WO2023013752A1 - 蓄冷材 - Google Patents

蓄冷材 Download PDF

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Publication number
WO2023013752A1
WO2023013752A1 PCT/JP2022/030029 JP2022030029W WO2023013752A1 WO 2023013752 A1 WO2023013752 A1 WO 2023013752A1 JP 2022030029 W JP2022030029 W JP 2022030029W WO 2023013752 A1 WO2023013752 A1 WO 2023013752A1
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Prior art keywords
cold storage
storage material
content
material according
thf
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Ceased
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PCT/JP2022/030029
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English (en)
French (fr)
Japanese (ja)
Inventor
博宣 町田
基啓 鈴木
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Panasonic Holdings Corp
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Panasonic Holdings Corp
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Application filed by Panasonic Holdings Corp filed Critical Panasonic Holdings Corp
Priority to JP2023540420A priority Critical patent/JP7403721B2/ja
Priority to US18/293,256 priority patent/US20250092297A1/en
Priority to CN202280054027.1A priority patent/CN117769587A/zh
Priority to EP22853170.3A priority patent/EP4382583A4/en
Publication of WO2023013752A1 publication Critical patent/WO2023013752A1/ja
Priority to JP2023208923A priority patent/JP7631489B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/066—Cooling mixtures; De-icing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present disclosure relates to cold storage materials.
  • Patent Document 1 discloses a heat storage gel material that includes a heat storage liquid and a shape retainer.
  • the heat storage liquid has a heat storage main agent dispersed in water and has a predetermined phase transition temperature.
  • the shape retainer has a network structure of organic molecules and is made of agar in an amount of 0.2% by weight or more of the heat storage liquid.
  • Tetrahydrofuran (THF) is cited as an example of the heat storage main agent.
  • Patent Document 1 describes examples using a 30% by weight THF aqueous solution and agar (see the ninth example, etc.).
  • Patent Document 2 discloses a heat storage material having a first gelling material, a second gelling material, and an inorganic or water-based heat storage material.
  • the second gelling material has a water retention capacity different from that of the first gelling material and is mixed with the first gelling material.
  • An inorganic or aqueous heat storage material is held between the first gelling material and the second gelling material.
  • Synthetic polymers such as polyacrylamide derivatives or crosslinked gelatin are used as the first gelling material.
  • Natural polymers such as polysaccharides, agar, or gelatin are used as the second gelling material, and locust bean gum, xanthan gum, dulan gum, or carrageenan are used as polysaccharides.
  • the present disclosure provides a cold storage material that contains tetrahydrofuran and is advantageous from the viewpoint of suppression of syneresis during use and gel strength.
  • the cold storage material in the present disclosure is tetrahydrofuran and water and, and a thickening and gelling agent,
  • the ratio of the tetrahydrofuran content to the total amount of the tetrahydrofuran content and the water content is 0.16 or more and 0.24 or less on a mass basis
  • the thickening and gelling agent contains main ingredients consisting only of locust bean gum and xanthan gum.
  • the cold storage material in the present disclosure tends to have desired gel strength and elasticity due to the action of the thickening gelling agent. Therefore, it is advantageous from the viewpoint of suppressing syneresis during use while containing tetrahydrofuran.
  • the present inventors took the hint that the heat of fusion of tetrahydrofuran clathrate hydrate is large, and came up with the idea of producing a cold storage material containing tetrahydrofuran, water, and a thickening gelling agent. got In order to realize the idea, the present inventors discovered that there is a problem that syneresis tends to occur during use of a cold storage material containing tetrahydrofuran, water, and a thickening gelling agent. , came to constitute the subject matter of the present disclosure in order to solve the problem.
  • the present disclosure provides a cold storage material that contains tetrahydrofuran and is advantageous from the viewpoint of suppressing syneresis during use and gel strength.
  • Embodiment 1 Embodiment 1 will be described below with reference to FIG.
  • the cold storage material in Embodiment 1 contains tetrahydrofuran (THF), water, and a thickening gelling agent.
  • THF tetrahydrofuran
  • the thickening and gelling agent contains a main component consisting solely of locust bean gum and xanthan gum.
  • main component means the component contained in the largest amount on a mass basis.
  • THF and water can form clathrate hydrate.
  • Clathrate hydrate is a crystal in which guest molecules other than water are arranged in a cage-like structure formed by hydrogen bonding of water molecules.
  • the concentration of guest molecules corresponding to the state in which water molecules and guest molecules are present in just the right amount to form a clathrate hydrate is called the harmonic concentration.
  • the harmonic concentration is approximately 19% by weight.
  • the above ratio is 0.16 or more and 0.24 or less, so the content of THF is adjusted to the harmonic concentration or the vicinity of the harmonic concentration.
  • the melting point of the cold storage material can be measured using, for example, a differential scanning calorimeter (DSC), as is well known in the technical field of cold storage materials.
  • DSC differential scanning calorimeter
  • FIG. 1 is a graph showing the characteristics of the cold storage material in Embodiment 1 when the cold storage material is allowed to cool. It shows time change.
  • the horizontal and vertical axes represent time t and temperature T, respectively.
  • the temperature of the cold storage material is maintained at a temperature equal to or lower than the melting point Tm. For example, while the lid of the cooler box is closed, the temperature inside the cooler box is set to the melting point Tm or less so that the temperature of the cold storage material arranged inside the cooler box is maintained at the melting point Tm or less.
  • the cold storage material is gradually warmed. See interval F in FIG.
  • the temperature inside the cooler box gradually rises.
  • Tm melting point
  • the temperature of the cold storage material is maintained near the melting point Tm of the cold storage material. See section G included in FIG. If there is no cold storage material inside the cooler box, the temperature inside the cooler box rises continuously as shown in zone Z included in FIG.
  • the temperature inside the cooler box is maintained near the melting point of the cold storage material during the certain period of section G.
  • cold heat stored in the cold storage material can be used for cold storage.
  • the THF hydrate crystals melt and disappear in the cold storage material.
  • the THF hydrate is liquefied in the cold storage material. The longer the time period during which the cold storage material can maintain the temperature near the melting point Tm, that is, the longer the section G, the higher the cold storage performance of the cold storage material.
  • the cold storage material can be cooled and reused.
  • condition (I) The melting point of the cold storage material is equal to or several degrees Celsius lower than the appropriate temperature for perishables or foods.
  • condition (II) The cold storage material has a latent heat quantity of 225 J/g or more.
  • Condition (III) The cold storage material is gelled, not liquid.
  • the temperature inside the cooler box can be kept below the appropriate temperature for perishables or food for a long period of time when the temperature inside the cooler box rises according to the environmental temperature. .
  • the cold storage material has a large amount of latent heat.
  • the latent heat amount means the heat of fusion.
  • n-tetradecane which has a melting point of 5.9° C.
  • the latent heat of n-hexadecane, which has a melting point of 18.2° C., is 229 J/g.
  • condition (III) in the unlikely event that the container of the cold storage material is damaged, the risk of the components of the cold storage material scattering over a wide area and contamination of perishables or food can be reduced.
  • the content of the thickening gelling agent in the cold storage material is not limited to a specific value.
  • the content is, for example, 1% or more and 10% or less on a mass basis.
  • the thickening gelling agent is not limited to a specific mode as long as it contains the above-described main component.
  • the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum is not limited to any particular value.
  • the ratio is, for example, 0.15 or more and 0.85 or less on a mass basis. This ratio is preferably 0.2 or more and 0.8 or less, more preferably 0.2 or more and 0.7 or less, and still more preferably 0.2 or more and less than 0.6.
  • the ratio of the content of xanthan gum to the total amount of thickening gelling agent is not limited to a specific value.
  • the thickening gelling agent may contain components other than the main component, or may contain only the main component.
  • the thickening gelling agent may contain a predetermined amount of a component other than the main component as long as it has desired properties from the viewpoint of suppressing syneresis and gel strength.
  • the content of components other than the main component in the thickening gelling agent is, for example, 20% by mass or less.
  • the content of components other than the main component in the thickening gelling agent may be 15% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less. may be
  • the cold storage material in Embodiment 1 may contain only THF, water, and a thickening gelling agent, or may contain components other than THF, water, and a thickening gelling agent.
  • the cold storage material may contain additives such as supercooling inhibitors, thickeners, and preservatives.
  • the cold storage material preferably does not contain a synthetic polymer produced by cross-linking a polyacrylamide derivative, polyvinyl alcohol, sodium polyacrylate, and sodium polymethacrylate.
  • the cold storage material may further contain at least one silver compound selected from the group consisting of silver phosphate, silver carbonate, and silver oxide.
  • silver phosphate is represented by the chemical formula Ag3PO4 .
  • Silver carbonate is represented by the chemical formula Ag2CO3 .
  • Silver oxide is represented by the chemical formula AgO.
  • the molar ratio of the content of the silver compound to the content of water in the cold storage material is not limited to a specific value.
  • the molar ratio is, for example, 2.64 ⁇ 10 ⁇ 8 or more and 3.75 ⁇ 10 ⁇ 4 or less.
  • the ratio of the content of the silver compound to the total amount of the THF content, the water content, and the thickening gelling agent content in the cold storage material is Not limited to any particular value.
  • the ratio is, for example, 0.00050 or more and 0.020 or less on a mass basis.
  • the ratio may be 0.0010 or more and 0.010 or less on a mass basis.
  • the method of manufacturing the cold storage material in Embodiment 1 is not limited to a specific method.
  • the cold storage material in Embodiment 1 can be produced, for example, by mixing THF, water, and a thickening gelling agent, and following a process including heating and cooling. A known process can be applied to this process.
  • the cold storage material can be provided in a state where it exists inside a sealed container as needed.
  • a mixture or cold storage material containing THF, water, and thickening gelling agent may be placed in a container and the container may be sealed.
  • cold storage and cooling are repeated.
  • THF hydrate is produced from THF and water. Upon standing to cool, the THF hydrate melts. For this reason, cold storage at 10° C. or less is possible using, for example, a cold storage material.
  • the cold storage material contains a thickening gelling agent and is gelled. For this reason, for example, even if the container of the cold storage material is damaged during transportation of the goods kept cool by the cold storage material, there is a low possibility that the cold storage material scatters over a wide area and contaminates the goods being transported. . Thus, this cold storage material is advantageous from the viewpoint of safety in storage, storage and transportation.
  • the ratio of the THF content to the total amount of the THF content and the water content is 0.16 or more and 0.24 or less on a mass basis. Therefore, in this cold storage material, the content of THF is adjusted to the harmonic concentration or near the harmonic concentration, and the amount of latent heat of the cold storage material tends to increase. This is because the heat of fusion of the cold storage material forming the clathrate hydrate tends to be the highest when the guest molecule concentration is near the harmonic concentration.
  • the cold storage material contains THF, water, and a thickening gelling agent.
  • the ratio of the THF content to the total amount of the THF content and the water content is 0.16 or more and 0.24 or less on a mass basis.
  • the thickening and gelling agent contains a main component consisting solely of locust bean gum and xanthan gum.
  • the cold storage material is advantageous from the viewpoint of suppressing syneresis during use while containing tetrahydrofuran.
  • the thickening and gelling agent may not contain a synthetic polymer produced by cross-linking a polyacrylamide derivative, polyvinyl alcohol, sodium polyacrylate, and sodium polymethacrylate. .
  • This makes it easier for the cold storage material to have desired gel strength and elasticity. Therefore, the cold storage material is more advantageous from the viewpoint of suppressing syneresis during use while containing tetrahydrofuran.
  • the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum may be 0.15 or more and 0.85 or less on a mass basis. This makes it easier for the cold storage material to have desired gel strength and elasticity. Therefore, the cold storage material is more advantageous from the viewpoint of suppressing syneresis during use while containing tetrahydrofuran.
  • the content of components other than the main component in the thickening gelling agent may be 20% by mass or less. Even in such a case, the cold storage material can have desired gel strength and elasticity. Therefore, the cold storage material is more advantageous from the viewpoint of suppressing syneresis during use while containing tetrahydrofuran.
  • the cold storage material may further contain at least one silver compound selected from the group consisting of silver phosphate, silver carbonate, and silver oxide.
  • the oxygen atoms (hydrophilic groups) in the THF molecule are more likely to be stabilized by coordinate bonding with the silver atoms of the silver compound than by hydrogen bonding with water molecules. For this reason, the proportion of THF molecules coordinated tends to increase.
  • the hydrophilic groups of the coordinated THF molecules are coordinated to the silver atoms, and the hydrophobic groups of the THF molecules are surrounded by water. As a result, the THF molecule becomes suitable for hydrophobic hydration.
  • the oxygen atom in the silver-oxygen bond of the silver compound plays a role in stabilizing the coordination bond.
  • THF molecules and water molecules are more likely to form clathrate hydrate through molecular motion. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the temperature at which THF hydrate is generated in the cold storage material tends to increase, for example, the temperature reaches 0° C. or higher, and THF clathrate hydrate is likely to be formed without ice being formed.
  • the silver compound may be silver phosphate as in the present embodiment.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the silver compound may be silver carbonate.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the silver compound may be silver oxide as in the present embodiment.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the molar ratio of the content of the silver compound to the content of water may be 2.64 ⁇ 10 ⁇ 8 or more and 3.75 ⁇ 10 ⁇ 4 .
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the ratio of the content of the silver compound to the total content of the tetrahydrofuran content, the water content, and the thickening gelling agent content is 0.00050 on a mass basis. It may be greater than or equal to 0.020 or less. This ratio may be 0.0010 or more and 0.010 or less on a mass basis.
  • the cold storage material in Embodiment 2 contains THF, water, and a thickening gelling agent.
  • Thickening and gelling agents include seed-derived polysaccharides and microorganism-derived polysaccharides. Thickening gelling agents are gellable by heating and cooling.
  • a thickening gelling agent can gel a mixture containing THF, water, and a thickening gelling agent only by adjusting the temperature without adding a cation.
  • Regenerator materials are determined to be solid by the ASTM D 4359-90 solid-liquid determination test.
  • the seed-derived polysaccharide contained in the thickening gelling agent is not limited to a specific polysaccharide.
  • An example of a seed-derived polysaccharide is locust bean gum.
  • the microbial-derived polysaccharide contained in the thickening gelling agent is not limited to a specific polysaccharide.
  • An example of a microbial polysaccharide is xanthan gum.
  • the thickening and gelling agent is not limited to a specific mode as long as it contains a seed-derived polysaccharide and a microorganism-derived polysaccharide.
  • the thickening gelling agent may contain multiple types of polysaccharides.
  • the thickening gelling agent may contain locust bean gum and xanthan gum.
  • the ratio of the content of xanthan gum to the total amount of thickening gelling agent is not limited to a specific value. For example, the ratio may be greater than or equal to 0.6 on a mass basis, or the ratio may be less than 0.6.
  • the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum is, for example, 0.15 or more and 0.7 or less on a mass basis. This ratio may be 0.2 or more and 0.7 or less, or may be 0.3 or more and 0.7 or less, based on mass.
  • the ratio of the THF content to the total amount of the THF content and the water content is not limited to a specific value.
  • the ratio is, for example, 0.16 or more and 0.24 or less on a mass basis.
  • the cold storage material in Embodiment 2 may contain only THF, water, and a thickening gelling agent, or may contain components other than THF, water, and a thickening gelling agent.
  • the cold storage material may contain additives such as supercooling inhibitors, thickeners, and preservatives.
  • the cold storage material preferably does not contain a synthetic polymer produced by cross-linking a polyacrylamide derivative, polyvinyl alcohol, sodium polyacrylate, and sodium polymethacrylate.
  • the cold storage material may further contain at least one silver compound selected from the group consisting of silver phosphate, silver carbonate, and silver oxide.
  • silver phosphate is represented by the chemical formula Ag3PO4 .
  • Silver carbonate is represented by the chemical formula Ag2CO3 .
  • Silver oxide is represented by the chemical formula AgO.
  • the molar ratio of the content of the silver compound to the content of water in the cold storage material is not limited to a specific value.
  • the molar ratio is, for example, 2.64 ⁇ 10 ⁇ 8 or more and 3.75 ⁇ 10 ⁇ 4 or less.
  • the ratio of the content of the silver compound to the total amount of the THF content, the water content, and the thickening gelling agent content in the cold storage material is Not limited to any particular value.
  • the ratio is, for example, 0.00050 or more and 0.020 or less on a mass basis.
  • the ratio may be 0.0010 or more and 0.010 or less on a mass basis.
  • the method of manufacturing the cold storage material in Embodiment 2 is not limited to a specific method.
  • the cold storage material in the second embodiment can be manufactured by referring to the manufacturing method of the cold storage material in the first embodiment.
  • cold storage production of THF hydrate
  • cooling melting of THF hydrate
  • the cold storage material contains a thickening gelling agent and is gelled. Additionally, the regenerator material is determined to be solid by the ASTM D 4359-90 solid-liquid determination test. Therefore, for example, even if the container of the cold storage material is damaged during transportation of the cold storage material, the cold storage material is less likely to scatter over a wide area and contaminate the items being transported. This cold storage material is advantageous from the viewpoint of safety in storage, storage and transportation.
  • the cold storage material contains THF, water, and a thickening gelling agent.
  • Thickening and gelling agents include seed-derived polysaccharides and microorganism-derived polysaccharides.
  • Regenerator materials are determined to be solid by the ASTM D 4359-90 solid-liquid determination test.
  • the cold storage material is advantageous from the viewpoint of suppressing separation of water during use while containing THF.
  • the thickening and gelling agents described above can be gelled by heating and cooling, for example, and can be gelled only by temperature adjustment without the addition of cations. For this reason, it is possible to avoid freezing point depression due to the addition of cations, and the melting point of THF hydrate in the cold storage material is unlikely to be lowered.
  • the amount of latent heat of the cold storage material tends to increase. For example, the latent heat amount of the cold storage material tends to be 225 J/g or more.
  • the thickening and gelling agent may contain locust bean gum and xanthan gum.
  • the ratio of the content of xanthan gum to the total amount of thickening and gelling agents may be 0.6 or more on a mass basis.
  • the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum may be 0.15 or more and 0.7 or less on a mass basis.
  • the cold storage material may further contain at least one silver compound selected from the group consisting of silver phosphate, silver carbonate, and silver oxide.
  • the THF molecules are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion in the cold storage material tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the temperature at which THF hydrate is generated in the cold storage material tends to increase, for example, the temperature tends to be 0° C. or higher.
  • the silver compound may be silver phosphate as in the present embodiment.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the silver compound may be silver carbonate.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the silver compound may be silver oxide as in the present embodiment.
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the molar ratio of the content of the silver compound to the content of water may be 2.64 ⁇ 10 ⁇ 8 or more and 3.75 ⁇ 10 ⁇ 4 .
  • the THF molecules in the cold storage material are brought into a state suitable for hydrophobic hydration, and the probability of THF molecules and water molecules forming clathrate hydrate through molecular motion tends to increase. Therefore, supercooling is likely to be suppressed in the cold storage material.
  • the ratio of the content of the silver compound to the total content of the THF content, the water content, and the thickening and gelling agent content is 0.00050 on a mass basis. It may be greater than or equal to 0.020 or less. This ratio may be 0.0010 or more and 0.010 or less on a mass basis.
  • Embodiment 3 (Embodiment 3) Embodiment 3 will be described below with reference to FIG.
  • FIG. 2 shows the cooler box 100 according to the third embodiment.
  • the cooler box 100 comprises an insulation box 101 having a bottom (not shown) and sides, and an insulation lid 102 .
  • the cold storage material in the first or second embodiment is placed along at least one selected from the group consisting of the inner bottom surface of the heat insulating box 101, the inner side surface of the heat insulating box 101, and the inner surface of the heat insulating lid 102.
  • a cold storage material pack 110 containing the cold storage material according to the first or second embodiment is provided so as to be in contact with each of the four inner side surfaces of a heat insulating box 101 having a rectangular parallelepiped shape.
  • the cold storage material in Embodiment 1 or 2 may be arranged in at least one selected from the group consisting of the inside of the bottom of the heat insulating box 101, the inside of the side portion of the heat insulating box 101, and the inside of the heat insulating lid 102. .
  • the cold storage material in Embodiment 1 or 2 may be arranged in the space inside the cooler box 100 while being enclosed in the cold storage material pack 110 .
  • the space inside cooler box 100 is, for example, a space formed by the inner bottom surface of heat insulating box 101 , the inner side surface of heat insulating box 101 , and the inner surface of heat insulating lid 102 .
  • the cold storage material in Embodiment 1 or 2 may be provided in at least one interior selected from the group consisting of the side portion of the heat insulation box, the heat insulation lid of the heat insulation box, and the heat insulation box itself. Also in this case, the cold storage material in the first or second embodiment may be arranged in a state of being enclosed in the cold storage material pack 110 .
  • At least one selected from the group consisting of pharmaceuticals, biological tissues, cells, foods, and flowers is placed inside the heat-insulating box 101, for example.
  • the cold storage material according to Embodiment 1 or 2 is used for storage, preservation, or transportation of objects that require freshness preservation, such as pharmaceuticals, living tissue, cells, foods, and flowers.
  • a medicine 120 is placed inside the heat insulating box 101 shown in FIG.
  • pharmaceuticals are liquid pharmaceuticals.
  • An example of a liquid pharmaceutical product is a vaccine. Since the cooler box according to the third embodiment includes the cold storage material according to the first or second embodiment, it is suitable for storing, storing, and transporting objects that require freshness retention.
  • THF tetrahydrofuran
  • Example 1A-1 As shown in Table 1, 0.38g of polysaccharide, 1.83g of THF and 7.78g of pure water were added to a screw tube with a capacity of 60ml to obtain a mixture.
  • the polysaccharides contained only locust bean gum and xanthan gum, and the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum was 0.5 on a mass basis.
  • the mixture was sufficiently stirred in a screw tube, heated to 60° C., and allowed to cool naturally. Thus, a cold storage material according to Example 1A-1 was obtained. In Example 1A-1, the mixture gelled only by heating and cooling. Screw tubes were glass tubes with screwed caps. The content of polysaccharides in the cold storage material was 4% by mass.
  • Example 1A-1 Average 10 mg of the cold storage material according to Example 1A-1 was subjected to differential scanning calorimetry (DSC) using a differential scanning calorimeter DSC-8500 manufactured by PerkinElmer Japan. This measurement was made with temperature adjustments as preprogrammed. First, the temperature of the reference material was maintained at 20 degrees Celsius for 10 minutes. The temperature of the reference material was then lowered at a rate of 1 degree Celsius/minute. During the cooling process, a temperature rise accompanying the formation of THF hydrate in the cold storage material was observed as an exothermic peak, after which the temperature of the cold storage material converged to the programmed temperature. This confirmed the completion of crystallization of THF hydrate.
  • DSC differential scanning calorimeter
  • the temperature of the cold storage material when the temperature of the cold storage material started to rise in this cooling process was determined as the crystallization temperature Tc of the cold storage material.
  • Tc crystallization temperature
  • the temperature of the reference material was maintained at minus 20 degrees Celsius for 10 minutes.
  • the temperature of the reference material was then increased from minus 20 degrees Celsius to 20 degrees Celsius at a rate of 1 degree Celsius/minute.
  • the endothermic peak temperature in this case was taken as the melting point Tm, and the endothermic amount was determined as the latent heat amount.
  • the melting point Tm and latent heat amount of the cold storage material according to Example 1A-1 were determined using a differential scanning calorimeter DSC-8500.
  • the melting point Tm of the cold storage material according to Example 1A-1 was 5.0 degrees Celsius, and the latent heat amount of the cold storage material was 240 J/g. Table 5 shows the results.
  • Example 1A-1 The cold storage material according to Example 1A-1 was allowed to stand in an environment of 40° C. for 4 hours or longer. After that, the screw tube containing the cold storage material according to Example 1A-1 was placed sideways (tilted at 90°) for 3 minutes in an environment of 40°C, and then the state of the cold storage material was visually confirmed. Based on this confirmation result, the gel strength of the cold storage material was evaluated according to the following criteria. Table 5 shows the results. A: The interface between the cold storage material and air extends vertically without deformation. B: A relatively small deformation is observed at the interface between the cold storage material and the air. C: Relatively large deformation is observed at the interface between the cold storage material and air.
  • Example 1A-1 The cold storage material according to Example 1A-1 was allowed to stand in an environment of 40° C. for 4 hours. After that, the screw tube containing the cold storage material was placed sideways (tilted at 90°) for 3 minutes in an environment of 40°C, and then the state of the cold storage material was visually confirmed. Based on this confirmation result, the separation of water from the cold storage material was evaluated according to the following criteria. Table 5 shows the results. A: Separation of liquid components is not clearly observed. NG: Separation of liquid components is clearly observed.
  • Example 1A-2 A cold storage material according to Example 1A-2 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 1. Silver (II) oxide was Silver (II) Oxide obtained from Fujifilm Wako Pure Chemical Industries, Ltd. and was added as a supercooling inhibitor. The cold storage material according to Example 1A-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1A-3 A cold storage material according to Example 1A-3 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 1. Silver(I) phosphate was silver(I) phosphate obtained from Mitsuwa Chemical Co., Ltd. and was added as a supercooling inhibitor. The cold storage material according to Example 1A-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1A-4 A cold storage material according to Example 1A-4 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 1. Silver carbonate was silver carbonate obtained from Fujifilm Wako Pure Chemical Industries, Ltd. and was added as a supercooling inhibitor. The cold storage material according to Example 1A-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1B-1 A cold storage material according to Example 1B-1 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 1. The cold storage material according to Example 1B-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1B-2 A cold storage material according to Example 1B-2 was prepared in the same manner as in Example 1A-2 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 1. The cold storage material according to Example 1B-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1B-3 A cold storage material according to Example 1B-3 was prepared in the same manner as in Example 1A-3 except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 1. The cold storage material according to Example 1B-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 1B-4 A cold storage material according to Example 1B-4 was prepared in the same manner as in Example 1A-4 except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 1. The cold storage material according to Example 1B-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2A-1 A cold storage material according to Example 2A-1 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 2. The polysaccharides contained only locust bean gum and xanthan gum, and the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum was 0.4 on a mass basis. The cold storage material according to Example 2A-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2A-2 A cold storage material according to Example 2A-2 was prepared in the same manner as in Example 2A-1 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 2. The cold storage material according to Example 2A-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2A-3 A cold storage material according to Example 2A-3 was prepared in the same manner as in Example 2A-1 except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 2. The cold storage material according to Example 2A-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2A-4 A cold storage material according to Example 2A-4 was prepared in the same manner as in Example 2A-1 except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 2. The cold storage material according to Example 2A-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2B-1 A cold storage material according to Example 2B-1 was prepared in the same manner as in Example 2A-1 except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 2. The cold storage material according to Example 2B-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2B-2 A cold storage material according to Example 2B-2 was prepared in the same manner as in Example 2A-2 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 2. The cold storage material according to Example 2B-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2B-3 A cold storage material according to Example 2B-3 was prepared in the same manner as in Example 2A-3, except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 2. The cold storage material according to Example 2B-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2B-4 A cold storage material according to Example 2B-4 was prepared in the same manner as in Example 2A-4, except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 2. The cold storage material according to Example 2B-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2C-1 A cold storage material according to Example 2C-1 was prepared in the same manner as in Example 1A-1 except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 2. The polysaccharides contained only locust bean gum and xanthan gum, and the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum was 0.25 on a mass basis. The cold storage material according to Example 2C-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2C-2 A cold storage material according to Example 2C-2 was prepared in the same manner as in Example 1A-2 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 2. The cold storage material according to Example 2C-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2C-3 A cold storage material according to Example 2C-3 was prepared in the same manner as in Example 1A-3, except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 2. The cold storage material according to Example 2C-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2C-4 A cold storage material according to Example 2C-4 was prepared in the same manner as in Example 1A-4, except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 2. The cold storage material according to Example 2C-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2D-1 A cold storage material according to Example 2D-1 was prepared in the same manner as in Example 2C-1, except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 2. The cold storage material according to Example 2D-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2D-2 A cold storage material according to Example 2D-2 was prepared in the same manner as in Example 2C-2, except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 2. The cold storage material according to Example 2D-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2D-3 A cold storage material according to Example 2D-3 was prepared in the same manner as in Example 2C-3, except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 2. The cold storage material according to Example 2D-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2D-4 A cold storage material according to Example 2D-4 was prepared in the same manner as in Example 2C-4, except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 2. The cold storage material according to Example 2D-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2E-1 A cold storage material according to Example 2E-1 was prepared in the same manner as in Example 1A-1, except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 3. The polysaccharides contained only locust bean gum and xanthan gum, and the ratio of the amount of locust bean gum to the total amount of locust bean gum and xanthan gum was 0.2 on a mass basis. The cold storage material according to Example 2E-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2E-2 A cold storage material according to Example 2E-2 was prepared in the same manner as in Example 1A-2 except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 3. The cold storage material according to Example 2E-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2E-3 A cold storage material according to Example 2E-3 was prepared in the same manner as in Example 1A-3, except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 3. The cold storage material according to Example 2E-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2E-4 A cold storage material according to Example 2E-4 was prepared in the same manner as in Example 1A-4 except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 3. The cold storage material according to Example 2E-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2F-1 A cold storage material according to Example 2F-1 was prepared in the same manner as in Example 2E-1 except for the following points. Polysaccharide, THF, and pure water were added in the amounts shown in Table 3. The cold storage material according to Example 2F-1 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2F-2 A cold storage material according to Example 2F-2 was prepared in the same manner as in Example 2E-2, except for the following points. Polysaccharide, THF, pure water, and silver (II) oxide were added in the amounts shown in Table 3. The cold storage material according to Example 2F-2 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2F-3 A cold storage material according to Example 2F-3 was prepared in the same manner as in Example 2E-3, except for the following points. Polysaccharide, THF, pure water, and silver (I) phosphate were added in the amounts shown in Table 3. The cold storage material according to Example 2F-3 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Example 2F-4 A cold storage material according to Example 2F-4 was prepared in the same manner as in Example 2E-4, except for the following points. Polysaccharide, THF, pure water, and silver carbonate were added in the amounts shown in Table 3. The cold storage material according to Example 2F-4 was evaluated in the same manner as in Example 1A-1. Table 5 shows the results.
  • Comparative example 1 A cold storage material according to Comparative Example 1 was prepared in the same manner as in Example 1A-1, except for the following points. Guar gum was used as the polysaccharide. Guar gum, THF, and pure water were added in the amounts shown in Table 4. In Comparative Example 1, a mixture of guar gum, THF, and pure water was heated to 60° C. and allowed to cool naturally. In Comparative Example 1, gelation could not be achieved only by heating and cooling. The cold storage material according to Comparative Example 1 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Example 2 A cold storage material according to Comparative Example 2 was prepared in the same manner as in Example 1A-1, except for the following points.
  • Low-Acyl (LA) gellan gum was used as the polysaccharide.
  • LA gellan gum is also called deacylated gellan gum.
  • LA gellan gum, THF, and pure water were added in the amounts shown in Table 4.
  • a mixture of LA gellan gum, THF, and pure water was heated to 40° C. and allowed to cool naturally.
  • gelation was not possible only by heating and cooling, and addition of calcium lactate (calcium ions) was necessary.
  • the cold storage material according to Comparative Example 2 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Comparative Example 3 A cold storage material according to Comparative Example 3 was prepared in the same manner as in Example 1A-1, except for the following points.
  • Agar was used as the polysaccharide.
  • Agar and pure water were added in the amounts shown in Table 4.
  • Comparative Example 3 a mixture of agar and pure water was heated to 90° C. and then allowed to cool naturally. After that, THF was added in the amounts shown in Table 4 and left to stir.
  • the cold storage material according to Comparative Example 3 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Comparative Example 4 A cold storage material according to Comparative Example 4 was prepared in the same manner as in Comparative Example 3 except for the following points.
  • a mixture of guar gum and agar was used instead of agar. The content of agar in this mixture was 50% by weight.
  • a mixture of guar gum and agar and pure water were added in the amounts shown in Table 4.
  • a mixture of guar gum, agar and pure water was heated to 90° C. and allowed to cool naturally. After that, THF was added in the amounts shown in Table 4 and left to stir.
  • the cold storage material according to Comparative Example 4 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Comparative Example 5 A cold storage material according to Comparative Example 5 was prepared in the same manner as in Comparative Example 3 except for the following points.
  • a mixture of guar gum and agar was used instead of agar. The content of agar in this mixture was 80% by weight.
  • a mixture of guar gum and agar and pure water were added in the amounts shown in Table 4.
  • a mixture of guar gum, agar and pure water was heated to 90° C. and then allowed to cool naturally. After that, THF was added in the amounts shown in Table 4 and left to stir.
  • the cold storage material according to Comparative Example 5 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Example 6 A cold storage material according to Comparative Example 6 was prepared in the same manner as in Example 1A-1, except for the following points.
  • sodium polyacrylate was added in the amounts shown in Table 4.
  • Sodium polyacrylate was Sodium polyacrylate Poly(acrylic acid), sodium salt, 20% soln. In water [MW ⁇ 225,000] manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the cold storage material according to Comparative Example 6 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • Comparative Example 7 A cold storage material according to Comparative Example 7 was prepared in the same manner as in Example 1A-1, except for the following points. In addition to the polysaccharide, THF, and pure water, sodium polyacrylate was added in the amounts shown in Table 4. The cold storage material according to Comparative Example 7 was evaluated in the same manner as in Example 1A-1. Table 6 shows the results.
  • the gel strength of the cold storage material according to each example was good.
  • syneresis was not clearly confirmed in the cold storage material according to each example, and it was shown that although the cold storage material according to each example contains THF, water separation is unlikely to occur during use.
  • a 1 L (liter) sample of the cold storage material was prepared so that the mass ratio of each component in the cold storage material according to each example was equal, and a solid-liquid determination test according to ASTM D 4359-90 was performed. As a result, it was determined that the cold storage material according to each example was solid.
  • Example 1B-1 This heating temperature is higher than the boiling point of THF, and if such heating is performed in the presence of THF, THF may boil and the properties of the cold storage material may deteriorate.
  • a comparison between Example 1B-1 and Comparative Examples 6 and 7 suggested that the addition of sodium polyacrylate was undesirable from the viewpoint of syneresis and gel strength. Comparing Comparative Examples 6 and 7, it was suggested that the higher the content of sodium polyacrylate, the greater the amount of syneresis and the lower the gel strength.
  • the cold storage material As shown in Table 5, according to comparison between Example 1A-1 and Examples 1A-2 to 1A-4, etc., when a predetermined silver compound is added as a supercooling inhibitor, the cold storage material It is understood that the crystallization temperature Tc of is likely to increase. For example, the crystallization temperature of the cold storage material is improved from a low temperature of minus 20 degrees Celsius to a high temperature of 0 degrees Celsius or more and 3 degrees Celsius or less.
  • the cold storage material according to the present disclosure can be used for storing, storing, or transporting objects that require freshness preservation, such as pharmaceuticals, living tissue, cells, foods, and flowers.

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