JP2004043543A - Method for manufacturing hydrogel by recyclingly used polysaccharide derivative - Google Patents
Method for manufacturing hydrogel by recyclingly used polysaccharide derivative Download PDFInfo
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- JP2004043543A JP2004043543A JP2002199745A JP2002199745A JP2004043543A JP 2004043543 A JP2004043543 A JP 2004043543A JP 2002199745 A JP2002199745 A JP 2002199745A JP 2002199745 A JP2002199745 A JP 2002199745A JP 2004043543 A JP2004043543 A JP 2004043543A
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、使用により粘度低下を起したデンプンやセルロース誘導体の有効利用に関するものである。
【0002】
即ち、ソジウムカルボキシメチルセルロース(CMC)に精製水を加え良く練ったペースト状態に電離性放射線を照射して得たハイドロゲルは、蓄冷剤や保温剤として長時間の使用した場合分解が起こる。これを有効利用するため、新しいCMC又はソジウムカルボキシメチルデンプン(CMS)を少量添加し、良く練りペースト状で再び照射することにより、最初のものと同じ弾性のあるハイドロゲルが得られ、CMCを廃棄することなく再利用できる。この再利用は数回繰り返し行えるが、天然類の多糖誘導体は生分解性であるため、焼却処分による廃棄は必要なく肥料として土に還元できる。本発明は資源を有効活用できる有用な技術である。
【0003】
【従来技術】
放射線によりハイドロゲルを製造する技術には、ポリエチレンオキサイド、ポリビニルアルコール、ポリアクリルアミド、ポリビニルピロリドなどの水溶液を電離性放射線の照射により容易に得られる。ハイドロゲルは水を多量に吸収し保持できるため、使い捨てオムツなどの衛生用品や保湿材として医療、化粧品の分野で使用されている。これらにはポリアクリル酸ソーダをベースとした材料が主に使われている。
【0004】
しかし、その使用後の処理に困り、大部分は焼却により処分されている。多量に処理した場合は焼却炉の温度が下がりダイオキシンの発生の恐れもある。そのため、照射橋かけにより得られるポリグルタミン酸ソーダやポリアスパラギンソーダのように土壌中で分解する環境に負荷を与えないハイドロゲルの応用が試みられている。
【0005】
【発明が解決しようとする課題】
デンプンやセルロース誘導体の橋かけには、ホルマリンやグルタルアルデヒドなどの化学橋かけ剤がよく使われている。この方法ではアルデヒドが作業環境を汚染することがあり、残留した場合は皮膚を刺激することがあるため安全な橋かけ技術が求められている。
【0006】
又、水溶性ポリマーを橋かけして得られるハイドロゲルは多量に吸水するため、使い捨てオムツなどの衛生用品に使われている。発明者らは、カルボキシメチル化したデンプン、セルロース、キチン・キトサンを水と良く練り高濃度のペースト状にしてから照射を行うと、放射線橋かけ反応が起き、ハイドロゲルになることを見出した(特願2000−15237、特願2001−362131、特開2001−2703)。
【0007】
しかし、これらのハイドロゲルを蓄冷剤や保温剤の媒体として長い期間使用すると分解により、粘度がしだいに低下してくる。このためゲル弾性がなくなってくる。このような粘度低下を起したハイドロゲルを焼却や捨てることなく、有効に再利用するための技術を開発し、本発明を達成した。
【0008】
【課題を解決するための手段】
ところで、ただ単に、デンプンやセルロース誘導体は固体状態や希薄水溶液(5%以下の濃度)の放射線照射では分解が優先して起こるため、放射線橋かけによる加工は困難であった。
【0009】
本発明者は、セルロース、デンプン及びキチン・キトサンの誘導体に精製水を加え良く練り高濃度ペースト状態にして電離性放射線の照射により橋かけ構造を導入し、ハイドロゲルを得ることに成功した(特願2000−152372、特願2001−362131、特開2001−2703)。
【0010】
しかし、セルロースやデンプンゲル誘導体ハイドロゲルを長い期間蓄冷剤や保温剤の媒体として使用すると、分解により粘度の低下が起こる。これを捨てることなく資源を有効に活用するため、再利用技術の開発研究を鋭意重ねた。
【0011】
その結果、使用により粘度低下を起したデンプンやセルロース誘導体にそれと同じ種類の新しい材料を添加し、ペースト状試料を調製し放射線照射を行うと、再び弾性のあるハイドロゲルが得られる。ハイドロゲルの軟らかさは新しい材料の添加の濃度と照射の線量により、制御できる。これらは蓄冷剤や保温剤に再利用することができ、本発明を達成した。
【0012】
【発明の実施の形態】
本発明においては、蓄冷剤や保温剤として使用し粘度低下を起したセルロース及びデンプン誘導体ハイドロゲルに同じ新しい材料を添加して良く練り、容器を傾けても流れないペーストを得る。これをポリ塩化ビニリデン製の袋に入れ、真空脱気の後、熱シールを行いγ線により照射した。照射前は柔らかいペーストであるが、照射によりゴム状を呈した弾力のあるハイドロゲルが得られる。
【0013】
放射線橋かけを行うためのセルロースやデンプン誘導体のペーストの濃度は、置換度により異なるが、好ましい濃度は10%以上である。ハイドロゲルの硬さは、ペーストの濃度と照射の線量により制御できる。
【0014】
電離性放射線は、γ線、電子線及びX線であり,橋かけの線量は0.5 〜 1,000たkGyである。好ましい橋かけの線量は1〜300 kGy である。
本発明で用いる再利用できるセルロース及び/又はデンプン誘導体のハイドロゲルは水に溶解するものであればいずれでも良い。置換度が高いほど水との親和性が増し、高濃度のペーストが得られるため好ましい。最も好ましい置換度は0.01から2.5である。
【0015】
本発明の再利用できるセルロース及び/又はデンプン誘導体ハイドロゲルは、CMC, メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、酸化セルロース、CMS、メチルデンプン、エチルデンプン、ヒドロキシエチルデンプン、ヒドロキシプロピルデンプン、酸化デンプン、又はそれらの混合物である。
【0016】
電離性放射線は、工業的生産のため、コバルト−60からのγ線と加速器による電子線が好ましい。電子加速器は厚物の照射ができる加速電圧1MeV以上の中エネルギーから高エネルギー電子加速器が最も好ましい。照射前の試料に圧力をかけフィルム状に加工すれば1MeV以下の低エネルギー電子加速器でも電子線が透過するため放射線橋かけによりゲルを得ることができる。照射中の酸素による橋かけへの影響はほとんどないが、照射中の水分の蒸発防止及び橋かけ密度の低下を抑制するため、ポリエステルなどのプラスチックフィルムなどにより上面をカバーして照射するのが望ましい。
【0017】
長期間の使用により粘度低下を起したセルロース及び/又はデンプン誘導体ハイドロゲルに新しい材料を添加し、照射して得られるハイドロゲルの評価法としては、径60mmのガラスシャーレに厚みが15mmになるようにハイドロゲルを充填し、そのゲルの上に厚み1.5mm、径35mmのプラスチックシートをのせ、その上から径5mm軸の厚み計で押し、厚みを計測した。軟らかいゲルであればプラスチックシートの円盤がゲル内にめり込み、厚みとして小さな値を示す。
【0018】
セルロース誘導体ハイドロゲルを蓄冷剤や保温剤として長い期間使用すると、粘度が低下し、厚みが0.5mmになる。これに新しい材料を添加し、ペースト状にし照射を行うと弾性のあるハイドロゲルが得られ、厚みが計の指示5から13mmのハイドロゲルが得られる。
【0019】
【実施例】
以下、本発明を比較例及び実施例に基づいて説明する。
(比較例1)
用いたCMCはダイセル化学株式会社で製造したもので、そのカルボキシメチル基の置換度は1.29である。この試料20gを精製水180gと良く練り、10%のペースト状に調製し、ポリ塩化ビニリデン袋に入れ、真空パックにしてからγ線により10kGy照射した。このようにして得た橋かけCMCハイドロゲルの厚み計の指示は12.5mmである。
【0020】
(実施例1)
比較例1で調製したハイドロゲルを50℃で3週間保持した。保温中に分解が進行し、ハイドロゲルの弾性がなくなり、粘度が著しく低下した。厚み計により測定した厚みは0.3mmに減少した。これに新しいCMCを3%〜10%添加し、10kGyの照射を行った。その結果が表1である。
【0021】
【表1】
【0022】
この表から、明らかに新しいCMCを添加することにより、厚みが増し、弾性のあるハイドロゲルが得られる。
粘度低下を起したCMC水溶液を再利用すると、5%の新しいCMCの添加により、新しいCMC10%とほぼ同じ弾力性を持ったハイドロゲル(比較例1)が得られる。
【0023】
さらに、粘度低下を起こしたCMC水溶液に新しいCMCを10%添加すると、厚み計の圧力では変形しない硬いハイドロゲルが得られる。
【0024】
【発明の効果】
以上のよう使用後粘度低下を起したCMCが、新しいCMCの添加により、焼却や捨てることなく再利用できる。最終的に使用できなくなったCMCは生分解性であるため、肥料として土に還元できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to effective use of starch and cellulose derivatives whose viscosity has been reduced by use.
[0002]
That is, the hydrogel obtained by adding purified water to sodium carboxymethyl cellulose (CMC) and irradiating ionizing radiation to a well-kneaded paste state is decomposed when used as a cold storage agent or a heat retaining agent for a long time. In order to make effective use of this, a small amount of new CMC or sodium carboxymethyl starch (CMS) is added, and the mixture is irradiated again in a well-kneaded paste form, whereby the same elastic hydrogel as the first one is obtained. Can be reused without discarding. This reuse can be repeated several times, but since natural polysaccharide derivatives are biodegradable, they can be reduced to soil as fertilizer without disposal by incineration. The present invention is a useful technology that can effectively utilize resources.
[0003]
[Prior art]
As a technique for producing a hydrogel by radiation, an aqueous solution of polyethylene oxide, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolide or the like can be easily obtained by irradiation with ionizing radiation. Since hydrogels can absorb and hold a large amount of water, they are used in the fields of medical care and cosmetics as sanitary articles such as disposable diapers and moisturizers. For these, materials based on sodium polyacrylate are mainly used.
[0004]
However, it is difficult to dispose of it after use, and most of it is disposed of by incineration. If the treatment is performed in a large amount, the temperature of the incinerator decreases, and there is a possibility that dioxin is generated. For this reason, application of hydrogels that do not impose an environment that degrades in soil, such as sodium polyglutamate and polyasparagine soda obtained by irradiation crosslinking, has been attempted.
[0005]
[Problems to be solved by the invention]
Chemical crosslinking agents such as formalin and glutaraldehyde are often used for crosslinking starch and cellulose derivatives. In this method, the aldehyde may contaminate the working environment, and if it remains, it may irritate the skin. Therefore, a safe crosslinking technique is required.
[0006]
Further, hydrogels obtained by crosslinking a water-soluble polymer absorb a large amount of water and are therefore used in sanitary articles such as disposable diapers. The present inventors have found that, when carboxymethylated starch, cellulose, and chitin / chitosan are kneaded well with water to form a high-concentration paste and then irradiated, a radiation crosslinking reaction occurs to form a hydrogel ( Japanese Patent Application No. 2000-15237, Japanese Patent Application No. 2001-362131, Japanese Patent Application Laid-Open No. 2001-2703).
[0007]
However, when these hydrogels are used for a long period of time as a medium of a cold storage agent or a heat retaining agent, the viscosity gradually decreases due to decomposition. For this reason, gel elasticity is lost. The present invention has been achieved by developing a technique for effectively reusing a hydrogel having such a viscosity decrease without incineration or discarding.
[0008]
[Means for Solving the Problems]
By the way, simply decomposing starch and cellulose derivatives in a solid state or in irradiation with a dilute aqueous solution (concentration of 5% or less) occurs preferentially, so that processing by radiation crosslinking was difficult.
[0009]
The present inventor succeeded in obtaining a hydrogel by adding purified water to cellulose, starch, and derivatives of chitin / chitosan, kneading the mixture into a high-concentration paste state, and introducing a crosslinked structure by irradiation with ionizing radiation. Japanese Patent Application No. 2000-152372, Japanese Patent Application No. 2001-362131, and Japanese Patent Application Laid-Open No. 2001-2703).
[0010]
However, when a cellulose or a starch gel derivative hydrogel is used as a medium of a cold storage agent or a heat retaining agent for a long period of time, the viscosity decreases due to decomposition. In order to make effective use of resources without throwing it away, we worked diligently to develop recycling technologies.
[0011]
As a result, when a new material of the same type is added to starch or a cellulose derivative whose viscosity has been reduced by use, and a paste-like sample is prepared and irradiated with radiation, an elastic hydrogel is obtained again. The softness of the hydrogel can be controlled by the concentration of new material added and the dose of irradiation. These can be reused as a cold storage agent and a heat retention agent, and achieved the present invention.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the same new material is added to the cellulose and starch derivative hydrogels which have been used as a cold storage agent or a heat retaining agent and have reduced viscosity to obtain a paste which does not flow even when the container is tilted. This was put in a bag made of polyvinylidene chloride, and after vacuum degassing, it was heat-sealed and irradiated with γ-rays. Before irradiation, the paste is a soft paste, but a rubbery elastic hydrogel is obtained by irradiation.
[0013]
The concentration of the paste of cellulose or starch derivative for performing radiation crosslinking varies depending on the degree of substitution, but the preferred concentration is 10% or more. The hardness of the hydrogel can be controlled by the paste concentration and the irradiation dose.
[0014]
Ionizing radiation is γ-rays, electron beams and X-rays, and the dose for crosslinking is 0.5-1,000 kGy. Preferred crosslinking doses are between 1 and 300 kGy.
The reusable cellulose and / or starch derivative hydrogel used in the present invention may be any as long as it can be dissolved in water. The higher the degree of substitution, the higher the affinity with water and the higher the concentration of the paste. The most preferred degree of substitution is from 0.01 to 2.5.
[0015]
The reusable cellulose and / or starch derivative hydrogel of the present invention comprises CMC, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, oxidized cellulose, CMS, methyl starch, ethyl starch, hydroxyethyl starch, hydroxypropyl starch, oxidized starch. Or a mixture thereof.
[0016]
The ionizing radiation is preferably a gamma ray from cobalt-60 and an electron beam from an accelerator for industrial production. The electron accelerator is most preferably a medium energy to high energy electron accelerator capable of irradiating a thick object with an acceleration voltage of 1 MeV or more. If pressure is applied to the sample before irradiation and the sample is processed into a film shape, the electron beam can pass through even a low energy electron accelerator of 1 MeV or less, so that a gel can be obtained by radiation crosslinking. Oxygen during irradiation has little effect on cross-linking, but it is desirable to irradiate by covering the top surface with a plastic film such as polyester to prevent evaporation of water during irradiation and to suppress a decrease in cross-linking density. .
[0017]
As a method for evaluating a hydrogel obtained by adding a new material to a cellulose and / or starch derivative hydrogel whose viscosity has been reduced due to long-term use and irradiating the same, a glass petri dish having a diameter of 60 mm has a thickness of 15 mm. Was filled with a hydrogel, a plastic sheet having a thickness of 1.5 mm and a diameter of 35 mm was placed on the gel, and the thickness of the plastic sheet was measured with a thickness gauge having a diameter of 5 mm. In the case of a soft gel, the disk of the plastic sheet sinks into the gel and shows a small value as the thickness.
[0018]
When the cellulose derivative hydrogel is used for a long time as a cold storage agent or a heat retaining agent, the viscosity decreases and the thickness becomes 0.5 mm. When a new material is added thereto, and the mixture is made into a paste and irradiated, an elastic hydrogel is obtained, and a hydrogel having a thickness of 5 to 13 mm from the indication of the meter is obtained.
[0019]
【Example】
Hereinafter, the present invention will be described based on Comparative Examples and Examples.
(Comparative Example 1)
The CMC used was manufactured by Daicel Chemical Industries, Ltd., and its carboxymethyl group substitution degree was 1.29. 20 g of this sample was kneaded well with 180 g of purified water, prepared as a 10% paste, placed in a polyvinylidene chloride bag, vacuum-packed, and irradiated with 10 kGy with γ-rays. The thickness gauge reading of the crosslinked CMC hydrogel thus obtained is 12.5 mm.
[0020]
(Example 1)
The hydrogel prepared in Comparative Example 1 was kept at 50 ° C. for 3 weeks. Decomposition progressed during the heat retention, the elasticity of the hydrogel was lost, and the viscosity was significantly reduced. The thickness measured by the thickness gauge was reduced to 0.3 mm. To this, 3% to 10% of new CMC was added, and irradiation was performed at 10 kGy. Table 1 shows the results.
[0021]
[Table 1]
[0022]
From this table, it is apparent that the addition of new CMC increases the thickness and gives an elastic hydrogel.
When the CMC aqueous solution having the reduced viscosity is reused, a hydrogel (Comparative Example 1) having almost the same elasticity as 10% of new CMC can be obtained by adding 5% of new CMC.
[0023]
Furthermore, when 10% of new CMC is added to the CMC aqueous solution whose viscosity has been reduced, a hard hydrogel that does not deform under the pressure of the thickness gauge can be obtained.
[0024]
【The invention's effect】
As described above, the CMC that has decreased in viscosity after use can be reused by adding new CMC without incineration or disposal. CMC that is finally unusable is biodegradable and can be reduced to soil as fertilizer.
Claims (9)
前記使用済み多糖類誘導体に、使用済みのものではない新しいセルロース及び/又はデンプンの多糖類誘導体を添加し、水と良く練りペースト(糊)状に調製し、再び放射線の照射により弾性のあるハイドロゲルを得ることを特徴とする、上記方法。Production of a hydrogel by recycling a used polysaccharide derivative whose viscosity has been reduced by decomposing by using the obtained hydrogel, using a polysaccharide derivative of cellulose and / or starch as a raw material, and irradiating the material with radiation. In the method,
A new cellulose and / or starch polysaccharide derivative that is not used is added to the used polysaccharide derivative, and the mixture is well mixed with water to prepare a paste (paste). The above method, wherein a gel is obtained.
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Cited By (5)
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JP2006274227A (en) * | 2005-03-30 | 2006-10-12 | National Food Research Institute | Method for preparing hydrogel component-containing composition and its application |
JP2006274226A (en) * | 2005-03-30 | 2006-10-12 | National Food Research Institute | Process for production of modified sugar beet pectin and its application |
JP2007238735A (en) * | 2006-03-08 | 2007-09-20 | Tnk Higashi Nippon Kk | Cold accumulating material |
WO2008059058A1 (en) * | 2006-11-17 | 2008-05-22 | Biomatlante | Hydrogel and biomedical applications thereof |
WO2011145214A1 (en) * | 2010-05-21 | 2011-11-24 | 高木 千代美 | Cold-storage agent |
-
2002
- 2002-07-09 JP JP2002199745A patent/JP2004043543A/en active Pending
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006274227A (en) * | 2005-03-30 | 2006-10-12 | National Food Research Institute | Method for preparing hydrogel component-containing composition and its application |
JP2006274226A (en) * | 2005-03-30 | 2006-10-12 | National Food Research Institute | Process for production of modified sugar beet pectin and its application |
JP2007238735A (en) * | 2006-03-08 | 2007-09-20 | Tnk Higashi Nippon Kk | Cold accumulating material |
JP4669416B2 (en) * | 2006-03-08 | 2011-04-13 | ティエヌケイ東日本株式会社 | Cold storage material |
WO2008059058A1 (en) * | 2006-11-17 | 2008-05-22 | Biomatlante | Hydrogel and biomedical applications thereof |
FR2908775A1 (en) * | 2006-11-17 | 2008-05-23 | Biomatlante Sarl | HYDROGEL AND ITS BIOMEDICAL APPLICATIONS |
WO2011145214A1 (en) * | 2010-05-21 | 2011-11-24 | 高木 千代美 | Cold-storage agent |
CN103038307A (en) * | 2010-05-21 | 2013-04-10 | 高木千代美 | Cold-storage agent |
KR20130115998A (en) * | 2010-05-21 | 2013-10-22 | 다케시 시미즈 | Cold-storage agent |
JP5705842B2 (en) * | 2010-05-21 | 2015-04-22 | 清水 剛 | Cold storage agent |
KR101655504B1 (en) | 2010-05-21 | 2016-09-07 | 다케시 시미즈 | Cold-storage agent |
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