JP2002080604A - Composite hydrogel consisting of alginine polymer and polyvinyl alcohol, and process for producing it - Google Patents
Composite hydrogel consisting of alginine polymer and polyvinyl alcohol, and process for producing itInfo
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルギニン重合体
を含む高分子複合体含水ゲルおよびその製造方法に関す
るものである。The present invention relates to a polymer composite hydrogel containing an arginine polymer and a method for producing the same.
【０００２】[0002]
【従来の技術】高分子複合体含水ゲルは生体類似構造を
持ち、医療面や人工筋肉などのメカノケミカル分野、あ
るいは細胞増殖のような先端的技術分野で有用なものと
期待されている。高分子含水ゲルについては、これまで
も各種の提案がされている。例えば、ポリビニルアルコ
ール含水ゲルについては特開昭５７−１３０５４３号、
特開昭５８−３６６３０号及び特開昭６１−８６１１０
号公報に示されるような製造方法が発表されており、こ
のものは生理活性をほとんど示さないので医療用材料に
使用されている。また、ポリビニルアルコール（以下Ｐ
ＶＡと略記）とポリアクリル酸からなる複合体含水ゲル
は、電場印加によって駆動するアクチュエーター材料と
して検討されているし、ＰＶＡとポリアリルアミンとポ
リアクリル酸からなる三成分系複合体含水ゲルもアクチ
ュエーター材料として検討されている。一方、生体と類
似した構造を持つアリルアミン−アリルビグアニド共重
合体（以下ＰＡＢと略記）については、本発明者の一人
がその合成法について検討し先に特許出願を行った（特
許第２０９９１２１号）。また、ＰＡＢとＰＶＡからな
る複合体含水ゲルおよびその製造方法についても先に特
許出願を行った（特許第１９６６６６８号）。しかし、
アルギニン重合体（以下ＰＡｒｇと略記）とＰＶＡから
なる複合体含水ゲルについては、現在に至るまで全く発
表されていない。2. Description of the Related Art A polymer composite hydrogel has a biologically similar structure and is expected to be useful in mechanochemical fields such as medical fields and artificial muscles, or in advanced technical fields such as cell proliferation. Various proposals have been made on polymer hydrogels. For example, polyvinyl alcohol hydrate gel is described in JP-A-57-130543,
JP-A-58-36630 and JP-A-61-86110
A production method as disclosed in Japanese Unexamined Patent Application Publication No. H11-27139 has been disclosed, which is used as a medical material because it hardly exhibits physiological activity. In addition, polyvinyl alcohol (hereinafter P
The composite hydrogel comprising VA and a polyacrylic acid has been studied as an actuator material driven by application of an electric field, and a ternary composite hydrogel comprising PVA, polyallylamine and polyacrylic acid is also an actuator material. It has been considered as. On the other hand, as for an allylamine-allylbiguanide copolymer having a structure similar to that of a living body (hereinafter abbreviated as PAB), one of the present inventors studied a synthesis method thereof and filed a patent application first (Japanese Patent No. 2099121). . A patent application was also made for a composite hydrogel comprising PAB and PVA and a method for producing the same (Japanese Patent No. 19666668). But,
A composite hydrogel comprising an arginine polymer (hereinafter abbreviated as PArg) and PVA has not been disclosed at all up to the present.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、ＰＡｒｇを
構成成分とする新規な複合体含水ゲルおよびその製造方
法を提供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel composite hydrogel comprising PArg as a component and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討を重ね、本発明を完成するに至っ
た。すなわち、本発明によれば、ＰＡｒｇとＰＶＡから
なる複合体含水ゲルが提供される。また、本発明によれ
ば、ＰＡｒｇとＰＶＡの混合物を含む水溶液を所要形状
に保持し、この状態で該水溶液の凍結と解凍を複数回に
わたって繰り返し行うことを特徴とするＰＡｒｇとＰＶ
Ａからなる複合体含水ゲルの製造方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and have completed the present invention. That is, according to the present invention, a composite hydrogel comprising PArg and PVA is provided. Further, according to the present invention, an aqueous solution containing a mixture of PArg and PVA is maintained in a required shape, and in this state, freezing and thawing of the aqueous solution are repeated a plurality of times, wherein PArg and PVA are repeatedly used.
A method for producing a composite hydrogel comprising A is provided.
【０００５】[0005]
【発明の実施の形態】本発明で用いるＰＡｒｇは次の構
造式化１で表される。BEST MODE FOR CARRYING OUT THE INVENTION PArg used in the present invention is represented by the following structural formula 1.
【０００６】[0006]
【化１】 Embedded image
【０００７】構造式化１中、ｎは８〜５００、好ましく
は１０〜２００の整数を示す。In the structural formula 1, n represents an integer of 8 to 500, preferably 10 to 200.
【０００８】本発明のＰＡｒｇ−ＰＶＡ複合体含水ゲル
はＰＡｒｇとＰＶＡを水に溶解して均一の混合状態の水
溶液を作製後、これを複数回にわたって凍結・解凍を繰
り返すことによって製造することができる。ＰＡｒｇと
ＰＶＡを水に溶解させる場合は加熱するのが望ましく、
加熱温度は一般に１００〜１２１℃であるが、１１０〜
１２１℃の範囲に加熱するのがより好ましい。また、水
溶液中の高分子濃度（ＰＡｒｇとＰＶＡの合計濃度）は
３〜２０重量％、好ましくは７〜１５重量％である。な
お、前記した凍結・解凍の繰り返し回数は一般に３回以
上、好ましくは８〜１２回である。以上のようにして形
成されるＰＡｒｇ−ＰＶＡ複合体含水ゲルの含水量は、
使用目的等に応じて適宜に定めることができるが、好ま
しくは８０〜９７重量％であり、含水量を８５〜９３重
量％にするのがより好ましい。また、ＰＡｒｇとＰＶＡ
の割合は特に限定されず、該複合体含水ゲルの用途に応
じて適宜定めればよい。The water-containing PAg-PVA composite gel of the present invention can be produced by dissolving PArg and PVA in water to prepare a homogeneous mixed aqueous solution, and then repeatedly freezing and thawing the aqueous solution a plurality of times. . When dissolving PArg and PVA in water, it is desirable to heat,
The heating temperature is generally 100 to 121 ° C.,
It is more preferable to heat to the range of 121 ° C. The polymer concentration (total concentration of PArg and PVA) in the aqueous solution is 3 to 20% by weight, preferably 7 to 15% by weight. In addition, the number of repetitions of the above-mentioned freezing / thawing is generally 3 or more times, preferably 8 to 12 times. The water content of the PArg-PVA composite hydrogel formed as described above is:
Although it can be appropriately determined according to the purpose of use and the like, it is preferably 80 to 97% by weight, and more preferably the water content is 85 to 93% by weight. PARG and PVA
Is not particularly limited, and may be appropriately determined according to the use of the composite hydrogel.
【０００９】[0009]
【実施例】次に、本発明を実施例および比較例によって
より具体的に説明するが、本発明はこの実施例によって
限定されるものではない。なお、本実施例に示されるＰ
Ａｒｇ−ＰＶＡ複合体中のＰＡｒｇ含有率（％）はモノ
マー単位のモル％を示したものであり、本発明の複合体
に含まれるＰＡｒｇのモノマー単位量（これはポリアル
ギニン中のアルギニンモノマー単位量と一致する）をＡ
モル、本発明の複合体に含まれるＰＶＡ中のビニルアル
コールモノマー単位量をＢモルとしたとき、ＰＡｒｇ含
有率（モル％）＝１００×Ａ／（Ａ＋Ｂ）で示される。Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that P shown in the present embodiment is
The PArg content (%) in the Arg-PVA composite indicates mol% of the monomer unit, and the PArg monomer unit amount (this is the arginine monomer unit amount in the polyarginine) contained in the composite of the present invention. A)
When the molar amount of vinyl alcohol monomer units in the PVA contained in the composite of the present invention is defined as B mole, PArg content (mol%) = 100 × A / (A + B).
【００１０】実施例１ 容量３０ｍｌのサンプル瓶にＰＡｒｇ塩酸塩（ｎ＝１
２）１９５．６３ｍｇとＰＶＡ（和光純薬製；重合度約
２，０００；ケン化度９８％以上）１０４．３７ｍｇお
よび純水２．７ｍｌを加え、長さ約１ｃｍ、内径約０．
５ｍｍのキャピラリーを入れ、オートクレーブ中で１１
０〜１２１℃に加熱して１０重量％溶液にした。次に溶
解したポリマー溶液を約−１８℃で凍結してから冷蔵庫
に戻して解凍した。この凍結・解凍を１０回繰り返すこ
とによって、モノマーモル比（ＰＡｒｇ／ＰＶＡ＝３０
／７０）、水分含有率９０重量％以上のＰＡｒｇ−ＰＶ
Ａ複合体含水ゲルを得た。Example 1 PAarg hydrochloride (n = 1) was placed in a sample bottle having a capacity of 30 ml.
2) 195.63 mg, 104.37 mg of PVA (manufactured by Wako Pure Chemical; degree of polymerization: about 2,000; saponification degree of 98% or more) and 2.7 ml of pure water were added, and the length was about 1 cm, and the inner diameter was about 0,0.
Insert a 5 mm capillary and place in an autoclave at 11
Heated to 0-121 ° C. to make a 10% by weight solution. Next, the dissolved polymer solution was frozen at about −18 ° C., returned to the refrigerator, and thawed. This freezing and thawing is repeated 10 times to obtain a monomer molar ratio (PAArg / PVA = 30).
/ 70), PArg-PV having a water content of 90% by weight or more
A composite hydrogel was obtained.
【００１１】実施例２ 実施例１と同様にして、ＰＡｒｇ含有量の異なるモノマ
ーモル比（ＰＡｒｇ／ＰＶＡ＝１０／９０）およびモノ
マーモル比（ＰＡｒｇ／ＰＶＡ＝５／９５）のＰＡｒｇ
−ＰＶＡ複合体含水ゲルを調製した。 実施例３ ＰＡｒｇ−ＰＶＡ複合体含水ゲルの膨潤および収縮の挙
動を調べた。ＰＡｒｇ含有率３０％の複合体含水ゲルを
用いて、ｐＨ３とｐＨ１３の水溶液を調製して、各々の
２０℃の水溶液にキャピラリーから取り出したハイドロ
ゲルを浸し、ゲルの直径の時間的変化を測定した。測定
結果を図１に示す。酸性側のｐＨ３と塩基性側のｐＨ１
３の両方とも５分前後から平衡に達している。ゲルの直
径の測定は、所定の水溶液に浸せき後、十分に平衡に達
している１５分後に測定した。測定後中性の純水に１５
分浸して元の状態に戻し、次の測定を行った。塩基性の
測定後は、２Ｎ−ＨＣｌに１５分浸せきし、元の塩酸塩
に戻し次の測定を行った。Example 2 In the same manner as in Example 1, a monomer molar ratio (PArg / PVA = 10/90) having a different PArg content and PAArg having a monomer molar ratio (PArg / PVA = 5/95) were used.
-A PVA composite hydrogel was prepared. Example 3 The swelling and shrinkage behavior of the PArg-PVA composite hydrogel was examined. Using a composite hydrogel having a PArg content of 30%, aqueous solutions of pH 3 and pH 13 were prepared, and the hydrogel taken out of the capillary was immersed in each of the aqueous solutions at 20 ° C., and the time-dependent change in the diameter of the gel was measured. . FIG. 1 shows the measurement results. PH 3 on the acidic side and pH 1 on the basic side
Both of the three reached equilibrium from around 5 minutes. The measurement of the diameter of the gel was carried out 15 minutes after immersion in a predetermined aqueous solution and a sufficient equilibrium was reached. After measurement, add 15
After being soaked, the sample was returned to the original state and the next measurement was performed. After the measurement of basicity, the sample was immersed in 2N-HCl for 15 minutes, returned to the original hydrochloride, and subjected to the next measurement.
【００１２】実施例４ ＰＡｒｇ含有率３０％の複合体含水ゲルを用いてｐＨ１
〜１３の水溶液における伸縮性を２０℃で測定した。所
定のｐＨの水溶液中で１５分後のゲルの直径を１０回測
定し、その平均値を算出した。その値を伸縮率で表し
た。ハイドロゲルの伸縮率は次式から算出した。 伸縮率(％)＝(測定した)ゲルの直径(ｄ)／キャピラリー
の内径(ｄ０))×１００ 所定のｐＨ水溶液は、塩酸水溶液と水酸化ナトリウム水
溶液を用いて調製した。測定結果を図２に示した。Example 4 A composite hydrogel having a PArg content of 30% was used to adjust the pH to 1
The elasticity in aqueous solutions of Nos. To 13 was measured at 20 ° C. The diameter of the gel after 15 minutes in an aqueous solution having a predetermined pH was measured 10 times, and the average value was calculated. The value was represented by a stretch ratio. The stretch ratio of the hydrogel was calculated from the following equation. Expansion ratio (%) = (measured) gel diameter (d) / capillary inner diameter (d 0 )) × 100 A predetermined pH aqueous solution was prepared using a hydrochloric acid aqueous solution and a sodium hydroxide aqueous solution. The measurement results are shown in FIG.
【００１３】実施例５ ＰＡｒｇ含有率３０％の複合体含水ゲルを用いて、その
伸縮性の食塩濃度依存性を測定した。その測定は、温度
を２０℃の一定に保ち、ＮａＣｌ（Ｍｗ：５８．４４）
を用いて、食塩濃度１０−５モル／Ｌから１モル／Ｌま
での水溶液濃度範囲において行った。具体的には、ハイ
ドロゲルを純水に浸せきして平衡状態にした後、所定の
食塩濃度水溶液に浸せきし、実施例４と同様な方法にて
測定した。測定結果を図３に示した。Example 5 A composite hydrogel having a PArg content of 30% was used to measure its elasticity-dependent salt concentration dependence. The measurement was performed by keeping the temperature constant at 20 ° C. and NaCl (Mw: 58.44).
Was performed in an aqueous solution concentration range from 10 −5 mol / L to 1 mol / L. Specifically, the hydrogel was immersed in pure water to be in an equilibrium state, then immersed in a predetermined aqueous solution of salt concentration, and measured in the same manner as in Example 4. The measurement results are shown in FIG.
【００１４】実施例６ ＰＡｒｇ含有率３０％の複合体含水ゲルを用いて、その
伸縮性のイオン強度一定下におけるｐＨ応答性を測定し
た。この場合その測定は、温度を２０℃一定に保ち、イ
オン強度μ＝０．１の一定の条件にＮａＣｌと酸性側で
ＨＣｌまた、塩基性側でＮａＯＨ水溶液を用いてそれぞ
れのｐＨ水溶液を調製し、あらかじめ純水に浸せきした
平衡状態のハイドロゲルを浸せきし、実施例３と同様に
して行った。測定結果を図４に示した。Example 6 The pH responsiveness of a hydrated composite gel having a PArg content of 30% under a constant ionic strength was measured. In this case, the measurement was performed by keeping the temperature constant at 20 ° C. and preparing a pH aqueous solution using NaCl and HCl on the acidic side and NaOH aqueous solution on the basic side under a constant condition of ionic strength μ = 0.1. The hydrogel in an equilibrium state previously immersed in pure water was immersed in the same manner as in Example 3. The measurement results are shown in FIG.
【００１５】[0015]
【発明の効果】本発明の複合体含水ゲルは、ｐＨ、イオ
ン濃度等の外部刺激によって伸縮性を示し、この特性を
利用することによりメカノケミカル材料に利用すること
ができる。The composite hydrogel of the present invention exhibits elasticity due to external stimuli such as pH and ion concentration, and can be used as a mechanochemical material by utilizing this property.
【図１】ＰＡｒｇ含有複合体含水ゲル（ＰＡｒｇ含有率
３０％）の膨潤挙動（ｐＨ３）および収縮挙動（ｐＨ１
３）の応答速度を示す図である。FIG. 1 shows the swelling behavior (pH 3) and shrinking behavior (pH 1) of a PAArg-containing composite hydrogel (PArg content 30%).
It is a figure which shows the response speed of 3).
【図２】ＰＡｒｇ含有複合体含水ゲル（ＰＡｒｇ含有率
３０％）の伸縮率のｐＨ依存性を示す図である。FIG. 2 is a diagram showing the pH dependence of the expansion and contraction rate of the PAHg-containing composite hydrogel (PArg content: 30%).
【図３】ＰＡｒｇ含有複合体含水ゲル（ＰＡｒｇ含有率
３０％）を食塩水中に浸せきした場合にその複合体含水
ゲルが示す伸縮率と食塩濃度の関係を示す図である。FIG. 3 is a graph showing the relationship between the expansion / contraction ratio of the composite hydrogel and the salt concentration when the PAGg-containing composite hydrogel (PArg content: 30%) is immersed in saline.
【図４】ＰＡｒｇ含有複合体含水ゲル（ＰＡｒｇ含有率
３０％）をイオン強度一定下での所定のｐＨ水溶液に浸
せきした場合にその複合体含水ゲルが示す伸縮率とｐＨ
の関係を示す図である。FIG. 4 shows the expansion ratio and pH of a composite hydrogel when the PArg-containing composite hydrogel (PArg content 30%) is immersed in a predetermined pH aqueous solution at a constant ionic strength.
FIG.
Claims (2)
ルからなる複合体含水ゲル。1. A composite hydrogel comprising an arginine polymer and polyvinyl alcohol.
ルの混合物を含む水溶液を所要形状に保持し、この状態
で該水溶液の凍結と解凍を複数回にわたって繰り返し行
うことを特徴とするアルギニン重合体とポリビニルアル
コールからなる複合体含水ゲルの製造方法。2. An aqueous solution containing a mixture of an arginine polymer and polyvinyl alcohol in a required shape, and in this state, freezing and thawing of the aqueous solution are repeated a plurality of times. A method for producing a composite hydrogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000270960A JP3421743B2 (en) | 2000-09-07 | 2000-09-07 | Composite hydrogel comprising arginine polymer and polyvinyl alcohol and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000270960A JP3421743B2 (en) | 2000-09-07 | 2000-09-07 | Composite hydrogel comprising arginine polymer and polyvinyl alcohol and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002080604A true JP2002080604A (en) | 2002-03-19 |
| JP3421743B2 JP3421743B2 (en) | 2003-06-30 |
Family
ID=18757313
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000270960A Expired - Lifetime JP3421743B2 (en) | 2000-09-07 | 2000-09-07 | Composite hydrogel comprising arginine polymer and polyvinyl alcohol and method for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107023A (en) * | 2011-01-30 | 2011-06-29 | 北京科技大学 | Preparation method of biological function composite auxetic hydrogel with shell core structure |
-
2000
- 2000-09-07 JP JP2000270960A patent/JP3421743B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107023A (en) * | 2011-01-30 | 2011-06-29 | 北京科技大学 | Preparation method of biological function composite auxetic hydrogel with shell core structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3421743B2 (en) | 2003-06-30 |
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