JP2007238735A - Cold accumulating material - Google Patents

Cold accumulating material Download PDF

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JP2007238735A
JP2007238735A JP2006062100A JP2006062100A JP2007238735A JP 2007238735 A JP2007238735 A JP 2007238735A JP 2006062100 A JP2006062100 A JP 2006062100A JP 2006062100 A JP2006062100 A JP 2006062100A JP 2007238735 A JP2007238735 A JP 2007238735A
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cold storage
cmc
storage material
freezing
regenerator
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JP4669416B2 (en
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Takeshi Shimizu
剛 清水
Naomi Shimizu
奈穂美 清水
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TNK HIGASHI NIPPON KK
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14Thermal energy storage

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cold accumulating material requiring a short cooling time for freezing and having a long effective cool keeping time. <P>SOLUTION: The cold accumulating material is obtained by the following processes, a process preparing a paste of water soluble corboxymethylcellulose (CMC), and gelling the polysaccharide derivative by crosslinking reaction caused from irradiating with a radiation. Then mixing the dried CMC gel which is obtained by drying the gelled CMC, with 1-15% of an aqueous solution of sodium chloride. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、食品や医薬品等の保存あるいは輸送時の冷却、保冷に利用される蓄冷材に関するものである。   The present invention relates to a cold storage material used for cooling and cold storage during storage or transportation of foods and pharmaceuticals.

従来のこの種の蓄冷材(蓄冷剤)として、塩化ナトリウム、塩化アンモニウム、塩化マグネシウム等の無機塩の水溶液、またはメタノール、エタノール等のアルコール水溶液、あるいは水溶性高分子に公知のゲル化剤を添加したものがある(例えば、特許文献1参照)。
特開平11−257814号公報(段落「0010」、図1)
As a conventional cold storage material (cool storage agent), an aqueous solution of an inorganic salt such as sodium chloride, ammonium chloride or magnesium chloride, an aqueous alcohol solution such as methanol or ethanol, or a known gelling agent is added to a water-soluble polymer. (For example, refer to Patent Document 1).
JP-A-11-257814 (paragraph “0010”, FIG. 1)

しかしながら、上述した従来の蓄冷材は、凍結までに要する時間が長く、保冷に対する有効時間が短いという問題がある。
その結果、例えば、早朝に出発して、夜遅く帰着するようなスケジュールで生鮮品を長距離運送する貨物自動車の荷物室の冷蔵等に用いる場合、当日使用した蓄冷材を帰着してから翌早朝に出発までの間に凍結させることが困難であり、また1日の運送の途中で中に保冷効果が著しく低下してしまうため、このような生鮮品の長距離運送等に適さず、そのため、凍結に要する冷却時間が短く、有効保冷時間が長い蓄冷材が要望されている。
However, the above-described conventional cold storage material has a problem that the time required for freezing is long and the effective time for cooling is short.
As a result, for example, when used for refrigeration of a luggage compartment of a truck that transports fresh products over long distances in a schedule that leaves early in the morning and returns late at night, the cold storage material used on that day is returned and the next morning It is difficult to freeze before departure, and the cooling effect is significantly reduced during the transportation of one day, so it is not suitable for long-distance transportation of such fresh products. There is a demand for a regenerator material having a short cooling time required for freezing and a long effective cooling time.

本発明は、上記の問題を解決することを課題とする。   An object of the present invention is to solve the above problems.

そのため、本発明の蓄冷材は、ペースト状の多糖類誘導体に放射線を照射することにより橋かけ反応を生じさせて前記多糖類誘導体をゲル化し、そのゲル化した多糖類誘導体を乾燥させることにより得られる乾燥ゲルを1〜15%の食塩水に混合したことを特徴とする。   Therefore, the cold storage material of the present invention is obtained by irradiating a paste-like polysaccharide derivative with radiation to cause a crosslinking reaction to gel the polysaccharide derivative and drying the gelled polysaccharide derivative. The dried gel is mixed with 1-15% saline.

このようにした本発明は、橋かけ反応を生じさせた多糖類誘導体を使用しているため凍結に要する冷却時間が短く、有効保冷時間が長いという効果が得られる。   In the present invention as described above, since the polysaccharide derivative that has caused the crosslinking reaction is used, the cooling time required for freezing is short, and the effect that the effective cooling time is long can be obtained.

以下、図面を参照して本発明による蓄冷材の実施例を説明する。   Embodiments of the regenerator material according to the present invention will be described below with reference to the drawings.

近年、安全性や環境保全の観点から、使用後資源として再利用可能な環境に負荷を与えない循環型材料が各分野において求められており、蓄冷材も例外ではなく、そのため植物を素材とする加工品が注目されており、その典型的な材料がセルロースなどの多糖類誘導体である。
セルロースに直接放射線を照射すると、分解が優先して橋かけ反応が起こらないため、ハイドロゲルにならないが、水に溶解するように加工されたつまりカルボキシメチル化された誘導体のカルボキシメチルセルロース(以下、CMC)を水に溶かして10%以上(好ましくは10〜60%)の高濃度のペースト状に調製し、そのペースト状のCMCに放射線照射を行うと、橋かけ反応が起きてゲル化する。
In recent years, from the viewpoint of safety and environmental conservation, recycling materials that do not burden the environment that can be reused as resources after use have been demanded in various fields, and cold storage materials are no exception, so plants are used as materials. Processed products are attracting attention, and a typical material is a polysaccharide derivative such as cellulose.
When radiation is directly applied to cellulose, decomposition does not occur and a crosslinking reaction does not occur, so it does not become a hydrogel, but is a carboxymethyl cellulose derivative (hereinafter referred to as CMC) that has been processed so as to dissolve in water. ) Is dissolved in water to prepare a paste having a high concentration of 10% or more (preferably 10 to 60%), and when the paste-like CMC is irradiated with radiation, a crosslinking reaction occurs and gels.

このようにゲル化したCMCを乾燥させて水分を除去することによりCMC乾燥ゲルが得られる。
このCMC乾燥ゲルは、純水につけると1グラムが400倍も吸水し、生理食塩水では100倍を吸水するという特性がある。
本実施例における蓄冷材はこのような吸水特性を持つCMC乾燥ゲルを食塩水と混合することによりして製造されるもので、この蓄冷材に用いる乾燥ゲルは、水に溶かして20%の濃度に調整したペースト状CMCに放射線を5kGy程度照射して、乾燥させたものが最も好ましく、0.5mm径程度の大きさに粉砕したものがポリマー同士の融着がなく加工に最も適している。
The CMC dried gel can be obtained by drying the gelled CMC to remove moisture.
This CMC dry gel has a characteristic that 1 gram absorbs 400 times as much water when put on pure water, and 100 times as much water in physiological saline.
The cold storage material in this example is manufactured by mixing CMC dry gel having such water absorption characteristics with saline, and the dry gel used for this cold storage material is dissolved in water and has a concentration of 20%. The paste-like CMC prepared in this manner is most preferably dried by irradiating it with radiation of about 5 kGy, and the one pulverized to a size of about 0.5 mm is most suitable for processing without fusion between polymers.

本実施例における蓄冷材は、冷蔵用のものと冷凍用のものがあり、冷蔵用のものとしては、食塩水にCMC乾燥ゲルを0.5%〜10%加えて良く混合することにより凝固点−5℃の蓄冷材を製造することができ、これにプロピレングリコールを1〜20%添加することで凝固点−27℃の冷凍用の蓄冷材を製造することができる。
冷蔵用の蓄冷材として好ましい組成は、1%〜5%の食塩水の中に前記の粉砕したCMC乾燥ゲルの濃度が1%〜5%になるように調整したものであり、更に言えばCMC乾燥ゲルの濃度を3%程度とするのが最も有効である。
The cold storage materials in this example are those for refrigeration and those for freezing. For refrigeration, freezing point is obtained by adding 0.5% to 10% of CMC dry gel to saline and mixing well. A 5 ° C. regenerator material can be produced, and by adding 1 to 20% propylene glycol thereto, a freezing regenerator material having a freezing point of −27 ° C. can be produced.
A preferable composition as a cold storage material for refrigeration is a composition in which the concentration of the pulverized CMC dry gel is adjusted to 1% to 5% in 1% to 5% saline. It is most effective to set the concentration of the dry gel to about 3%.

また、冷凍用の蓄冷材としては、5%〜15%の食塩水にCMC乾燥ゲルを1%〜5%加えて混合した後、プロピレングリコールを10〜20%加えることが好ましい。
本実施例による冷蔵用の蓄冷材と市販の冷蔵用の蓄冷材との凍結及び保冷効果の比較例について説明する。
1%の食塩水にCMC乾燥ゲルを3%添加して作った本実施例の蓄冷材と市販品の蓄冷材(高分子吸水ポリマーを水に溶かして粘性をくわえたもの)を−35℃のファン式冷凍庫で10時間冷却し、それぞれの蓄冷材の温度推移を計測した。
In addition, as a refrigerating material for freezing, it is preferable to add 10% to 20% of propylene glycol after adding 1% to 5% of CMC dry gel to 5% to 15% saline.
A comparative example of the freezing and cooling effect of the refrigeration storage material and the commercial refrigeration storage material according to this embodiment will be described.
A cold storage material of this example prepared by adding 3% of CMC dry gel to 1% saline and a commercial cold storage material (a polymer water-absorbing polymer dissolved in water and added with viscosity) at −35 ° C. It cooled in the fan type freezer for 10 hours, and measured the temperature transition of each cool storage material.

図1及び図3はこのときの蓄冷材の温度推移を示すグラフで、各々温度を縦軸に表し、時間を横軸に表している。
図1及び図3においてAは冷凍庫内の温度推移であり、図1におけるBは本実施例による蓄冷材の温度推移、図3におけるCは市販品の蓄冷材の温度推移を示している。
ここで用いた本実施例の蓄冷材は、容器に入れたものを12個、市販品の蓄冷材は容器に入れたものが10個であるが、内容量は本実施例の蓄冷材が約9,042.6g、市販品の蓄冷材が約9,732.7gであり、大きな差が生じないようにした。
1 and 3 are graphs showing the temperature transition of the regenerator material at this time, in which each temperature is represented on the vertical axis and time is represented on the horizontal axis.
1 and 3, A is the temperature transition in the freezer, B in FIG. 1 is the temperature transition of the regenerator material according to the present embodiment, and C in FIG. 3 is the temperature transition of the commercial regenerator material.
The cold storage material of the present embodiment used here is 12 pieces put in a container, and the commercial cold storage material is 10 pieces put in a container, but the internal capacity is about the cold storage material of this embodiment. It was 9,042.6g, and the commercial cold storage material was about 9,732.7g, so that there was no big difference.

計測の結果、市販品の蓄冷材は図3に示したように10時間冷却しても−10度に達することができず、凍結が不十分なであるのに対し、本実施例による蓄冷材は図1に示したようにおよそ5時間25分で−10度に達し、凍結に要する時間は市販品の蓄冷材に比べて半分以下の時間で済むことが分かった。
次に、このように10時間冷却した本実施例の蓄冷材を、内寸法が概ね、縦500mm×横900mm×深さ480mmで、板厚約250mmの発泡スチロール製のBOX(箱)内に7個入れ、蓋をして外気温の環境下で9時から24時までの15時間の温度推移を計測し、同様の条件で市販品の蓄冷材の温度推移を計測した。
As a result of the measurement, the commercially available regenerator material cannot reach −10 ° C. even if it is cooled for 10 hours as shown in FIG. As shown in FIG. 1, it reached -10 degrees in about 5 hours and 25 minutes, and it was found that the time required for freezing was less than half that of a commercially available cold storage material.
Next, seven of the regenerator materials of this example cooled for 10 hours in this way are contained in a styrene foam BOX (box) having an internal dimension of approximately 500 mm in length, 900 mm in width, and 480 mm in depth, and a plate thickness of about 250 mm. Then, the temperature was changed for 15 hours from 9 o'clock to 24 o'clock under the environment of the outside temperature with the lid covered, and the temperature change of the commercial regenerator material was measured under the same conditions.

蓄冷材を入れる際のBOX内の温度は外気温と同じにした。
図2及び図4はこのときのそれぞれの蓄冷材とBOX内の温度推移を示すグラフで、各々温度を縦軸、時間を横軸に表している(但し、図4は9時から21時までの12時間分)。
図2におけるBは本実施例による蓄冷材の温度推移、図4におけるCは市販品の蓄冷材の温度推移を示し、また図3及び図4においてDは平均外気温であり、本実施例による蓄冷材の計測時の場合、37.7℃、市販品の蓄冷材の場合は37.3℃である。
The temperature inside the BOX when the cold storage material was added was the same as the outside air temperature.
FIG. 2 and FIG. 4 are graphs showing the temperature transition in each regenerator and BOX at this time, with the temperature on the vertical axis and the time on the horizontal axis (however, FIG. 4 is from 9:00 to 21:00) For 12 hours).
B in FIG. 2 shows the temperature transition of the regenerator material according to the present embodiment, C in FIG. 4 shows the temperature transition of the commercial regenerator material, and in FIGS. 3 and 4, D is the average outside air temperature. In the case of measuring the regenerator material, it is 37.7 ° C., and in the case of a commercially available regenerator material, it is 37.3 ° C.

また、Eはそれぞれの蓄冷材直下部、FはBOX内中心部、GはBOX底部の温度推移を表わしている。
尚、9時00分から18時00分まで、54分毎に10回2分間ずつ蓋を開いた。
計測の結果、市販品の蓄冷材では、図4に示したようにBOXに入れてから4時間足らずで温度が0℃に達し、11時間で8℃に温度が上昇した。また、BOX内の各部の温度は0℃に下がることはなく、11時間で約10℃に上昇した。
Further, E represents the temperature immediately below each regenerator material, F represents the central portion of the BOX, and G represents the temperature transition at the bottom of the BOX.
In addition, from 9:00 to 18:00, the lid was opened 10 times every 2 minutes for 2 minutes.
As a result of the measurement, in the commercial regenerator material, the temperature reached 0 ° C. in less than 4 hours after being put in the BOX as shown in FIG. 4, and the temperature rose to 8 ° C. in 11 hours. Moreover, the temperature of each part in the BOX did not drop to 0 ° C., but increased to about 10 ° C. in 11 hours.

これに対して本実施例の蓄冷材は、図1に示したようにBOXに入れてから9時間を過ぎるまで温度は0℃以下の温度を保ち、8℃に温度が上昇するまでに15時間を要している。また、BOX内の各部の温度は蓄冷材を入れてから1時間以内で0℃以下達し、0℃に上がるまで4時間ほどかかり、10℃になるのに15時間を要した。
このように本実施例の蓄冷材は、市販品の蓄冷材に比べて凍結に要する冷却時間が短く、有効保冷時間が長いという結果が得られた。
In contrast, as shown in FIG. 1, the cool storage material of this example kept the temperature at 0 ° C. or less until 9 hours passed after being put in the BOX, and 15 hours until the temperature rose to 8 ° C. Is needed. Further, the temperature of each part in the BOX reached 0 ° C. or less within 1 hour after putting the regenerator material, took about 4 hours to reach 0 ° C., and took 15 hours to reach 10 ° C.
As described above, the regenerator material of this example had a shorter cooling time required for freezing and a longer effective cool time as compared with a commercially available regenerator material.

これにより、本実施例の蓄冷材は、凍結に要するエネルギーが節約でき、作業効率の改善にも繋がるので、医療分野、食品分野の保存、運搬等の際の冷蔵、冷凍用の蓄冷材とし有効に利用できるという効果が得られる。
また、本実施例の蓄冷材は、橋かけ処理したCMC乾燥ゲルと食塩水を主成分とするため、使用後資源として再利用可能であり、環境に対してもあまり負荷を与えないという効果も得られる。
As a result, the regenerator material of this embodiment can save energy required for freezing and leads to improved work efficiency, so it is effective as a regenerator material for refrigeration and freezing during storage and transportation in the medical field and food field. The effect that it can be used is obtained.
Moreover, since the cold storage material of the present embodiment is mainly composed of a cross-linked CMC dry gel and saline, it can be reused as a post-use resource and has an effect of not giving much load to the environment. can get.

本発明の蓄冷材は、凍結までに要する時間が短く、保冷に対する有効時間が長いので、例えば早朝に出発し、夜遅く帰着するようなスケジュールで生鮮食品や冷凍品等を長距離運送する貨物自動車に利用する冷蔵用、冷凍用の蓄冷材として極めて有効なものとなる。   The cool storage material of the present invention has a short time required for freezing and a long effective time for cold storage. For example, a lorry that transports fresh food, frozen products, etc. over a long distance on a schedule that leaves early in the morning and returns late at night. It is extremely effective as a cold storage material for refrigeration and freezing.

実施例による蓄冷材の冷却時における温度推移を示すグラフThe graph which shows the temperature transition at the time of cooling of the cool storage material by an Example 実施例による蓄冷材の保冷時における温度推移を示すグラフThe graph which shows the temperature transition at the time of the cold storage of the cool storage material by an Example 市販品の蓄冷材の冷却時における温度推移を示すグラフGraph showing temperature transition during cooling of commercial regenerator materials 市販品の蓄冷材の冷却時における温度推移を示すグラフGraph showing temperature transition during cooling of commercial regenerator materials

Claims (3)

ペースト状の多糖類誘導体に放射線を照射することにより橋かけ反応を生じさせて前記多糖類誘導体をゲル化し、そのゲル化した多糖類誘導体を乾燥させることにより得られる乾燥ゲルを1〜15%の食塩水に混合したことを特徴とする蓄冷材。   The pasty polysaccharide derivative is irradiated with radiation to cause a crosslinking reaction to gel the polysaccharide derivative, and the dried gel obtained by drying the gelled polysaccharide derivative is 1 to 15% A regenerator material mixed with saline. 請求項1に記載の蓄冷材において、
前記多糖類誘導体として、水溶性のカルボキシメチルセルロースを用いることを特徴とする蓄冷材。
The regenerator material according to claim 1,
A cold storage material characterized by using water-soluble carboxymethylcellulose as the polysaccharide derivative.
請求項1に記載の蓄冷材において、
前記乾燥ゲルは、0.5mm径程度の大きさに粉砕して食塩水に混合したことを特徴とする蓄冷材。
The regenerator material according to claim 1,
A cold storage material, wherein the dried gel is pulverized to a size of about 0.5 mm and mixed with saline.
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CN103038307A (en) * 2010-05-21 2013-04-10 高木千代美 Cold-storage agent
CN103756643A (en) * 2013-12-24 2014-04-30 厦门浩添冷链科技有限公司 Non-freezing icing glue for preparing low-temperature phase change bags

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JP2004002829A (en) * 2002-04-23 2004-01-08 Sanyo Chem Ind Ltd Low temperature insulating material and low temperature insulating agent
JP2004043543A (en) * 2002-07-09 2004-02-12 Japan Atom Energy Res Inst Method for manufacturing hydrogel by recyclingly used polysaccharide derivative

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Publication number Priority date Publication date Assignee Title
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
CN103756643A (en) * 2013-12-24 2014-04-30 厦门浩添冷链科技有限公司 Non-freezing icing glue for preparing low-temperature phase change bags
CN103756643B (en) * 2013-12-24 2017-01-04 厦门浩添冷链科技有限公司 A kind of non-freezing icing glue for preparing low temperature phase change bag

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