201142002 六、發明說明 【發明所屬之技術領域】 本發明是關於蓄冷劑，特別是關於全由天然素材所組 成’可在短時間內就凍結而可發揮很長的保冷效果之蓄冷 劑。 【先前技術】 蓄冷劑的用途是使用於將生鮮食品之類的製品維持在 低溫下進行運送。使用在生鮮食品之類的製品的運送用途 的蓄冷劑，係必須配合運送行程而要在5〜8小時/ 4個 (在通常的使用態樣中，係將複數個蓄冷劑同時進行冷 凍。這種情況下，必須讓所有的蓄冷劑都完成凍結。通常 最短爲5小時，最長爲8小時，在冷凍庫中被冷凍起來） 的短時間內加以凍結，以謀求在長距離運送、長時間的保 管中，也不至於降低保冷效果，但是目前市面上的蓄冷劑 中，尙未有能夠符合這種要件的。 習知的蓄冷劑’係使用：氯化鈉、氯化胺、氯化鎂等 的無機鹽的水溶液、或乙二醇、丙二醇等的多元醇來當作 寒劑；而且係使用：羧甲基纖維素、聚乙烯醇、聚丙烯酸 鈉、聚丙烯醯胺之類的親水性高分子聚合物來當作凝膠化 劑，針對於蓄冷劑之每1 〇〇份重量部，添加入0.0 1〜1 〇 份重量部，並且添加入碘化銀、硫化銅、黃原膠（Xanthan Gum)、α -吩哚、焦磷酸鈉等來當作可令蓄冷劑凍結的核 劑（請參考專利文獻Π 。但是，這些蓄冷劑係有：凍結 -5- 201142002 所需時間很長，保冷效果卻在短時間內就降低之缺點。 爲了解決上述問題，本發明人等曾經提出一種方案， 係將水溶性的羧甲基纖維素作成軟脊狀之後，照射放射線 使其產生架橋作用而成爲凝膠，將這個凝膠以1〜5%的比 例混合到1〜5 %的食鹽水中而形成保冷用蓄冷劑；以及將 該凝膠以1〜5%的比例混合到5〜1 5%的食鹽水中，並且 添加丙二醇1〜20%來當作寒劑而組成的冷凍用蓄冷材 (請參考專利文獻2 )。這種冷凍用蓄冷材係可達成-27 °C的凝固點。但是，近年來基於安全性、環境保護的觀 點，開始謀求：在廢棄處分之後還能夠作爲資源予以再利 用的循環型的製品。本發明者先前所提案的冷凍用蓄冷 材，雖然是具有：可在短時間就凍結且可維持長時間保冷 效果之優點，但是，其中係含有丙二醇來當作寒劑，並非 完全的天然素材製品。此外，已經確認出專利文獻2所記 載的蓄冷劑，在將羧甲基纖維素製作成軟膏狀的時候，係 在大氣狀態中進行的’因此，如果照射放射線時的程度有 不一致的話’將會因此而產生氣泡，無法成爲充分均勻的 凝膠，在吸水性方面將會產生不一致的現象，凍結以及保 冷性能並不充分。 [先行技術文獻] [專利文獻] [專利文獻1]日本特開平1 1 -293 234號公報 [專利文獻2]曰本特開20〇7-238735號公報 201142002 【發明內容】 [發明所欲解決之問題] 本發明之目的係要提供一種蓄冷劑，這種蓄冷劑係： 在廢棄時無需特別的化學處理之完全由天然物素材所組 成，可在短時間內就凍結且可發揮長時間的保冷效果。 [用以解決問題之技術手段] 根據本發明所提供的蓄冷劑，是由：將15〜25 wt%的 纖維素與水在真空下進行混練而成的軟膏狀纖維素混練物 加以照射電子線而得的乾燥架橋纖維素凝膠2〜4wt%、1 〜2 1 wt%的岩鹽以及水所組成的。 本發明中所採用的架橋纖維素凝膠係以：將已經吸水 達24小時的凝膠除以吸水前的乾燥架橋纖維素凝膠的初 期重量所得的吸水倍率爲1 5 0〜2 5 0倍者爲宜，更好的是 15〇〜200倍的乾燥凝膠。藉由採用這種具有高吸水倍率 的乾燥架橋纖維素凝膠，能夠在架橋纖維素凝膠中保持大 量的水。被保持在架橋纖維素凝膠中的大量的水一旦被冷 凍之後’需要較長時間才會解凍，因此可延長保冷時間。 但是’吸水倍率如果太高的話，冷凍所需的時間會變得很 長，凝膠本身的強度也會變差，因此還是上述的範圍爲 宜。 本發明中所使用的纖維素是羧甲基纖維素鈉，較佳的 是即使在食鹽水中其黏度也不會降低的羧甲基纖維素鈉。 最好的是：即使在1〜5 %食鹽水中仍可呈現出2 6 0 0 m P a . 201142002 s以上的黏度（根據B型黏度計所測得 10%食鹽水中仍可呈現出4600mPa. s B型黏度計所測得的黏度）之羧甲基纖 蓄冷劑的構成方式係將乾燥架橋纖維素 中。如果架橋纖維素在食鹽水中的黏度 發揮作爲凝膠化劑的功能，架橋凝膠構 降低，因此作爲原料來使用的纖維素係 度爲佳。 本發明中所使用的乾燥架橋纖維素 上述纖維素的含量趨於15〜25wt°/〇， 15〜20 wt%的方式添加到水中，在真空 軟膏狀纖維素混練物，並且對於這種 物，以8〜16kGy的強度，較佳是以9 照射電子線而製得的。 在調製軟膏狀的纖維素混練物時所 分爲宜，因此係以離子交換水爲佳。此 進行混練。藉由在真空下進行混練的做 入，可在纖維素粉末均勻地分散於離· 下，充分地進行混練。 纖維素混練物中的纖維素的含量與 影響到因照射電子線而形成的架橋構造 冷劑所需的吸水性以及保水性而實施各 現了上述範圍的纖維素含量與電子線照 子線照射量太多的話，架橋構造的網目 的黏度），而且在 以上的黏度（根據 維素鈉。本發明的 凝膠存在於食鹽水 降低的話，就無法 造內的保水力將會 具有上述範圍的黏 凝膠，係以可使得 較佳的含量爲趨於 下進行混練而得的 軟膏狀纖維素混練 〜14kGy的強度來 使用的水係不含鹽 外，必須在真空下 法，不會有氣泡混 子交換水中的狀態 電子線照射量都會 。爲了達成作爲蓄 種實驗的結果，發 射量係最佳的。電 變小。網目係可用 -8- 201142002 來保持水分子，因此一個網目所保持的水分子愈少的話’ 就可以縮短凍結所需的時間，而且網目形成較密’所以解 凍時間會變長，可以延長保冷時間。但是，如果網目是小 到無法保持住水分子程度的微小程度的話，就無法使用。 本發明人等已經確認出：只要是在上述照射量範圍的話， 即可製得既可縮短凍結時間而且又可維持較長的保冷時間 之適合作爲本發明的蓄冷劑之網目構造。根據上述照射條 件所製得的架橋纖維素凝膠，乾燥時的吸水倍率爲1 5 0〜 2 〇〇倍，非常適合當作本發明的蓄冷劑。 本發明的蓄冷劑係以上述乾燥架橋纖維素凝膠的含量 趨於2〜4wt%，較佳是趨於2.5〜3.5wt%的方式添加到含 有1〜21 wt %岩鹽的食鹽水中，充分地攪拌混合之後，充 塡到容器或由薄膜、不織布等所做的袋子而製造出來的。 在本發明中’食鹽水係具有寒劑的作用。本發明所使 用的食鹽水，並不是精製鹽’而是使用天然的岩鹽。天然 的岩鹽係與精製鹽（依據財團法人日本鹽事業中心的品質 規格：氯化鈉99 wt%以上、鈣0.02wt%以下、鎂〇_〇2wt% 以下、鉀〇.25wt%以下）不同，因爲含有豐富的礦物質， 所以可發揮優異的寒劑作用。本發明所使用的岩鹽係 NaCl含量99wt%以上，Na+及Mg2+的總含量係大於〇且 0.3 wt%以下的岩鹽爲宜，尤其是中國湖北省所產的岩鹽特 別適合。 食鹽水濃度則7H依據蓄冷劑所被要求的溫度範圍而 異，作爲0 °C〜-1 7 °c的冷藏範圍用蓄冷劑來使用的情況 -9- 201142002 下’岩鹽的含量係1〜17 wt% ;作爲-1 8°C以下的冷凍範圍 用蓄冷劑來使用的情況下，岩鹽的含量係18〜2丨wt%爲 宜。想要使蓄冷劑的凝固點將低1 °C的話，只要多添加岩 鹽1 w t %即可。 [發明之效果] 根據本發明，係可提供：短時間即可結凍而且保冷效 果的維持時間很長的蓄冷劑。 又’本發明的蓄冷劑因爲是由：乾燥架橋纖維素凝 膠、食鹽、水所組成之具有天然分解性之完全天然素材的 製品，所以蓄冷劑本身無須做廢棄處理，即使不小心發生 了洩漏，也是安全的，因此不僅極爲容易運用，也最適合 運用在：生鮮食品或醫藥品之類的特別要求安全性的製品 的保管、運送方面。 【實施方式】 茲佐以實施例及比較例來詳細說明本發明如下。 〔製造例1〕<冷藏範圍用蓄冷劑> 將離子交換水1 2公升注入到真空混練裝置的混練鍋 槽（內容量爲60公升）內，再添加粉末羧甲基纖維素鈉 (曰本製紙株式會社製的「SUN ROSE系列商品型號 F3 50HC-4」）3公斤，水與羧甲基纖維素的總量共計置入 1 5公升。此時，爲了抑制粉末羧甲基纖維素鈉的粉末上 -10- 201142002 飄’一邊從粉末的上方噴水霧一邊進行添加。原料添加 後’將真空混練裝置的蓋子關閉，一邊進行真空吸引，一 邊在真空混練裝置內進行攪拌4 0分鐘而調製成纖維素混 練物。 接下來，在真空下將纖維素混練物成形，並照射電子 線1 4kGy ’以調製成架橋纖維素凝膠。再將架橋纖維素凝 膠移置到乾燥機內以大約70°C進行乾燥。 將中國湖北省產的岩鹽5 5公克（總量丨，1 0 0公克的 5% )溶解到離子交換水中以調製成5%的食鹽水。在這個 5 %的食鹽水中添加入乾燥架橋纖維素凝膠2 7 · 5公克（總 量1，1〇〇公克的2_5wt% ) ’進行50分鐘的攪拌，5分鐘 的靜置’然後再進行1 0分鐘的攪拌使其均勻地混合而調 製成蓄冷劑。 〔比較製造例1〕 除了所使用的乾燥架橋纖維素凝膠係採用本案申請人 的先前申請案之日本特開2007-238735號公報的實施例所 記載的乾燥架橋纖維素凝膠之外，其他的條件都與製造例 1相同來調製出蓄冷劑。亦即，對於使用開放型的混練鍋 槽進行混練而成的軟膏狀羧甲基纖維素，照射鈷6 0 r射 線5kGy之後，令其乾燥後而成的乾燥架橋纖維素凝膠的 添加量爲27.5公克以及添加5%食鹽水，進行攪拌而調製 成蓄冷劑》(總量1 1 0 0公克，凝膠2 · 5 %〈 2 7 · 5公克〉、 食鹽 5%〈 55 公克〉、水 i〇17.5cc) -11 - 201142002 〔實施例1〕 將製造例1所調製的蓄冷劑1100公克充塡到蓄冷劑 保存盒（橫19.5公分X縱26公分X厚度3.5公分）內，並 且測定了凍結時間及保冷時間。 <凍結時間的測定> 先將蓄冷劑保存盒放置成室溫之後，再放入-3 5 °C的 無風扇冷凍庫內進行24小時的冷卻，並且測定其完全凍 結爲止所需的時間。將結果顯示於第1圖。 蓄冷劑的初期溫度爲1 0.4°C，放入冷凍庫之後大約1 小時1 〇分鐘的程度，蓄冷劑的溫度急遽地降低到-1 〇°C， 大約2小時20分鐘的程度，完全地凍結，6小時之後， 達到-17.6°C。 <保冷時間的測定> 將已經在-3 5 °C的冷凍庫內冷卻了 24小時後的蓄冷劑 保存盒，靜置在保利龍製的箱子（橫32公分X縱51公分X 高1 5公分）內，將保利龍製的箱子放置在室溫下’進行 測定保利龍製的箱子內的溫度。將結果顯示於第2圖。 將蓄冷劑剛放入保利龍製的箱子內時的初期溫度爲 -12.5¾，約8.5小時後，上昇至〇°C，約9.5小時後’上 昇至3 . 1°C。 -12- 201142002 〔比較例1〕 使用比較製造例〗所製造的蓄冷劑，執行了與實施例 1相同的實驗。將結果顯示於第1圖及第2圖。 <凍結時間的測定> 初期溫度爲1 1 · 8 °C ’放進冷凍庫之後大約1小時1 〇 分鐘後’變成-5 °C ’約4小時後完成凍結’約6小時後， 變成-1 3.9 °C。 <保冷時間的測定> 初期溫度爲-1 1 . 1 °C ’放進保利龍製的箱子之後大約 7.5小時後’變成〇 °C，約9 _5小時後’上昇至1 〇丨七。 <實施例1與比較例1之比較> 本發明的蓄冷劑至完全凍結爲止所需的時間只要2小 時的程度，非常地短’只需6小時的冷凍即可達到_丨7 6 °C，只要極短的時間就可達成凍結。而比較例1至完全凍 結爲止需要大約4小時’ 6小時之後也只能達到-1 3 _ 9 °C而 已。 又，本發明的蓄冷劑上昇至〇°C爲止大約需要8.5小 時，即使是9 · 5小時之後還是停留在3 · 1 °C，相對地，比 較例1是在大約7 ·5小時就上昇至0 °C ’在9 · 5小時之後 就達到1 0.1 °C。蓄冷劑只要超過1 〇 °C的話’就喪失了保 冷性，因此，比較例1可以說是只能夠當作大約9小時的 -13- 201142002 蓄冷劑來使用。相對地，本發明的蓄冷劑在到達3 . 1 °C之 後的溫度上昇的坡度係較之比較例1更爲趨緩，可以說是 具有長時間的保冷性。 〔實施例2〕 將製造例1所調製的蓄冷劑650公克充塡到蓄冷劑保 存盒（橫15公分X縱26.5公分X厚度2公分），並測定其 凍結時間及保冷時間。 <凍結時間的測定> 將蓄冷劑保存盒放置成室溫之後，放進-35 °C的無風 扇冷凍庫內冷卻24小時並且測定其至凍結爲止的時間。 將結果顯示於第3圖。 蓄冷劑的初期溫度爲13°C，放進冷凍庫之後約50分 鐘的程度，蓄冷劑的溫度急遽降低到-5 °C ’ 3小時10分 鐘的程度就完全凍結，6小時後，達到-27.1 °C。 <保冷時間的測定> 將已經在-3 5 °C的冷凍庫內冷卻達24小時後的蓄冷劑 保存盒靜置在保利龍製的箱子（橫32公分X縱5 1公分X高 1 5公分）內，再將保利龍製的箱子放置於室溫內’並且 測定了保利龍製的箱子內的溫度。將結果顯示於第4圖。 將蓄冷劑剛放進保利龍製的箱子內時的初期溫度爲 -1 7。(：，約6小時後，上昇爲0。(：，約6.5小時之後’上昇 -14- 201142002 爲 2.9〇C 。 〔比較例2〕 除了使用市售的蓄冷劑（凝膠化劑··高分子聚合物、 寒劑：丙二醇）的這個條件不同之外，其餘條件均與實施 例2相同，並且測定了凍結時間及保冷時間。將結果顯示 於第3圖及第4圖。 <實施例2與比較例2之比較> 本發明的蓄冷劑至完全凍結爲止所需的時間只要3小 時的程度非常地短’經過 6小時的冷凍即可達到-2 7 . 1 °C，在極短的時間內即可達成凍結。市售的蓄冷劑則需要 約4小時才會完全凍結，即使約6小時後，也只能夠達 到-25.1°C而已。 又，本發明的蓄冷劑上昇至0 °C爲止大約需要6小 時，6.5小時之後溫度還是停留在2.9 °C，相對地，市售 的蓄冷劑，約5小時就上昇至0 °C，經過6小時後溫度就 急遽地上昇，6.5小時之後就達到9 . 1。(：。冷藏範圍用的 蓄冷劑，只要超過1 〇 °c的話，就喪失了保冷性，因此， 比較例可以說是只能夠當作約6 _5小時的蓄冷劑來使用。 相對地，本發明的蓄冷劑在到達2.9 °c之後的溫度上昇的 坡度是較之市售的蓄冷劑更爲趨緩，可以說是具有長時間 的保冷性。 -15- 201142002 〔製造例2〕<冷凍範圍用蓄冷劑> 將1 2公升的離子交換水注入到真空混練 鍋槽（內容量60公升）內，添加入3公斤的 纖維素鈉（日本製紙株式會社製「SUN ROSE 號F350HC-4」），水與羧甲基纖維素的總量主 公升。此時，爲了抑制粉末羧甲基纖維素鈉的 一邊從粉末的上方噴水霧一邊進行添加。原料 真空混練裝置的蓋子關閉，一邊進行真空吸引 空混練裝置內進行攪拌40分鐘而調製成纖維素 接下來，在真空下將纖維素混練物成形， 線14kGy，以調製成架橋纖維素凝膠。再將架 膠移置到乾燥機內以大約70°C進行乾燥。 將中國湖北省產的岩鹽1 3 0公克（總量 20%)溶解到離子交換水中以調製成20%的食 個20%的食鹽水中添加入乾燥架橋纖維素凝膠 (總量650公克的3wt% )，進行50分鐘的攪 的靜置，然後再進行1 0分鐘的攪拌使其均勻 製成蓄冷劑。 〔實施例3〕 將製造例2所調製的蓄冷劑650公克充塡 存盒（橫15公分X縱26.5公分X厚度2公分） 定其凍結時間及保冷時間。 裝置的混練 粉末羧甲基 系列商品型 ^計置入1 5 粉末上飄， 添加後，將 ，一邊在真 丨混練物。 並照射電子 橋纖維素凝 65 0公克的 鹽水。在這 1 9.5公克 拌，5分鐘 地混合而調 到蓄冷劑保 內，並且測 -16- 201142002 <凍結時間的測定> 將蓄冷劑保存盒放置於室溫之後’放進-扇冷凍庫冷卻2 4小時’測定其至凍結爲止的 果顯示於第5圖。 蓄冷劑的初期溫度爲7.9°C，放進冷凍庫； 3 0分鐘的程度，蓄冷劑的溫度急遽地降低至_ 時3 0分鐘的程度就完全凍結’ 4小時之後’溫 -23.9〇C 。 <保冷時間的測定> 將已經在-3 5 °C的冷凍庫內冷卻達2 4小時 保存盒靜置在保利龍製的箱子（橫3 2公分x縱 1 5公分）內，再將保利龍製的箱子放置於室 測定了保利龍製的箱子內的溫度。將結果顯示 蓄冷劑剛放進保利龍製的箱子內時的初期 -21.7T：，約3小時半後，溫度上昇至〇°C。 〔比較例3〕 除了使用市售的蓄冷劑（凝膠化劑：高分 寒劑：丙二醇）的這個條件不同之外，其餘條 例3相同，並且測定了凍結時間及保冷時間。 於第5圖及弟όΗ ° <實施例3與比較例3之比較> 3 5 °C的無風 時間。將結 之後1小時 20°C，2 小 度達到 後的蓄冷劑 5 1公分X高 溫內，並且 於第6圖。 溫度爲 子聚合物、 件均與實施 將結果顯不 -17- 201142002 本發明的蓄冷劑至完全凍結爲止所需的時間只要2小 時3 0分鐘的程度非常地短，經過4小時的冷凍即可達到 -2 3 · 9 °C，在極短的時間內即可達成凍結。市售的蓄冷劑 則需要約3小時才會完全凍結，即使約4小時後，也只能 夠達到-2 2.8 T：而已。 又，本發明的蓄冷劑上昇至〇 °C爲止大約需要約3小 時30分鐘，相對地，市售的蓄冷劑，約2小時40分鐘就 上昇至0 °C，經過4小時後溫度就達到8.2。(：。冷凍範圍 用的蓄冷劑，只要超過0 °C的話，就喪失了保冷性，因 此，比較例可以說是只能夠當作約2小時40分鐘程度的 蓄冷劑來使用。相對地，本發明的蓄冷劑在到達之前 的溫度上昇的坡度是較之市售的蓄冷劑更爲趨緩，可以說 是具有長時間的保冷性。 〔製造例3〕<冷凍用蓄冷劑> 將1 2公升的離子交換水注入到真空混練裝置的混練 鍋槽（內容量60公升）內，添加入3公斤的粉末羧甲基 纖維素鈉（日本製紙株式會社製「S U N R Ο S E系列商品型 號F350HC-4」），水與羧甲基纖維素的總量共計置入15 公升。此時’爲了抑制粉末羧甲基纖維素鈉的粉末上飄， 一邊從粉末的上方噴水霧一邊進行添加。原料添加後，將 真空混練裝置的蓋子關閉，一邊進行真空吸引，一邊在真 空混練裝置內進行攪拌40分鐘而調製成纖維素混練物。 接下來’在真空下將纖維素混練物成形，並照射電子 -18- 201142002 線1 4 k G y，以調製成架橋纖維素凝膠。再將架橋纖維素凝 膠移置到乾燥機內以大約70°C進行乾燥。 將中國湖北省產的岩鹽1〇〇公克（總量5 00公克的 20% )溶解到離子交換水中以調製成20%的食鹽水。在這 個20%的食鹽水中添加入乾燥架橋纖維素凝膠15公克 (總量500公克的3wt% )，進行50分鐘的攪拌，5分鐘 的靜置，然後再進行1 〇分鐘的攪拌使其均勻地混合而調 製成蓄冷劑。 〔實施例4〕 將製造例3所調製的蓄冷劑5 〇 0公克充塡到蓄冷劑保 存盒（橫1 4公分X縱2 0公分X厚度2 3公分）內，並且測 定其凍結時間及保冷時間。 <凍結時間的測定> 將蓄冷劑保存盒放置於室溫之後’放進_ 3 5它的無風 扇冷凍庫冷卻24小時，測定其至凍結爲止的時間。將結 果顯示於第7圖。 蓄冷劑的初期溫度胃2.7t ,放進冷凍庫之後大約} 小時50 #鐘的f壬度’就完全凍結，*小時之後，溫度達 到-2 3.0 °C。 <保冷時間的測定> 將已經在-3 5 °C的冷凍庫 內冷卻達 2 4小時後的蓄冷劑 -19- 201142002 保存盒靜置在保利龍製的箱子（橫32公分χ縱5 1 5公分）內，再將保利龍製的箱子放置於室溫 測定了保利龍製的箱子內的溫度。將結果顯示於 蓄冷劑剛放進保利龍製的箱子內時的初期溫 -23.4 °C，即使經過約6小時之後，溫度還是信 °C 。 〔比較例4〕 除了使用比較製造例1所製造的乾燥架橋纖 的這個條件不同之外，其餘的條件都與製造例4 調製出蓄冷劑。亦即，係添加了比較製造例1的 纖維素凝膠15公克及20%食鹽水來進行攪拌， 蓄冷劑。除了使用以這種方式調製出來的蓄冷劑 餘條件都與實施例4相同，並且測定了凍結時間 間。將其結果顯示於第7圖及第8圖。 <實施例4與比較例4之比較> 本發明的蓄冷劑至完全凍結爲止所需的時間 時50分鐘的程度非常地短，經過4小時的冷凍f -2 3.0 °C，在極短的時間內即可達成凍結。比較1 冷劑則需要約2小時50分鐘才會完全凍結，即 時後，也只能夠達到-22.9t而已。 又，本發明的蓄冷劑約6小時之後，依舊可 -9.0°C，相對地，比較例4的蓄冷劑，約6小時 1公分χ高 內，並且 第8圖。 度爲 $留在-9.0 維素凝膠 相同，來 乾燥架橋 以調製成 之外，其 及保冷時 只要1小 P可達到 π 4的蓄 使約4小 維持在 後就上昇 -20- 201142002 至_4. 〇 。又，本發明的蓄冷劑在6小時之前的溫度上昇 的坡度係較之比較例4的蓄冷劑更爲趨緩，因此可以說是 具有長時間的保冷性。 <總結> 由以上的比較結果可知本發明的蓄冷劑與習知的蓄冷 劑比較之下，具有極優異的凍結性及保冷性。在上述實施 例及比較例中，雖然是針對一個蓄冷劑的凍結時間及保冷 時間進行測定，但是通常都是將複數個同時進行凍結。要 將複數個同時進行凍結時’所需的時間會較之上述實施例 更長的時間，但是本發明的蓄冷劑即使是在一般的使用態 樣之4個同時進行凍結的情況下，也是在5小時以內即可 完成凍結。 [產業上的利用性] _本發明的蓄冷劑係由：可自然分解的天然素材所組 成’可在極短的凍結時間內就凍結，並且保冷時間很長， 對於生鮮食料品或醫藥品的長距離運送或保管等方面非常 有效。 【圖式簡單說明】 第1圖係顯示實施例1及比較例1的凍結時間的測定 結果之圖表。 第2圖係顯示實施例1及比較例1的保冷時間的測定 -21 - 201142002 結果之圖表。 第3圖係顯示實施例2及比較例2的凍結時間的測定 結果之圖表。 第4圖係顯示實施例2及比較例2的保冷時間的測定 結果之圖表。 第5圖係顯示實施例3及比較例3的凍結時間的測定 結果之圖表。 第6圖係顯示實施例3及比較例3的保冷時間的測定 結果之圖表。 第7圖係顯示實施例4及比較例4的凍結時間的測定 結果之圖表。 第8圖係顯示實施例4及比較例4的保冷時間的測定 結果之圖表。 -22-。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Prior Art] The use of a coolant is used to maintain a product such as fresh food at a low temperature for transportation. The cold storage agent used for the transportation of products such as fresh foods must be carried out for 5 to 8 hours/four times in accordance with the transportation route (in the normal use state, a plurality of cold storage agents are simultaneously frozen. In this case, all the cold storage agents must be frozen. Usually, they are frozen for a short period of time of 5 hours and up to 8 hours in the freezer, so that they can be transported over long distances and stored for a long time. In the middle, it does not reduce the cooling effect, but currently there are no cold accumulators on the market that can meet this requirement. The conventional cold storage agent is used as an aqueous solution of an inorganic salt such as sodium chloride, ammonium chloride or magnesium chloride, or a polyhydric alcohol such as ethylene glycol or propylene glycol; and is used as a cold agent; A hydrophilic polymer such as polyvinyl alcohol, sodium polyacrylate or polypropylene decylamine is used as a gelling agent, and is added to 0.01 1 〜1 每 for every 1 part by weight of the coolant. The weight portion is added with silver iodide, copper sulfide, Xanthan Gum, α-terminal, sodium pyrophosphate, etc. as a nucleating agent that can freeze the cold storage agent (please refer to the patent document 。. However, these The cold accumulators are: freeze--5- 201142002. The time required for long-term cooling and the effect of cooling is reduced in a short period of time. In order to solve the above problems, the present inventors have proposed a scheme in which a water-soluble carboxymethyl group is used. After the cellulose is formed into a soft ridge, the radiation is irradiated to form a gel, and the gel is mixed in a ratio of 1 to 5% in 1 to 5% of saline to form a cold storage coolant; Gel in a ratio of 1 to 5% A refrigerating cold storage material which is composed of a cold storage material which is a cold agent (1 to 20% of propylene glycol) (1 to 20%) is added to the brine (see Patent Document 2). In the case of the safety of the environmental protection and the environmental protection, the refrigerating cold storage material which has been previously proposed by the inventors of the present invention has been proposed. It has the advantage that it can be frozen in a short period of time and can maintain a long-term cooling effect, but it contains propylene glycol as a cold agent, and is not a complete natural material. Further, the cold storage described in Patent Document 2 has been confirmed. When the carboxymethyl cellulose is formed into an ointment, it is carried out in an atmospheric state. Therefore, if the degree of irradiation of the radiation is inconsistent, the bubbles will be generated and the gel will not be sufficiently uniform. Inconsistent phenomenon will occur in water absorption, and freezing and cold preservation performance are not sufficient. [Priority Technical Literature] [Patent Literature] [Patents Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Coolant, this kind of cold storage system: It is composed of natural materials without special chemical treatment when it is discarded, it can be frozen in a short time and can exert long-term cold preservation effect. [Technical means to solve the problem The cold storage agent according to the present invention is a dry bridge cellulose gel obtained by irradiating an electron beam with an ointment-like cellulose kneaded product obtained by kneading 15 to 25 wt% of cellulose and water under vacuum. Glue 2~4wt%, 1~2 1 wt% of rock salt and water. The bridging cellulose gel used in the present invention is such that the water absorption ratio obtained by dividing the gel which has been absorbed for 24 hours by the initial weight of the dry bridged cellulose gel before water absorption is 150 to 250 times. Preferably, it is better to dry the gel from 15〇 to 200 times. By using such a dry bridged cellulose gel having a high water absorption ratio, it is possible to maintain a large amount of water in the bridging cellulose gel. The large amount of water held in the bridging cellulose gel, once frozen, takes a long time to thaw, thus extending the cooling time. However, if the water absorption ratio is too high, the time required for freezing becomes long, and the strength of the gel itself is also deteriorated, so the above range is preferable. The cellulose used in the present invention is sodium carboxymethylcellulose, preferably sodium carboxymethylcellulose which does not have a reduced viscosity even in saline. The best is: even in 1~5 % saline can still show 2 600 m P a. Viscosity above 201142002 s (according to the B-type viscometer measured 10% saline can still show 4600mPa. s The viscosity of the carboxymethyl fiber coolant measured by the B-type viscometer is formed by drying the bridged cellulose. If the viscosity of the bridging cellulose in the saline solution functions as a gelling agent and the bridging gel structure is lowered, the cellulose system used as a raw material is preferred. The content of the above-mentioned cellulose of the dry bridge cellulose used in the present invention tends to be 15 to 25 wt ° / 〇, 15 to 20 wt %, added to water in a vacuum ointment-like cellulose kneaded material, and for such a substance, It is obtained by intensifying an electron beam at an intensity of 8 to 16 kGy, preferably 9. It is preferable to prepare a paste-like cellulose kneaded material, and therefore ion-exchanged water is preferred. This is a kneading. By kneading under vacuum, the cellulose powder can be uniformly dispersed and dispersed, and kneading can be sufficiently performed. The content of cellulose in the cellulose kneaded material and the water absorption and water retention required to affect the bridging structure refrigerant formed by the irradiation of the electron beam are carried out to achieve the cellulose content and the electron beam irradiation amount in each of the above ranges. Too much, the viscosity of the mesh of the bridging structure), and the viscosity above (according to the sodium sulphate. The gel of the present invention is present in the saline solution, the water retention capacity in the inner layer will not have the above range of cohesion. The glue is a salt which is obtained by kneading the ointment-like cellulose which is obtained by kneading a preferable content, and the water used in the strength of ~14 kGy does not contain salt. It must be under vacuum and there is no bubble. In the exchange of water, the state electron beam exposure will be the best. In order to achieve the results of the seeding experiment, the emission is the best. The electricity is smaller. The mesh can be used to maintain water molecules from -8 to 201142002, so the water molecules retained by one mesh The less the words 'can shorten the time required for freezing, and the mesh is formed densely' so the thawing time will be longer and the cold preservation time can be extended. However, If the net mesh is so small that it is impossible to maintain the degree of the water molecule, it cannot be used. The present inventors have confirmed that as long as it is in the above-mentioned irradiation amount range, the freezing time can be shortened and maintained. A longer cold storage time is suitable as the mesh structure of the cold storage agent of the present invention. The bridged cellulose gel obtained by the above irradiation conditions has a water absorption ratio of 150 to 2 times when dried, and is very suitable as a The cold accumulating agent of the present invention is added to the rock salt containing 1 to 21 wt% in such a manner that the content of the above-mentioned dry bridging cellulose gel tends to be 2 to 4 wt%, preferably 2.5 to 3.5 wt%. In the saline solution, the mixture is sufficiently stirred and mixed, and then filled into a container or a bag made of a film, a nonwoven fabric, or the like. In the present invention, the "saline solution has a cold agent effect. The saline solution used in the present invention. It is not a refined salt, but a natural rock salt. Natural rock salt and refined salt (according to the quality specifications of the Japan Salt Business Center: sodium chloride 99 wt% or more, calcium 0.02 w It is different from t% or less, magnesium 〇 〇 2 wt% or less, and potassium 〇. 25 wt% or less, and is rich in minerals, so that it can exert an excellent cold agent effect. The rock salt-based NaCl content used in the present invention is 99 wt% or more. The total content of Na+ and Mg2+ is more than 〇 and less than 0.3 wt% of rock salt, especially the rock salt produced in Hubei Province of China is particularly suitable. The salt water concentration is 7H depending on the temperature range required by the cold storage agent, as 0 °C~-1 7 °c refrigerated range using cold storage agent-9- 201142002 Lower 'rock salt content is 1~17 wt%; used as a cold storage range below -1 °C °C In the case, the content of the rock salt is preferably 18 to 2% by weight. If you want to lower the freezing point of the coolant by 1 °C, you can add 1 w t % of the rock salt. [Effects of the Invention] According to the present invention, it is possible to provide a cold accumulating agent which can be frozen for a short period of time and has a long cooling effect. Further, since the cold accumulating agent of the present invention is a product having a natural decomposable completely natural material composed of a dry bridge cellulose gel, salt, and water, the coolant itself does not need to be disposed of, even if it is accidentally leaked. It is also safe, so it is not only extremely easy to use, but also suitable for use in the storage and transportation of products that require safety, such as fresh food or pharmaceuticals. [Embodiment] The present invention will be described in detail by way of examples and comparative examples. [Production Example 1] <Cooling Range Coolant> 1 2 liters of ion-exchanged water was injected into a kneading tank of a vacuum kneading apparatus (content amount was 60 liters), and powdered sodium carboxymethylcellulose (曰3 kg of "SUN ROSE series product model F3 50HC-4" manufactured by Toyo Paper Co., Ltd., and a total of 15 liters of water and carboxymethyl cellulose. At this time, in order to suppress the powder of the sodium carboxymethylcellulose powder, it was added while spraying water mist from the upper side of the powder. After the addition of the raw material, the lid of the vacuum kneading apparatus was closed, and vacuum suction was performed, and the mixture was stirred in a vacuum kneading apparatus for 40 minutes to prepare a cellulose kneaded product. Next, the cellulose kneaded material was shaped under vacuum, and irradiated with an electron beam of 14 kGy' to prepare a bridged cellulose gel. The bridging cellulose gel was then transferred to a dryer and dried at about 70 °C. 5 5 g of rock salt (total 丨, 5% of 100 g) produced in Hubei Province, China was dissolved in ion-exchanged water to prepare 5% saline. Add 7 7 · 5 g of dry bridging cellulose gel (2 _ 5 wt % of total 1,1 〇〇g) to this 5% saline solution, stir for 50 minutes, let stand for 5 minutes, and then carry out 1 The mixture was uniformly mixed for 0 minutes to prepare a cold accumulating agent. [Comparative Production Example 1] In addition to the dry bridged cellulose gel used in the examples of the Japanese Patent Application Laid-Open No. 2007-238735, the entire disclosure of the present application, The conditions were the same as in Production Example 1 to prepare a coolant. That is, the amount of the dry bridging cellulose gel obtained by drying the ointment-like carboxymethyl cellulose which is kneaded by using an open type kneading tank is 5 kGy, and then drying it is 27.5 grams and 5% salt water, stirred to prepare a cold storage agent (total amount 1 1 0 0 grams, gel 2 · 5 % < 2 7 · 5 grams), salt 5% < 55 grams>, water i 〇17.5cc) -11 - 201142002 [Example 1] 1100 g of the cold accumulating agent prepared in Production Example 1 was charged into a coolant storage box (19.5 cm in length, 2 in length, 26 cm in thickness, and 3.5 cm in thickness), and the freezing was measured. Time and cold storage time. <Measurement of Freezing Time> After the storage container was placed at room temperature, it was placed in a fanless freezer at -3 °C for 24 hours, and the time required for complete freezing was measured. The results are shown in Figure 1. The initial temperature of the coolant is 1 0.4 ° C, and about 1 hour and 1 minute after being placed in the freezer, the temperature of the coolant is drastically lowered to -1 〇 ° C, and is completely frozen for about 2 hours and 20 minutes. After 6 hours, it reached -17.6 °C. <Measurement of cold storage time> The cool storage container which has been cooled in the freezer at -3 ° C for 24 hours is allowed to stand in a box made of Polytron (32 cm in length, X in length, 51 cm in height, 1 in height 1 5) Within the centimeter, place the box made of Polylon at room temperature' to determine the temperature inside the box made of Poly. The results are shown in Figure 2. The initial temperature of the coolant immediately after it was placed in a box made of Polytron was -12.53⁄4. After about 8.5 hours, it rose to 〇 ° C, and after about 9.5 hours, it rose to 3.1 ° C. -12-201142002 [Comparative Example 1] The same experiment as in Example 1 was carried out using the cold accumulating agent manufactured by Comparative Production Example. The results are shown in Figures 1 and 2. <Measurement of freezing time> The initial temperature is 1 1 · 8 °C. After about 1 hour and 1 minute after putting it into the freezer, it becomes '-5 °C'. After about 4 hours, the freezing is completed. After about 6 hours, it becomes - 1 3.9 °C. <Measurement of cold storage time> The initial temperature was -1 1. 1 °C. After about 7.5 hours after putting into a box made of Polytron, it became 〇 °C, and after about 9 _ 5 hours, it rose to 1 〇丨7. <Comparative Example 1 and Comparative Example 1> The time required for the cold storage agent of the present invention to completely freeze is as long as 2 hours, and is extremely short 'only 6 hours of freezing can be achieved _ 丨 7 6 ° C, a freeze can be achieved in a very short time. In Comparative Example 1, it takes about 4 hours to completely freeze, and only after -6 hours, it can only reach -1 3 _ 9 °C. Further, the cold accumulating agent of the present invention takes about 8.5 hours to rise to 〇 ° C, and stays at 3 · 1 ° C even after 9.5 hours. In contrast, Comparative Example 1 rises to about 7.5 hours. 0 °C '1 0.1 °C after 9 · 5 hours. As long as the coolant exceeds 1 〇 °C, the cold retention property is lost. Therefore, Comparative Example 1 can be said to be used only as a coolant of -13-201142002 for about 9 hours. On the other hand, the temperature of the cold accumulating agent of the present invention which rises after reaching a temperature of 3.1 °C is slower than that of Comparative Example 1, and it can be said that it has a long-term cold retention property. [Example 2] 650 g of the cold accumulating agent prepared in Production Example 1 was charged to a coolant storage box (crosswise 15 cm X longitudinal 26.5 cm X thickness 2 cm), and the freezing time and the cold retention time were measured. <Measurement of Freezing Time> After storing the cool storage container at room temperature, it was placed in a fanless freezer at -35 °C for 24 hours, and the time until freezing was measured. The results are shown in Figure 3. The initial temperature of the coolant is 13 ° C, about 50 minutes after being placed in the freezer, the temperature of the coolant is rapidly reduced to -5 ° C '3 hours and 10 minutes to completely freeze, after 6 hours, reach -27.1 ° C. <Measurement of cold storage time> The cold storage container which has been cooled in the freezer at -3 °C for 24 hours is allowed to stand in a box made of Polytron (32 cm in length X 5 in centimeters in height X 1 in height 1 5) Within the centimeter, the box made of Polytron was placed at room temperature' and the temperature inside the box made by Polytron was measured. The results are shown in Figure 4. The initial temperature when the coolant was just placed in a box made of Polytron was -1 7. (: After about 6 hours, it rises to 0. (:, after about 6.5 hours, 'rise-14-201142002 is 2.9 〇C. [Comparative Example 2] In addition to using a commercially available coolant (gelling agent··high The conditions of the molecular polymer, the cold agent: propylene glycol were different, and the other conditions were the same as in Example 2, and the freezing time and the cold retention time were measured. The results are shown in Fig. 3 and Fig. 4. <Examples 2Comparative with Comparative Example 2> The time required for the cold storage agent of the present invention to completely freeze is as short as 3 hours. 'After 6 hours of freezing, it can reach -27. 1 ° C, in a very short time. The freezing can be achieved within a short period of time. The commercially available coolant takes about 4 hours to completely freeze, and even after about 6 hours, it can only reach -25.1 ° C. Moreover, the coolant of the present invention rises to 0 ° It takes about 6 hours until C, and the temperature stays at 2.9 °C after 6.5 hours. In contrast, the commercially available coolant rises to 0 °C in about 5 hours. After 6 hours, the temperature rises sharply, after 6.5 hours. It reaches 9.1 (:: cold storage for cold storage) As long as it exceeds 1 〇 °c, the cold retention property is lost. Therefore, the comparative example can be said to be used only as a cold storage agent for about 6 to 5 hours. In contrast, the cold storage agent of the present invention reaches 2.9 ° C after reaching The gradient of the temperature rise is slower than that of the commercially available coolant, and it can be said that it has a long-term cold retention property. -15- 201142002 [Production Example 2] <Cooling Range Coolant>> The ion-exchanged water was poured into a vacuum kneading tank (content: 60 liters), and 3 kg of cellulose sodium ("SUN ROSE No. F350HC-4" manufactured by Nippon Paper Industries Co., Ltd.), water and carboxymethyl cellulose were added. In this case, in order to suppress the powdered sodium carboxymethyl cellulose, the water mist was sprayed from above the powder while the lid of the raw material vacuum kneading device was closed, and the inside of the vacuum suction kneading apparatus was stirred for 40 minutes. Modification into cellulose Next, the cellulose kneaded material was formed under vacuum at a line of 14 kGy to prepare a bridged cellulose gel, and the frame rubber was again placed in a dryer to be dried at about 70 °C. 1 300 g (20% of total) rock salt produced in Hubei Province, China, dissolved in ion-exchanged water to prepare 20% of a 20% saline solution, added to dry bridging cellulose gel (3 wt% of total 650 g) The mixture was allowed to stand for 50 minutes, and then stirred for 10 minutes to uniformly form a cold accumulating agent. [Example 3] 650 g of the cold accumulating agent prepared in Production Example 2 was filled in a storage case (horizontal 15) Centimeters X longitudinal 26.5 cm X thickness 2 cm) Set the freezing time and cold storage time. The mixing powder of the device is carboxymethyl series. The product type is placed on the powder of 1 5 powder. And irradiated the electron bridge cellulose to condense 65 0 grams of brine. In this 1 9.5 gram mix, mix for 5 minutes and transfer to the coolant, and measure -16- 201142002 <Measurement of freezing time> After placing the coolant storage box at room temperature, put it in - fan freezer cooling The fruit obtained by measuring it to 2 hours in 2 hours is shown in Fig. 5. The initial temperature of the coolant was 7.9 ° C, and it was placed in a freezer; at the temperature of 30 minutes, the temperature of the coolant was drastically lowered to _ 30 minutes to completely freeze '4 hours later' temperature - 23.9 〇C. <Measurement of cold storage time> The storage box which has been cooled in the freezer at -3 °C for 24 hours is allowed to stand in a box made of Polytron (horizontal 3 2 cm x vertical 15 cm), and then Poly The box made of dragon was placed in the room to measure the temperature inside the box made of Poly. The results show that the coolant was just placed in the box made of Polylon -21.7T: After about 3 hours and a half, the temperature rose to 〇 °C. [Comparative Example 3] The same conditions as in the case of using a commercially available cold accumulating agent (gelling agent: high cold component: propylene glycol) were the same, and the freezing time and the cold retention time were measured. Figure 5 and όΗ ° <Comparative Example 3 vs. Comparative Example 3> 3 5 °C no wind time. After the knot is reached at 20 ° C for 1 hour, the cold accumulator reaches 5 1 cm X high temperature, and is shown in Fig. 6. The temperature is a sub-polymer, and the results are not consistent with the implementation. The time required for the cold storage agent of the present invention to completely freeze is as short as 2 hours and 30 minutes, and can be frozen after 4 hours. At -2 3 · 9 °C, freezing can be achieved in a very short time. Commercially available coolants take about 3 hours to completely freeze, and even after about 4 hours, they can only reach -2 2.8 T: only. Further, it takes about 3 hours and 30 minutes for the cold accumulating agent of the present invention to rise to 〇 ° C. In contrast, the commercially available cold accumulating agent rises to 0 ° C in about 2 hours and 40 minutes, and the temperature reaches 8.2 after 4 hours. . (: The cold storage agent for the freezing range loses the cold retention property when it exceeds 0 °C. Therefore, the comparative example can be said to be used only as a cold storage agent of about 2 hours and 40 minutes. The gradient of the temperature increase of the cold accumulating agent of the invention is slower than that of the commercially available cold accumulating agent, and it can be said that it has a long-term cold retention property. [Production Example 3] <Chilling Coolant> 2 liters of ion-exchanged water was injected into a kneading tank of a vacuum kneading device (content: 60 liters), and 3 kg of powdered sodium carboxymethylcellulose ("NRNR Ο SE series product model F350HC-made by Nippon Paper Industries Co., Ltd." was added. 4"), a total of 15 liters of water and carboxymethylcellulose were added. At this time, in order to suppress the powder of the sodium carboxymethylcellulose powder, it was added while spraying water mist from above the powder. Thereafter, the lid of the vacuum kneading apparatus was closed, and while vacuum suction was applied, the mixture was stirred in a vacuum kneading apparatus for 40 minutes to prepare a cellulose kneaded product. Next, 'the fiber was vacuumed. The kneaded material was formed and irradiated with electrons of 1 - 4 k G y to form a bridging cellulose gel. The bridging cellulose gel was then transferred to a dryer and dried at about 70 ° C. 1 gram of rock salt produced in Hubei Province (20% of total 500 gram) was dissolved in ion-exchanged water to prepare 20% saline solution. Add 15 grams of dry bridge cellulose gel to this 20% saline solution. (3 wt% of a total amount of 500 g), the mixture was stirred for 50 minutes, and allowed to stand for 5 minutes, and then further stirred for 1 minute to prepare a cold accumulating agent. [Example 4] Production Example 3 The prepared cold accumulating agent 5 〇 0 g was charged into the coolant storage box (1 4 cm X vertical 2 0 cm X thickness 2 3 cm), and the freezing time and cold storage time were measured. <Measurement of freezing time > After placing the coolant storage box at room temperature, it was placed in its fanless freezer for 24 hours, and the time until freezing was measured. The results are shown in Fig. 7. The initial temperature of the coolant is 2.7t. , put into the freezer after about 5 hours 50 #钟f壬' is completely frozen, and after *hour, the temperature reaches -2 3.0 °C. <Measurement of cold storage time> Coolant -19 after cooling in a freezer at -3 5 °C for 24 hours - 201142002 The storage box was placed in a box made of Polytron (32 cm in length and 32 cm in length), and the temperature in the box made of Polytron was measured by placing the box made of Poly Dragon at room temperature. At the initial temperature of -23.4 °C when the coolant was placed in the box made of Polytron, the temperature was still after about 6 hours. [Comparative Example 4] A cold accumulating agent was prepared in the same manner as in Production Example 4 except that the conditions of the dry bridging fiber produced in Comparative Production Example 1 were different. In other words, 15 g of the cellulose gel of Comparative Production Example 1 and 20% of saline solution were added to carry out stirring and a cold storage agent. The conditions of the cold accumulating agent prepared in this manner were the same as in Example 4, and the freezing time was measured. The results are shown in Figures 7 and 8. <Comparative Example 4 and Comparative Example 4> The time required for the cold storage agent of the present invention to completely freeze was extremely short at 50 minutes, and after 4 hours of freezing f -2 3.0 ° C, extremely short The freeze can be reached within the time. Comparing 1 refrigerant takes about 2 hours and 50 minutes to completely freeze, and after that, it can only reach -22.9t. Further, after about 6 hours, the cold accumulating agent of the present invention can still be used at -9.0 ° C, and the cold accumulating agent of Comparative Example 4 is relatively high for about 6 hours and 1 cm, and Fig. 8 is obtained. The degree is the same as the -9.0 vegetal gel, which is used to dry the bridge to prepare it. When it is kept cold, as long as 1 small P can reach π 4, it will rise after about 4 hours to maintain -20- 201142002 _4. 〇. Further, the gradient of the temperature increase of the cold storage agent of the present invention before 6 hours is slower than that of the cold storage material of Comparative Example 4, so that it can be said that it has a long-term cold retention property. <Summary> From the above comparison results, it is understood that the cold storage agent of the present invention has extremely excellent freezeability and cold retention property as compared with a conventional cold storage agent. In the above-described examples and comparative examples, the freezing time and the cooling time of one of the coolants were measured, but usually, a plurality of them were simultaneously frozen. When a plurality of freezes are simultaneously performed, the time required is longer than that of the above embodiment, but the cold accumulator of the present invention is frozen even in the case of simultaneously freezing four of the general use patterns. Freeze is completed within 5 hours. [Industrial Applicability] _ The cold storage agent of the present invention is composed of natural materials that can be naturally decomposed 'can be frozen in a very short freezing time, and the cold storage time is long, for fresh foods or pharmaceuticals. It is very effective in long-distance transportation or storage. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing measurement results of freezing time in Example 1 and Comparative Example 1. Fig. 2 shows the measurement of the cold retention time of Example 1 and Comparative Example 1 -21 - 201142002 The graph of the results. Fig. 3 is a graph showing the measurement results of the freezing time in Example 2 and Comparative Example 2. Fig. 4 is a graph showing the results of measurement of the cold retention time in Example 2 and Comparative Example 2. Fig. 5 is a graph showing the results of measurement of the freezing time in Example 3 and Comparative Example 3. Fig. 6 is a graph showing the results of measurement of the cold retention time of Example 3 and Comparative Example 3. Fig. 7 is a graph showing the measurement results of the freezing time of Example 4 and Comparative Example 4. Fig. 8 is a graph showing the results of measurement of the cold retention time of Example 4 and Comparative Example 4. -twenty two-