is a hydrogen bond between a polymer compound produced at low temperature and a water molecule. The hydrate (oxonium hydroxide) depending on is decomposed at a high temperature, and polymer compounds are aggregated and precipitated by dehydration. LCS
T (Lower Critical Solution Temperature) refers to the transition temperature of hydration and dehydration of such a temperature-sensitive polymer compound (eg M. Haskins et al.
See J. Macromol, Sci.-Chem., A2 (8), 1441 (1986)). That is, the temperature-sensitive polymer compound of the present invention is L
It is hydrophilic at temperatures below CST and dissolves in water, but LCS
At temperatures above T, it becomes hydrophobic and precipitates, and this change is reversible. In the present invention, the LCST of the temperature-sensitive polymer compound is 0 to 90 ° C, more preferably 10 to 50 ° C.
Is preferred.
【０００６】本発明に用いられる温度感応性高分子化合
物としては、ポリＮ置換アクリルアミド誘導体、ポリＮ
置換メタアクリルアミド誘導体およびこれらの共重合
体、ポリビニルメチルエーテル、ポリビニルアルコール
部分酢化物などが挙げられる。好ましい温度感応性高分
子化合物を以下にＬＣＳＴが低い順に列挙する。Examples of the temperature-sensitive polymer compound used in the present invention include poly N-substituted acrylamide derivatives and poly N
Examples thereof include substituted methacrylamide derivatives and copolymers thereof, polyvinyl methyl ether, and polyvinyl alcohol partial acetic acid. Preferred temperature-sensitive polymer compounds are listed below in the order of increasing LCST.
【０００７】ポリ−Ｎ−アクリロイルピペリジン；ポリ
ーＮ−ｎ−プロピルメタアクリルアミド；ポリーＮ−イ
ソプロピルアクリルアミド；ポリーＮ,Ｎ−ジエチルア
クリルアミド；ポリーＮ−イソプロピルメタアクリルア
ミド；ポリーＮ−シクロプロピルアクリルアミド；ポリ
ーＮ−アクリロイルピロリジン；ポリーＮ,Ｎ−エチル
メチルアクリルアミド；ポリーＮ−シクロプロピルメタ
アクリルアミド；ポリーＮ−エチルアクリルアミド 上記の高分子化合物は、単一の単量体を重合したもので
あっても、他の単量体と共重合させたものであってもよ
い。共重合する単量体は、親水性単量体、疎水性単量体
のいずれでも用いることができる。一般的には、親水性
単量体と共重合すると生成物のＬＣＳＴは上昇し、疎水
性単量体と共重合すると生成物のＬＣＳＴは下降する。
したがって、これらを適宜選択することによっても所望
のＬＣＳＴを有する高分子化合物を得ることができる。Poly-N-acryloylpiperidine; poly-N-n-propylmethacrylamide; poly-N-isopropylacrylamide; poly-N, N-diethylacrylamide; poly-N-isopropylmethacrylamide; poly-N-cyclopropylacrylamide; poly-N- Acryloylpyrrolidine; poly-N, N-ethylmethyl acrylamide; poly-N-cyclopropyl methacrylamide; poly-N-ethyl acrylamide The above-mentioned polymer compound may be obtained by polymerizing a single monomer or another monomer. It may be a copolymer with a monomer. As the monomer to be copolymerized, either a hydrophilic monomer or a hydrophobic monomer can be used. Generally, copolymerization with a hydrophilic monomer increases the LCST of the product, and copolymerization with a hydrophobic monomer decreases the LCST of the product.
Therefore, a polymer compound having a desired LCST can be obtained by appropriately selecting these.
【０００８】親水性単量体としては、Ｎ−ビニルピロリ
ドン、ビニルピリジン、アクリルアミド、メタアクリル
アミド、Ｎ−メチルアクリルアミド、ヒドロキシエチル
メタアクリレート、ヒドロキシエチルアクリレート、ヒ
ドロキシメチルメタアクリレート、ヒドロキシメチルア
クリレート、酸性基を有するアクリル酸、メタアクリル
酸およびそれらの塩、ビニルスルホン酸、スチレンスル
ホン酸など、並びに塩基性を有するＮ,Ｎ−ジメチルア
ミノエチルメタクリレート、Ｎ,Ｎ−ジエチルアミノエ
チルメタクリレート、Ｎ,Ｎ−ジメチルアミノプロピル
アクリルアミドおよびそれらの塩などが挙げられるが、
これらに限定されるものではない。Examples of the hydrophilic monomer include N-vinylpyrrolidone, vinylpyridine, acrylamide, methacrylamide, N-methylacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxymethyl acrylate, and acidic groups. Having acrylic acid, methacrylic acid and salts thereof, vinyl sulfonic acid, styrene sulfonic acid, etc., and basic N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl Examples include acrylamide and salts thereof,
It is not limited to these.
【０００９】一方、疎水性単量体としては、エチルアク
リレート、メチルメタクリレート、グリシジルメタクリ
レートなどのアクリレート誘導体およびメタクリレート
誘導体、Ｎ−ｎ−ブチルメタアクリルアミドなどのＮ置
換アルキルメタアクリルアミド誘導体、塩化ビニル、ア
クリロニトリル、スチレン、酢酸ビニルなどが挙げられ
るが、これらに限定されるものではない。On the other hand, as the hydrophobic monomer, acrylate derivatives and methacrylate derivatives such as ethyl acrylate, methyl methacrylate and glycidyl methacrylate, N-substituted alkyl methacrylamide derivatives such as Nn-butyl methacrylamide, vinyl chloride, acrylonitrile, Examples thereof include, but are not limited to, styrene and vinyl acetate.
【００１０】一方、本発明に用いられる水溶性高分子化
合物は、水に可溶な高分子化合物であれば特に制限はな
く、例えば、ポリエチレンオキシド、ポリビニルアルコ
ール、ポリ−Ｎ−ビニルピロリドン、ポリビニルピリジ
ン、ポリアクリルアミド、ポリメタアクリルアミド、ポ
リ−Ｎ−メチルアクリルアミド、ポリヒドロキシエチル
メタアクリレート、ポリヒドロキシエチルアクリレー
ト、ポリヒドロキシメチルメタアクリレート、ポリヒド
ロキシメチルアクリレート、ポリアクリル酸、ポリメタ
クリル酸、ポリビニルスルホン酸、ポリスチレンスルホ
ン酸およびそれらの塩、ポリ−Ｎ,Ｎ−ジメチルアミノ
エチルメタクリレート、ポリ−Ｎ,Ｎ−ジエチルアミノ
エチルメタクリレート、ポリ−Ｎ,Ｎ−ジメチルアミノ
プロピルアクリルアミドおよびそれらの塩などが挙げら
れる。On the other hand, the water-soluble polymer compound used in the present invention is not particularly limited as long as it is a water-soluble polymer compound, and examples thereof include polyethylene oxide, polyvinyl alcohol, poly-N-vinylpyrrolidone and polyvinylpyridine. , Polyacrylamide, polymethacrylamide, poly-N-methylacrylamide, polyhydroxyethylmethacrylate, polyhydroxyethylacrylate, polyhydroxymethylmethacrylate, polyhydroxymethylacrylate, polyacrylic acid, polymethacrylic acid, polyvinylsulfonic acid, polystyrene Sulfonic acid and salts thereof, poly-N, N-dimethylaminoethyl methacrylate, poly-N, N-diethylaminoethyl methacrylate, poly-N, N-dimethylaminopropyl acrylamide And thereof, and the like salts.
【００１１】ＬＣＳＴを有する温度感応性高分子化合物
と水溶性高分子化合物との結合は、例えば、いずれかの
高分子化合物中に重合性官能基を導入し、他方の高分子
化合物を与える単量体を共重合させて行うことができ
る。また、ＬＣＳＴを有す温度感応性高分子化合物と水
溶性高分子化合物との結合は、温度感応性高分子化合物
を与える単量体と、水溶性高分子化合物を与える単量体
とのブロック共重合によっても行うことができる。さら
に、ＬＣＳＴを有する温度感応性高分子化合物と水溶性
高分子化合物との結合は、あらかじめ両者に反応活性な
官能基を導入し、両者を化学反応により結合させること
によっても行える。このとき、水溶性高分子化合物中に
反応活性な官能基を複数導入する必要がある。The bond between the temperature-sensitive polymer compound having LCST and the water-soluble polymer compound can be obtained, for example, by introducing a polymerizable functional group into one of the polymer compounds to give the other polymer compound. It can be carried out by copolymerizing the body. Further, the bond between the temperature-sensitive polymer compound having LCST and the water-soluble polymer compound is a block copolymer of the monomer giving the temperature-sensitive polymer compound and the monomer giving the water-soluble polymer compound. It can also be carried out by polymerization. Furthermore, the temperature-sensitive polymer compound having an LCST and the water-soluble polymer compound can be bonded by previously introducing a reactive functional group into both and bonding them by a chemical reaction. At this time, it is necessary to introduce a plurality of reactive functional groups into the water-soluble polymer compound.
【００１２】本発明の熱可逆性ハイドロゲル材料は、分
子内に存在する温度感応性高分子化合物のＬＣＳＴ以下
の温度においては、該温度感応性高分子化合物部分、水
溶性高分子化合物部分ともに水溶性であるので、完全に
水に溶解する。しかし、この水溶液の温度を、分子内に
存在する温度感応性高分子化合物のＬＣＳＴ以上の温度
に加温すると、該温度感応性高分子化合物部分が疎水性
となり、疎水的相互作用によって、別個の分子間で会合
する。一方、水溶性高分子化合物部分は、このときでも
水溶性であるので、本発明の熱可逆性ハイドロゲル材料
は水中において、温度感応性高分子化合物部分間の疎水
性会合部を架橋点とした、三次元網目構造をもつハイド
ロゲルを生成する。このハイドロゲルの温度を再び、分
子内に存在する温度感応性高分子化合物のＬＣＳＴ以下
の温度に冷却すると、該温度感応性高分子化合物部分が
水溶性となり疎水性会合による架橋点が解放され、ハイ
ドロゲル構造が消失する。このため、本発明の熱可逆性
ハイドロゲル材料は、再び完全な水溶液となる。このよ
うに、本発明の熱可逆性ハイドロゲル材料のゲル化は、
分子内に存在する温度感応性高分子化合物のＬＣＳＴに
おける可逆的な親水性、疎水性の変化に基づくものであ
るので、温度変化に対応して完全な可逆性を有する。The thermoreversible hydrogel material of the present invention is water-soluble at both the temperature-sensitive polymer compound portion and the water-soluble polymer compound portion at a temperature below the LCST of the temperature-sensitive polymer compound existing in the molecule. Soluble in water. However, when the temperature of this aqueous solution is heated to a temperature equal to or higher than the LCST of the temperature-sensitive polymer compound existing in the molecule, the temperature-sensitive polymer compound portion becomes hydrophobic, and the hydrophobic interaction causes a distinction between them. It associates between molecules. On the other hand, since the water-soluble polymer compound portion is water-soluble even at this time, the thermoreversible hydrogel material of the present invention has a hydrophobic association portion between the temperature-sensitive polymer compound portions in water as a crosslinking point. , Produces hydrogels with a three-dimensional network structure. When the temperature of the hydrogel is cooled again to a temperature equal to or lower than the LCST of the temperature-sensitive polymer compound existing in the molecule, the temperature-sensitive polymer compound portion becomes water-soluble and the cross-linking point due to hydrophobic association is released, The hydrogel structure disappears. Therefore, the thermoreversible hydrogel material of the present invention becomes a complete aqueous solution again. Thus, the gelling of the thermoreversible hydrogel material of the present invention is
Since it is based on the reversible changes in hydrophilicity and hydrophobicity in the LCST of the temperature-sensitive polymer compound present in the molecule, it has complete reversibility in response to temperature changes.
【００１３】[0013]
【実施例】以下に実施例を示して本発明をより具体的に
説明する。EXAMPLES The present invention will be described more specifically by showing examples.
【００１４】実施例１ （１）Ｎ−アクリロキシスクシンイミドの合成 Ｎ−ヒドロキシスクシンイミド１１.５ｇ、トリエチル
アミン１１ｇをクロロホルム１５０mlに溶解し、０℃に
冷却してアクリルロイルクロライド１０ｇを滴下した。
０℃で３０分間撹拌後、冷蒸留水８０mlを加えた。クロ
ロホルム層に無水硫酸マグネシウムを加え脱水、濾過
後、２,６−ジ−ｔ−ブチル−４−メチルフェノール１
０mgを加え、溶液を３０mlまで濃縮、氷冷し、酢酸エチ
ル３mlとヘキサン２０mlの混合溶液を滴下した。析出沈
殿を濾集し、酢酸エチル／ヘキサン＝１／４の混合溶液
で洗浄、さらに酢酸エチル／ヘキサン＝１／９の混合溶
液で洗浄後、真空乾燥して８.６ｇのＮ−アクリロキシ
スクシンイミドを得た。 Example 1 (1) Synthesis of N-acryloxysuccinimide 11.5 g of N-hydroxysuccinimide and 11 g of triethylamine were dissolved in 150 ml of chloroform, cooled to 0 ° C. and 10 g of acryloyl chloride was added dropwise.
After stirring for 30 minutes at 0 ° C., 80 ml of cold distilled water was added. Anhydrous magnesium sulfate was added to the chloroform layer for dehydration, filtration, and 2,6-di-t-butyl-4-methylphenol 1
0 mg was added, the solution was concentrated to 30 ml, ice-cooled, and a mixed solution of 3 ml of ethyl acetate and 20 ml of hexane was added dropwise. Precipitation The precipitate was collected by filtration, washed with a mixed solution of ethyl acetate / hexane = 1/4, further washed with a mixed solution of ethyl acetate / hexane = 1/9, and then vacuum dried to obtain 8.6 g of N-acryloxysuccinimide. Got
【００１５】（２）ポリ（Ｎ−イソプロピルアクリルア
ミド−コーＮ−アクリロキシスクシンイミド）の合成 Ｎ−イソプロピルアクリルアミド１０,２ｇ、Ｎ−アク
リロキシスクシンイミド１.７１ｇをクロロホルム４０
０mlに溶解、窒素置換後、Ｎ,Ｎ'−アゾビスイソブチロ
ニトリル０.１３５ｇを加え、６０℃にて６時間重合さ
せた。濃縮後、ジエチルエーテルに再沈した。凝集、真
空乾燥して８.８ｇのポリ（Ｎ−イソプロピルアクリル
アミド−コーＮ−アクリロキシスクシンイミド）を得
た。(2) Synthesis of poly (N-isopropylacrylamide-co-N-acryloxysuccinimide) 10,2 g of N-isopropylacrylamide, 1.71 g of N-acryloxysuccinimide and chloroform 40
After dissolving in 0 ml and purging with nitrogen, 0.135 g of N, N'-azobisisobutyronitrile was added, and the mixture was polymerized at 60 ° C for 6 hours. After concentration, it was reprecipitated in diethyl ether. After aggregation and vacuum drying, 8.8 g of poly (N-isopropylacrylamide-co-N-acryloxysuccinimide) was obtained.
【００１６】（３）熱可逆性ハイドロゲル材料Ｉの調製 ポリ（Ｎ−イソプロピルアクリルアミド−コーＮ−アク
リロキシスクシンイミド）１.０ｇ、両末端アミノ化ポ
リエチレンオキシド（分子量６,０００；川研ファイン
ケミカル（株）製）０.５ｇをクロロホルム１００mlに
溶解し、５０℃で３時間反応させた。室温まで冷却後、
イソプロピルアミン０.１ｇを加え、１時間放置した。
濃縮後、ジエチルエーテル中に沈殿させた。凝集、真空
乾燥して、１.５ｇの本発明の熱可逆性ハイドロゲル材
料Ｉを得た。(3) Preparation of Thermoreversible Hydrogel Material I Poly (N-isopropylacrylamide-co-N-acryloxysuccinimide) 1.0 g, both-end aminated polyethylene oxide (molecular weight 6,000; Kawaken Fine Chemicals Co., Ltd.) )) Was dissolved in 100 ml of chloroform and reacted at 50 ° C. for 3 hours. After cooling to room temperature,
0.1 g of isopropylamine was added and left for 1 hour.
After concentration, it was precipitated in diethyl ether. After coagulation and vacuum drying, 1.5 g of the thermoreversible hydrogel material I of the present invention was obtained.
【００１７】（４）熱可逆的ゲル化試験 熱可逆性ハイドロゲル材料Ｉ ０.５ｇを１０mlの蒸留水
に氷冷下で溶解した。この水溶液を徐々に加温すると、
約３０℃以上で流動性を失い、ゲル化した。このゲルを
冷却すると、約３０℃以下で流動性を取り戻し、再び水
溶液に戻った。この変化は可逆的に繰り返し観測され
た。(4) Thermoreversible gelation test 0.5 g of thermoreversible hydrogel material I was dissolved in 10 ml of distilled water under ice cooling. When gradually heating this aqueous solution,
At about 30 ° C or higher, it lost fluidity and gelled. When this gel was cooled, it recovered its fluidity at about 30 ° C. or lower and returned to the aqueous solution again. This change was repeatedly observed reversibly.
【００１８】実施例２ （１）ポリ（Ｎ−イソプロピルアクリルアミド−コーＮ
−アクリロキシスクシンイミドーコーｎ−ブチルメタク
リレート）の合成 Ｎ−イソプロピルアクリルアミド９.６１ｇ、Ｎ−アク
リロキシスクシンイミド１.７１ｇ、ｎ−ブチルメタク
リレート０.７１ｇをクロロホルム４００mlに溶解し、
窒素置換後、Ｎ,Ｎ'−アゾビスイソブチロニトリル０.
１３５ｇを加え、６０℃にて６時間重合させた。濃縮後
ジエチルエーテルに再沈した。濾集、真空乾燥して、
７.８ｇのポリ（Ｎ−イソプロピルアクリルアミド−コ
ーＮ−アクリロキシスクシンイミドーコーｎ−ブチルメ
タクリレート）を得た。 Example 2 (1) Poly (N-isopropylacrylamide-corn N)
-Acryloxysuccinimide-co-n-butylmethacrylate) 9.61 g of N-isopropylacrylamide, 1.71 g of N-acryloxysuccinimide and 0.71 g of n-butylmethacrylate were dissolved in 400 ml of chloroform,
After substitution with nitrogen, N, N'-azobisisobutyronitrile 0.
135g was added and it was made to polymerize at 60 degreeC for 6 hours. After concentration, it was reprecipitated in diethyl ether. Filter collection, vacuum dry,
7.8 g of poly (N-isopropylacrylamide-co-N-acryloxysuccinimide-co-n-butylmethacrylate) was obtained.
【００１９】（２）熱可逆性ハイドロゲル材料IIの調製 ポリ（Ｎ−イソプロピルアクリルアミド−コーＮ−アク
リロキシスクシンイミドーコーｎ−ブチルメタクリレー
ト）１.０ｇ、両末端アミノ化ポリエチレンオキシド
（分子量６,０００；川研ファインケミカル（株）製）
０.５ｇをクロロホルム１００mlに溶解し、５０℃にて
３時間反応させた。室温まで冷却後、イソプロピルアミ
ン０.１ｇを加え、１時間放置した。濃縮後、ジエチル
エーテル中に沈殿させた。濾過、真空乾燥して、１.５
ｇの本発明の熱可逆性ハイドロゲル材料IIを得た。(2) Preparation of thermoreversible hydrogel material II Poly (N-isopropylacrylamide-co-N-acryloxysuccinimide-co-n-butylmethacrylate) 1.0 g, aminated polyethylene oxide having both ends (molecular weight 6,000) ; Kawaken Fine Chemicals Co., Ltd.)
0.5 g was dissolved in 100 ml of chloroform and reacted at 50 ° C. for 3 hours. After cooling to room temperature, 0.1 g of isopropylamine was added and left for 1 hour. After concentration, it was precipitated in diethyl ether. Filter and vacuum dry to 1.5
g of thermoreversible hydrogel material II of the invention was obtained.
【００２０】（３）熱可逆的ゲル化試験 熱可逆性ハイドロゲル材料II ０.５ｇを１０mlの蒸留水
に氷冷下で溶解した。この水溶液を徐々に加温すると、
約２０℃以上で流動性を失い、ゲル化した。このゲルを
冷却すると、約２０℃以下で流動性を取り戻し、再び水
溶液に戻った。この変化は可逆的に繰り返し観測され
た。(3) Thermoreversible gelation test 0.5 g of thermoreversible hydrogel material II was dissolved in 10 ml of distilled water under ice cooling. When gradually heating this aqueous solution,
At about 20 ° C or higher, it lost fluidity and gelled. When this gel was cooled, it recovered its fluidity at about 20 ° C. or lower and returned to the aqueous solution again. This change was repeatedly observed reversibly.
【００２１】[0021]
【発明の効果】以上詳しく説明したように、本発明の熱
可逆性ハイドロゲル材料は、特定の温度以下では水溶
性、その温度以上ではハイドロゲルとなる。本発明の熱
可逆性ハイドロゲル材料のゲル化は、分子内に存在する
温度感応性高分子化合物のＬＣＳＴにおける可逆的な親
水性、疎水性の変化に基づくものであるので、温度変化
に対応して完全な可逆性を有する。また、上記ＬＣＳＴ
は任意に制御可能であるのでゲル化温度も任意に制御で
きる。このように、本発明の熱可逆性ハイドロゲル材料
は従来にない特徴を有するので、物質の分離や医薬品、
食品、農薬、化粧品などに広く利用される。As described in detail above, the thermoreversible hydrogel material of the present invention is water-soluble below a specific temperature and becomes a hydrogel above that temperature. The gelation of the thermoreversible hydrogel material of the present invention is based on the reversible hydrophilicity / hydrophobicity change in the LCST of the temperature-sensitive polymer compound present in the molecule, and therefore, it corresponds to the temperature change. It has complete reversibility. In addition, the LCST
Can be controlled arbitrarily, so the gelation temperature can also be controlled arbitrarily. As described above, since the thermoreversible hydrogel material of the present invention has characteristics that have not existed in the past, separation of substances and pharmaceuticals,
Widely used in food, agricultural chemicals, cosmetics, etc.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 有一 神奈川県横浜市金沢区釜利谷町1642−212 Ｂ−４ ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yuichi Mori 1642-212 B-4, Kamariya-cho, Kanazawa-ku, Yokohama, Kanagawa
Claims (1)
と水溶性高分子化合物が結合されてなる高分子化合物で
あって、該ＬＣＳＴを有する温度感応性高分子化合物部
分が一分子内に複数存在する熱可逆性ハイドロゲル材
料。1. A polymer compound in which a temperature-sensitive polymer compound having LCST and a water-soluble polymer compound are bound to each other, and a plurality of temperature-sensitive polymer compound portions having the LCST are present in one molecule. Thermo-reversible hydrogel material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04016114A JP3121660B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible hydrogel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04016114A JP3121660B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible hydrogel material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05262882A true JPH05262882A (en) | 1993-10-12 |
| JP3121660B2 JP3121660B2 (en) | 2001-01-09 |
Family
ID=11907491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04016114A Expired - Fee Related JP3121660B2 (en) | 1992-01-31 | 1992-01-31 | Thermoreversible hydrogel material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3121660B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000275A3 (en) * | 1995-06-16 | 1997-03-06 | Gel Sciences Inc | Responsive polymer networks and methods of their use |
| US5834007A (en) * | 1993-09-16 | 1998-11-10 | Ogita Biomaterial Laboratories Co. Ltd. | Wound-covering material and wound-covering composition |
| JP2001096104A (en) * | 1999-07-29 | 2001-04-10 | Univ Kansai | Method and apparatus for removing organic matter in liquid |
| WO2001070022A1 (en) * | 2000-03-21 | 2001-09-27 | Yuichi Mori | Coating materials for biological tissues, coated biological tissues and method of coating biological tissues |
| JP2005534732A (en) * | 2002-06-14 | 2005-11-17 | ポリメーレクスペール エス アー | Thermosensitive polymer and thermoreversible gel obtained from the polymer |
| JP2006501824A (en) * | 2002-10-03 | 2006-01-19 | アグロシールド リミテッド ライアビリティー カンパニー | Polymers to protect materials from damage |
| JP2006525093A (en) * | 2003-04-30 | 2006-11-09 | ドゥレクセル ユニヴァーシティ | Thermally gelled polymer blends for biomaterial applications |
| CN1305916C (en) * | 2004-12-10 | 2007-03-21 | 武汉大学 | Temperature sensitive linear polymer containing siloxane side chain and its water gel and preparing method |
| US7456275B2 (en) | 2002-04-18 | 2008-11-25 | Chugai Seiyaku Kabushiki Kaisya | Hyaluronic acid modification product |
| US7786194B2 (en) | 2004-04-02 | 2010-08-31 | Agroshield, Llc | Compositions and methods for protecting materials from damage |
| US8557583B2 (en) | 2007-03-15 | 2013-10-15 | Dai Nippon Printing Co., Ltd. | Cell culture support and manufacture thereof |
| WO2015155852A1 (en) * | 2014-04-09 | 2015-10-15 | 株式会社クレアテラ | Device and method for removing salts from food |
| WO2019194022A1 (en) * | 2018-04-05 | 2019-10-10 | 三菱電機株式会社 | Heat storage material, method for preparing same, and heat storage tank |
-
1992
- 1992-01-31 JP JP04016114A patent/JP3121660B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834007A (en) * | 1993-09-16 | 1998-11-10 | Ogita Biomaterial Laboratories Co. Ltd. | Wound-covering material and wound-covering composition |
| WO1997000275A3 (en) * | 1995-06-16 | 1997-03-06 | Gel Sciences Inc | Responsive polymer networks and methods of their use |
| JP2001096104A (en) * | 1999-07-29 | 2001-04-10 | Univ Kansai | Method and apparatus for removing organic matter in liquid |
| WO2001070022A1 (en) * | 2000-03-21 | 2001-09-27 | Yuichi Mori | Coating materials for biological tissues, coated biological tissues and method of coating biological tissues |
| US7456275B2 (en) | 2002-04-18 | 2008-11-25 | Chugai Seiyaku Kabushiki Kaisya | Hyaluronic acid modification product |
| JP2005534732A (en) * | 2002-06-14 | 2005-11-17 | ポリメーレクスペール エス アー | Thermosensitive polymer and thermoreversible gel obtained from the polymer |
| JP2006501824A (en) * | 2002-10-03 | 2006-01-19 | アグロシールド リミテッド ライアビリティー カンパニー | Polymers to protect materials from damage |
| JP2006525093A (en) * | 2003-04-30 | 2006-11-09 | ドゥレクセル ユニヴァーシティ | Thermally gelled polymer blends for biomaterial applications |
| JP4917885B2 (en) * | 2003-04-30 | 2012-04-18 | ドゥレクセル ユニヴァーシティ | Thermally gelled polymer blends for biomaterial applications |
| US7786194B2 (en) | 2004-04-02 | 2010-08-31 | Agroshield, Llc | Compositions and methods for protecting materials from damage |
| CN1305916C (en) * | 2004-12-10 | 2007-03-21 | 武汉大学 | Temperature sensitive linear polymer containing siloxane side chain and its water gel and preparing method |
| US8557583B2 (en) | 2007-03-15 | 2013-10-15 | Dai Nippon Printing Co., Ltd. | Cell culture support and manufacture thereof |
| WO2015155852A1 (en) * | 2014-04-09 | 2015-10-15 | 株式会社クレアテラ | Device and method for removing salts from food |
| JP6052701B2 (en) * | 2014-04-09 | 2016-12-27 | 株式会社クレアテラ | Apparatus and method for removing salts from food |
| WO2019194022A1 (en) * | 2018-04-05 | 2019-10-10 | 三菱電機株式会社 | Heat storage material, method for preparing same, and heat storage tank |
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|---|---|
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