200417361 玖、發明說明： 【發明所屬之技術領域】 本發明為關於一種具有低溫柔軟性，且保冷能力大的保 冷袋。 【先前技術】 内藏有保冷材料之保冷袋，以往被使用作為身體發熱時 冷敷頭部或冷敷患部之用。保冷材料對其内容物之保冷組 成物有各種提議使其可長時間保持保冷時間，具有卓越的 低溫柔軟性，反覆使用時柔軟性不會減低等。例如：配合 羧甲基纖維素、聚乙烯醇等的水溶性高分子、甘油脂肪酸 酯等的界面活性劑、乙二醇等的凝固點下降劑之材料（曰 本專利特公昭5 9 - 3 5 9 4 4號公報），以聚乙烯醇和硼酸（鹽） 使醇溶液凝膠化之材料（日本專利特開昭 5 6 - 3 6 5 3 8號公 報），以水溶性環氧化物使聚丙稀酸納凝膠化之材料（日本 專利特開昭5 6 - 7 9 1 2 2號公報），在聚乙烯醇中配合氯化鎂 之材料（日本專利特開昭5 7 - 1 9 0 0 7 2號公報），配合高分子 吸收劑和多元醇水溶液之材料（日本專利特開平1 - 2 2 3 1 9 0 號公報），和高吸水性樹脂、聚乙稀醇和水混練之材料（曰 本專利特開平5 - 2 3 9 4 4號公報），配合吸水性樹脂、丙烯醯 胺系共聚體、水及丙三醇等的親水性醇類之材料（日本專 利特開平5 - 3 2 0 6 2 7號公報），在含有水溶性高分子和多元 醇之水溶性凝膠配合多價金屬化合物的交聯劑之材料（曰 本專利特開平6 - 2 5 6 5 7號公報），在形成以分子狀態連續基 體層之吸水性樹脂配合凝固點下降劑之材料（日本專利特 5 312/發明說明書(補件)/93-02/92134157 200417361 開平6 - 6 5 5 6 0號公報），配合水不溶性吸水性聚合物的吸水 凝膠、水溶性聚合物之.水性凝膠及丙三醇等的親水性醇類 之材料（日本特開平6 - 1 2 2 8 7 1號公報），使用N -乙烯醯胺 (共）聚合體之材料（日本專利特開平U - 8 0 7 1 6號公報、 特開2 0 0 0 - 3 1 3 8 7 6號公報、特開2 0 0 2 - 1 6 1 1 8 3號公報），藉 配合凝固點下降劑、凝膠化劑等來作試驗以改良使用感。 又，在保冷袋上貼緩衝墊材料或和不凍液構成雙重構造 等，而從包覆材料之方面也被予以實施改良。 但是，一般家庭用的冰箱有逐漸低溫化之傾向，特別是 隨著冷凍箱的普及，以往的保冷材料組成物會凍結，而不 能保持柔軟性。因此，填充有這些保冷材料的保冷袋變成 對頭部或患部之適用性不佳，同時，由於保冷材料也會在 0 ° C 以下被冷卻，因此直接貼在要冷敷的頭部或患部時會 有發生凍傷之虞。 為了暫時解決此問題，雖然可以毛巾等包著這些保冷袋 而使用，但其仍然適用感不佳，假如過厚包住保冷袋來冷 敷時要使頭部或患部冷卻時則需要花很長的時間。 又，即使運動員想要使用此種類型的保冷袋來冷敷患部 時，在身邊如沒有冷凍庫之野外場所則無法被使用。 又，使冷媒之結晶性無機化合物的水溶液填充入保冷袋 中，該結晶會自外部熱源（例如，人的發熱）吸收熱而熔 解，當保冷袋表面再放熱而變成結晶時，則在保冷袋的内 部會發生熱還流，而藉利用反覆熔解和再結晶經常自熱源 繼續吸收熱之原理，例如：在枕頭等使用保冷袋時，人的 6 312/發明說明書(補件)/93-02/92134157 200417361 頭部會變成外部熱源，由於從此處可奪去熱，因此可冷卻 頭部，而得到冷卻效果之枕頭。此種保冷袋使用磷酸鈉或 硫酸鈉已為眾所周知（日本專利實開昭5 8 - 1 9 6 6 7號公報、 實開平6 - 5 2 8 1 5號公報）。 但是，此種結晶性無機化合物之結晶很大，由於難以炼 解，冷卻效果很低，在物理上也缺少流動性，因此，在觸 感上有很大的不調和感。又，在密封結晶性無機化合物之 冷卻袋則容易發生氣孔且有壽命短之缺點，在實用上有問 題。 為了解決此種問題，已提議有使由硫酸鈉和鋁矽酸質所 構成的蒙脫石（m ο n m 〇 r i 1 1 ο n i t e黏土為主成分之活性膨潤 土作為主成分加入水中調和，更佳者是再對其混入含有碳 纖維之填充劑而密封入保冷袋中（日本專利特開平 9 - 2 9 6 1 6 5號）。但是，該提案也仍不能完全克服如上述之 缺點。 因此，本發明之目的為提供一種可提高對頭部或患部之 適用性，可不會過度冷卻而可保持適當溫度的保冷袋。 【發明内容】 本發明為鑑於上述問題而所完成，本發明人對保冷袋所 使用之保冷材料反覆專心研究結果，出乎意料地發現對保 冷材料不使用高分子聚合物等，而在具有0 ° C以上之熔點 的潛熱蓄熱材料之水溶液中，藉加入無機微粒子及醇類 後，潛熱蓄熱材料不會過度冷卻且可迅速析出結晶，在冷 卻時也可保持柔軟性而可一舉改善對頭部或患部之觸感或 7 312/發明說明書(補件)/93-02/92134157 200417361 適用性，而完成本發明。 亦即，本發明之保冷袋為，在具有0 ° C以上之熔點的潛 熱蓄熱材料之水溶液中，添加無機微粒子及醇類之保冷袋 而充填入合成樹脂製袋内，如此為其特徵。 具有0。C以上之熔點的潛熱蓄熱材料，可列舉：硫酸鈉 水合物（芒确# )、亞硫酸鈉、填酸納等。 無機粒子可列舉：微粉末二氧化矽（煙霧狀二氧化矽）、 沈澱二氧化矽（含水矽酸）、微粉末氧化鋁、微粉末中空陶 瓷等的微粒子。 醇類則可列舉：乙醇、丙醇、丁醇、丙二醇等。 【實施方式】 本發明之保冷袋為，在具有0 ° C以上之熔點的潛熱蓄熱 材料之水溶液中，添加無機微粒子及醇類之保冷袋填充入 合成樹脂製袋内，如此所成。 具有0。C以上之熔點的潛熱蓄熱材料可被列舉：硫酸鈉 水合物（芒硝）、亞硫酸鈉、磷酸鈉等。潛熱蓄熱材料為， 對保冷材料1 0 0重量份被使用1 0〜7 0重量份，較佳為2 0〜6 0 重量份。凝固點如眾所周知，可藉添加氯化鈉、氯化銨、 尿素等可更減低凝固點。因此，併用此種凝固點下降劑也 是本發明實施的一種態樣。凝固點下降劑為，對保冷材料 100重量份，使用5〜90重量份，較佳為10〜80重量份。 無機微粒子可被列舉：微粉末二氧化矽（煙霧狀二氧化 矽）、沈澱二氧化矽（含水矽酸）、微粉末氧化鋁、微粉末 中空陶瓷等的微粒子。此些無機微粒子的粒徑（一次粒子 8 312/發明說明書(補件)/93-02/92134157 200417361 徑，個數平均）為5〜5 0 n m，較佳為8〜4 0 n m。此些 子也可混合使用。無機微粒子為，對保冷材料1 Ο Ο 使用1〜2 0重量份，較佳為2〜1 0重量份。200417361 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a cold storage bag having low temperature flexibility and large cold storage capacity. [Previous Technology] A cold storage bag with a cold insulation material has been used to cool the head or the affected area when the body is hot. The cold-insulating material has various proposals for the cold-insulating composition of its contents so that it can maintain the cold-keeping time for a long time, has excellent low-temperature softness, and does not reduce its softness when used repeatedly. For example: materials containing water-soluble polymers such as carboxymethyl cellulose, polyvinyl alcohol, surfactants such as glycerin fatty acid esters, and freezing point lowering agents such as ethylene glycol (Japanese Patent Publication No. 5-9-3 5 Publication No. 9 4), a material that gels an alcohol solution with polyvinyl alcohol and boric acid (salt) (Japanese Patent Laid-Open No. Sho 5 6-3 6 5 3 8), and polypropylene is diluted with water-soluble epoxide Sodium acid gelled material (Japanese Patent Laid-Open No. 5 6-7 9 1 2 2), a material containing magnesium chloride in polyvinyl alcohol (Japanese Patent Laid-Open No. 5 7-1 9 0 0 7 2 Bulletin), a material mixed with a polymer absorbent and a polyhydric alcohol aqueous solution (Japanese Patent Laid-Open No. 1-2 3 1 190), and a material mixed with a super absorbent resin, polyvinyl alcohol and water (referred to as the patent Kaihei 5-2 3 9 4 4), water-absorbent resin, acrylamide-based copolymer, water, glycerol and other hydrophilic alcohols (Japanese Patent Laid-Open No. 5-3 2 0 6 2 7 Bulletin), a polyvalent metal is mixed with a water-soluble gel containing a water-soluble polymer and a polyhydric alcohol Material of the cross-linking agent (Japanese Patent Laid-Open No. 6-2 5 6 5 7), a material in which a water-absorbent resin forming a continuous matrix layer in a molecular state is mixed with a freezing point depressant (Japanese Patent No. 5 312 / Invention Specification (Supplement) / 93-02 / 92134157 200417361 Kaiping No. 6-6 5 5 60 0), water-absorbing gel with water-insoluble water-absorbing polymer, water-soluble polymer. Water-based gel and glycerol Materials such as hydrophilic alcohols (Japanese Patent Laid-Open No. 6-1 2 2 8 7 1), and materials using N-vinylamine (co) polymer (Japanese Patent Laid-open No. U-8 0 7 1 6 (Japanese Gazette, Japanese Patent Laid-Open No. 2000-3 1 3 8 7 6 and Japanese Patent Laid-Open No. 2000-1 6 1 1 8 3), tests are performed by blending a freezing point lowering agent, a gelling agent, etc. Improved use. In addition, a cushion material is attached to the cold storage bag or a double structure is formed with the antifreeze, etc., and improvements have also been made in terms of the covering material. However, refrigerators for general households tend to be gradually lowered in temperature. In particular, with the popularization of freezers, conventional cold-insulating material compositions may freeze without maintaining flexibility. Therefore, the cold storage bag filled with these cold insulation materials has poor applicability to the head or the affected part. At the same time, since the cold insulation material is also cooled below 0 ° C, it will be directly attached to the head or affected area to be cold-applied. There is a risk of frostbite. In order to temporarily solve this problem, although you can use these cold bags with towels, they still have a poor applicability. If the cold bag is wrapped too thick to cool the head or affected part, it will take a long time. time. In addition, even when athletes want to use this type of cold bag to apply cold to the affected area, they cannot be used in the field without a freezer nearby. In addition, an aqueous solution of a crystalline inorganic compound of a refrigerant is filled into the cooling bag, and the crystals absorb heat from an external heat source (for example, human heat) and melt. When the surface of the cooling bag is re-heated to become crystals, it is placed in the cooling bag. The internal flow of heat will also occur, and by using the principle of repeated melting and recrystallization, it continues to absorb heat from the heat source. For example, when using a cold storage bag such as a pillow, the human 6 312 / Invention Specification (Supplement) / 93-02 / 92134157 200417361 The head will become an external heat source. Since heat can be taken from here, the head can be cooled to obtain a cooling effect pillow. It is well known to use sodium phosphate or sodium sulfate for this type of cooler bag (Japanese Patent Laid-Open No. 5 8-119 6 67, Shi Kai Hei 6-5 2 8 15). However, such a crystalline inorganic compound has a large crystal size, is difficult to be refined, has a low cooling effect, and lacks physical fluidity. Therefore, it has a great sense of incongruity in touch. In addition, the cooling bag that seals the crystalline inorganic compound is prone to pores and has a short life, and has a practical problem. In order to solve this problem, it has been proposed that active bentonite (m ο nm 〇ri 1 1 ο nite clay) composed of sodium sulfate and aluminosilicate as the main component is added to the water as a main component to make it better. One is to mix it with a carbon fiber-containing filler and seal it in a cooler bag (Japanese Patent Laid-Open No. 9-2 9 6 1 6 5). However, this proposal still cannot completely overcome the disadvantages described above. Therefore, the present The object of the present invention is to provide a cold storage bag which can improve the applicability to the head or the affected part, and can maintain an appropriate temperature without excessive cooling. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and the present inventor has The results of repeated intensive research on the cold-keeping materials used have unexpectedly found that instead of using high-molecular polymers for the cold-keeping materials, inorganic fine particles and alcohols are added to the aqueous solution of latent heat storage materials with a melting point of 0 ° C or higher. After that, the latent heat storage material will not be excessively cooled and crystals can be quickly precipitated. It can also maintain softness during cooling, which can improve the contact with the head or the affected part in one fell swoop. Or 7 312 / Invention Specification (Supplement) / 93-02 / 92134157 200417361 applicability to complete the present invention. That is, the cold storage bag of the present invention is in an aqueous solution of a latent heat storage material having a melting point of 0 ° C or more It is characterized by adding inorganic microparticles and alcohol-based cold storage bags and filling them into synthetic resin bags. Latent heat storage materials with a melting point of 0 ° C or higher include sodium sulfate hydrate (awning #) and sodium sulfite. Inorganic particles include fine powder silicon dioxide (smoke-like silicon dioxide), precipitated silicon dioxide (hydrous silicic acid), fine powder alumina, fine powder hollow ceramics, and other fine particles. Examples include: ethanol, propanol, butanol, propylene glycol, etc. [Embodiment] The cold storage bag of the present invention is a cold storage bag in which an inorganic fine particle and an alcohol are added to an aqueous solution of a latent heat storage material having a melting point of 0 ° C or more. Filled into a bag made of synthetic resin, it is made in this way. Latent heat storage materials with a melting point of 0 C or more can be listed: sodium sulfate hydrate (Glauber's salt), sodium sulfite, sodium phosphate The latent heat storage material is 100 to 70 parts by weight, preferably 20 to 60 parts by weight, of 100 parts by weight of the heat-retaining material. If the freezing point is well known, sodium chloride, ammonium chloride, Urea and the like can further reduce the freezing point. Therefore, the use of such a freezing point lowering agent is also a form of implementation of the present invention. The freezing point lowering agent is 100 parts by weight of the cooling material, 5 to 90 parts by weight, preferably 10 to 80 parts by weight The inorganic fine particles can be exemplified by fine particles of fine powdered silica (smoke-like silica), precipitated silica (hydrous silicic acid), fine powdered alumina, fine powdered hollow ceramics, and the like. The diameter (primary particle 8 312 / Invention Specification (Supplement) / 93-02 / 92134157 200417361 diameter, number average) is 5 to 50 nm, preferably 8 to 40 nm. These can also be mixed. The inorganic fine particles are used in an amount of 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight, for the cooling material 1 〇.
醇類可被列舉：不會溶解潛熱蓄熱材料之乙醇 丁醇等。由此，在保冷材料水溶液的溫度降低時 會過冷卻，可容易析出水合物之結晶。醇類雖然 熱蓄熱材料的種類而適當選擇其使用量，但是對 材料1 0 0重量份為使用1〜2 0重量份，較佳為1〜1 C 合成樹脂製袋的材質只要具有柔軟性即可。但 列舉：尼龍·聚乙烯層壓片、乙烯·醋酸乙烯共 乙烯·曱基丙烯酸曱酯共聚體。其保冷袋也可再 成樹脂製或布製的外裝袋内而使用。 (實施例） 以下藉實施例具體說明本發明之構成。 (實施例1 ) 在水400g中加入硫酸鈉160g，在28°C —面攪 使其溶解。在溶解液變成透明時，再加入微粉末 (煙霧狀二氧化矽，平均粒徑 4 0 n m ) 2 0 g，繼續 時再加入乙醇4 0 g並快速攪拌，填充入合成樹脂 密封。以室溫1 8。C下，放置該保冷袋。在3小時 析出微細的結晶，内容物變成帶有黏性之凝膠狀 的柔軟性及觸感非常良好。當貼在患部時其冷卻 績大約5小時。 為了觀察上述保冷袋的冷卻效果，使保冷袋放 312/發明說明書(補件)/93-02/92134157 無機微粒 重量份， 、丙醇、 ，溶液不 可因應潛 潛熱蓄熱 丨重量份。 較佳者可 聚體、或 收容在合 拌下一面 二氧化矽 攪拌，此 製袋中而 後溶液可 。保冷袋 效果可持 入恆溫槽 9 200417361 中，圖1表示其表面溫度的時間變化之圖。恆溫槽為設定 在40°C。保冷袋預先在-10°C冷卻。為了比較起見，準備 只有水和微粉末二氧化矽的保冷袋，同樣在-1 0 ° C冷卻。 在各個保冷袋上貼附溫度感測器，放入恆溫槽而測定溫度 的時間變化。橫軸表示時間，縱軸表示溫度，線1為槽内 的溫度，線2為本發明之保冷袋，線3為比較用的保冷袋 之各個溫度變化。 槽内的溫度由於有放入保冷袋雖然其一時會下降，但又 會回到原來的4 0 °C。為了比較用的保冷袋，在自0 ° C〜1 0 ° C 之間一時溫度上升會變慢，而線部有出現彎曲部，這是因 為冰在熔化時會奪去潛熱。其後溫度會上升，3小時後會 達到4 0 ° C。本發明之保冷袋，雖然從0 °C至1 0 ° C不會有彎 曲部，但3小時後會到達大約3 0 ° C後而不會成為4 0 ° C， 因此可明白其緩缓地保持在大致一定的溫度。這是因為硫 酸鈉的1 0水合物在溶解過程中會奪去潛熱。亦即，在人體 使用時其經常可保持冷卻感。 (比較例1 ) 除不使用醇以外，和實施例1同樣製作保冷袋。保冷材 料溶液會持續在過冷卻狀態，在室溫由於長時間未析出結 晶，因此，為了要析出水合物的結晶，必須要放入冰箱中 冷卻。 (比較例2 ) 除不使用無水超微粒子二氧化矽和醇以外，和實施例 1 同樣製作保冷袋。由於原來液體就不會凝膠化，溶化時的 10 312/發明說明書(補件)/93-02/92134157 200417361 内容物為液狀，假如放入冰箱冷卻時所析出的結晶彼此會 凝固而變成板狀，因此不能作為保冷袋使用。 【圖式簡單說明】 圖1為冷卻後的本發明之保冷袋在常溫槽内，以隨時間 表示溫度變化之圖。 (產業上之利用性） 本發明之保冷袋即使在冷卻時也不會變成板狀，可保持 柔軟性，其觸感非常好。當設定溫度在2 0Q C左右則其並不 一定要放入冰箱中冷卻而在室溫亦可使保冷袋再生。又， 由於使用無機微粒子作為凝膠化物質，因此，如高分子聚 合物一般使用鹽類使熔點下降時，其保水能力也不會降低。 11 312/發明說明書(補件)/93-02/92134157Alcohols can be enumerated: ethanol butanol which does not dissolve the latent heat storage material. Accordingly, when the temperature of the cooling material aqueous solution is lowered, it is supercooled, and hydrate crystals can be easily precipitated. Although the amount of alcohol is appropriately selected according to the type of the heat storage material, 100 to 100 parts by weight is 1 to 20 parts by weight, preferably 1 to 1 C. The material of the synthetic resin bag is as long as it is flexible can. However, examples include nylon / polyethylene laminates, ethylene / vinyl acetate copolymers, and fluorenyl acrylate copolymers. The cooler bag can also be used as an outer bag made of resin or cloth. (Embodiment) The structure of the present invention will be specifically described below with reference to the embodiment. (Example 1) 160 g of sodium sulfate was added to 400 g of water, and the mixture was stirred at 28 ° C to dissolve. When the dissolving solution becomes transparent, add 20 g of fine powder (smoke-like silica, average particle size 40 nm), and then continue to add 40 g of ethanol and stir quickly. Fill with synthetic resin and seal. Take room temperature 1 8. Under C, place the cooler bag. Fine crystals were precipitated in 3 hours, and the contents became sticky gel-like softness and touch. When applied to the affected area, its cooling performance is about 5 hours. In order to observe the cooling effect of the above-mentioned cooling bag, the cooling bag is placed in 312 / Instruction Manual (Supplement) / 93-02 / 92134157 Inorganic fine particles, parts by weight, propanol, and the solution should not be stored in accordance with latent heat 丨 parts by weight. The better one can be polymerized, or stored under the mixture and stirred with silicon dioxide. The solution can be made in this bag. The effect of the cooling bag can be held in the thermostatic bath 9 200417361. Figure 1 shows the time change of the surface temperature. The thermostat was set at 40 ° C. The cooling bag is cooled in advance at -10 ° C. For comparison, prepare a cold storage bag with only water and fine powdered silica, and also cool at -10 ° C. A temperature sensor was attached to each cold storage bag, and the temperature change was measured by placing the temperature sensor in a constant temperature bath. The horizontal axis represents time, and the vertical axis represents temperature. Line 1 is the temperature in the tank, line 2 is the cooling bag of the present invention, and line 3 is the temperature change of the cooling bag for comparison. Although the temperature in the tank is lowered for a while, it will return to the original 40 ° C. For comparison purposes, the temperature rise will slow down between 0 ° C and 10 ° C, and there will be bends in the wire. This is because the ice will take away latent heat when it melts. The temperature then rises and reaches 40 ° C after 3 hours. Although the cooling bag of the present invention does not have a bent portion from 0 ° C to 10 ° C, it will reach about 30 ° C after 3 hours instead of 40 ° C. Therefore, it can be understood that it is slowly Keep it at approximately a constant temperature. This is because the sodium hydrate of 10 hydrate dissipates latent heat during the dissolution process. That is, it often maintains a cooling sensation when used by the human body. (Comparative Example 1) A cold storage bag was produced in the same manner as in Example 1 except that no alcohol was used. The cooling material solution will continue to be in the supercooled state, and no crystals will precipitate at room temperature for a long time. Therefore, in order to precipitate the hydrate crystals, it must be cooled in a refrigerator. (Comparative Example 2) A cooling bag was produced in the same manner as in Example 1 except that anhydrous ultrafine particles of silica and alcohol were not used. Since the original liquid does not gel, the contents of 10 312 / Invention Specification (Supplement) / 93-02 / 92134157 200417361 when dissolved are liquid. If the crystals precipitated when they are cooled in the refrigerator, they will solidify and become It is plate-shaped, so it cannot be used as a cooler bag. [Brief description of the drawings] Fig. 1 is a diagram showing the temperature change of the cold storage bag of the present invention in a normal temperature tank after cooling. (Industrial Applicability) The cold storage bag of the present invention does not become a plate shape even when it is cooled, it can maintain flexibility, and its touch is very good. When the set temperature is around 20Q C, it is not necessary to put it in the refrigerator for cooling, and the cold storage bag can be regenerated at room temperature. In addition, since inorganic fine particles are used as the gelling substance, when the melting point is lowered by using salts, such as polymer polymers, its water retention capacity will not be lowered. 11 312 / Invention Specification (Supplement) / 93-02 / 92134157