Classifications

• • 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
• • 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 invention relates to a method for producing a heat storage agent composition.
• Some pharmaceuticals and specimens handled by medical institutions such as hospitals, and food products handled by supermarkets, etc., need to be kept cold or warm within a predetermined temperature range during transportation in order to maintain their quality.
• a method for keeping cold or warm articles such as medicines, specimens, and foods of this type
• a method using a latent heat storage material that utilizes phase transition such as melting of a substance and latent heat is known.
• a heat storage material that has been melted or solidified in advance is placed in an adiabatic transport container, and the latent heat of this heat storage material is used to keep the goods stored in the transport container cool or warm.
• a predetermined temperature range (hereinafter sometimes referred to as "controlled temperature”) for a long time.
• a heat storage material having a melting temperature and/or a solidification temperature within a predetermined temperature range.
• Patent Literature 1 discloses a heat storage agent composition containing an aqueous solution of at least one water-soluble salt that is insoluble in polyalkylene glycol and polyalkylene glycol.
• Patent Document 2 discloses a heat storage agent composition containing methyl laurate, 12-hydroxystearic acid and sorbitan fatty acid ester.
• the weight ratio of methyl laurate and 12-hydroxystearic acid is within a specific range
• the weight ratio of methyl laurate and sorbitan fatty acid ester is within a specific range. .
• the conventional heat storage agent composition described above still has room for improvement from the viewpoint of safety and melting temperature range.
• the present invention has been made in view of the above problems, and its object is to be able to maintain the temperature of a temperature-controlled article in various controlled temperature ranges, and not fall under the dangerous goods under the Fire Service Act of Japan. , to provide a novel heat storage agent composition.
• the present inventor has completed the present invention as a result of diligent studies to solve the above problems.
• a method for producing a heat storage agent composition comprises a polyalkylene glycol solution (I) containing a polyalkylene glycol and a metal soap (A) soluble in the polyalkylene glycol, a metal ion ( and C), wherein the metal ion (C) converts the metal soap (A) into the polyalkylene glycol-insoluble metal soap (B).
• the heat storage agent composition disclosed in Patent Document 1 still has room for improvement from the viewpoint of safety. Specifically, the heat storage agent composition disclosed in Patent Document 1 is highly probable to be regarded as belonging to the fourth category of hazardous materials under the Fire Service Act of Japan. In other words, the heat storage agent composition disclosed in Patent Document 1 is considered to be a hazardous material when (a) stored or (b) transported by means of transportation such as vehicles, aircraft, ships, etc. It is highly probable. Therefore, the heat storage agent composition disclosed in Patent Document 1 is required to be stored/managed in a warehouse for hazardous materials, and when special restrictions are imposed on storage such as a limited amount of storage.
• the heat storage agent composition disclosed in Patent Document 1 requires labeling/procedures as a dangerous substance when transported by transportation means such as vehicles, aircraft, and ships, and the amount of loading is In some cases, there may be special restrictions on transportation, such as being restricted.
• the heat storage agent composition disclosed in Patent Document 2 still has room for improvement from the viewpoint of the melting temperature range.
• the heat storage agent composition disclosed in Patent Document 2 is a composition containing methyl laurate as a main component. Therefore, the heat storage agent composition disclosed in Patent Document 2 has a melting temperature of 1°C to 10°C.
• some articles such as medicines, specimens, and foods have a temperature that should be kept cold or warm (that is, a controlled temperature) in a temperature range higher than 10°C.
• the present inventors conducted extensive studies in order to obtain a heat storage agent composition that can maintain the temperature of articles to be temperature-controlled in various controlled temperature ranges and that does not fall under the category of dangerous substances under the Fire Service Act of Japan. .
• the present inventors investigated the use of polyalkylene glycol whose melting temperature can change depending on the number average molecular weight.
• the present inventor conducted extensive research in order to provide a heat storage agent composition that contains polyalkylene glycol and does not fall under the category of hazardous materials under the Fire Service Act of Japan. More specifically, the present inventors conducted extensive studies with the aim of retaining the shape of a heat storage agent composition containing polyalkylene glycol (for example, containing it as a main component) even at 40°C.
• organic gelling agents e.g., carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose
• organic gelling agents e.g., carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose
• these organic gelling agents are insoluble in polyalkylene glycol, and could not retain the shape of the heat storage agent composition containing polyalkylene glycol even at 40°C. Therefore, the present inventor further searched for a compound capable of retaining the shape of a heat storage agent composition containing polyalkylene glycol even at 40°C.
• the metal soap (B) is insoluble in polyalkylene glycol, and the metal soap (B) can be deposited in a uniformly dispersed state in the composition;
• the produced metal soap (B) functions as a gelling agent (thickening agent), so that the resulting composition (heat storage agent composition) retains its shape at 40°C.
• soluble in polyalkylene glycol means that the solubility in polyethylene glycol at 23°C is 3% (weight/weight%) or more.
• insoluble in polyalkylene glycol is intended to have a solubility of less than 3% (wt/wt%) in polyethylene glycol at 23°C.
• metal soaps (A) that are soluble in polyalkylene glycol.
• metal soaps lithium stearate, lithium laurate, lithium montanate, sodium laurate, sodium stearate, sodium 12-hydroxystearate, sodium behenate, sodium montanate, lauric acid.
• the polyalkylene glycol may retain its shape at 40°C.
• the metal soap (B) since the metal soap (B) is insoluble in polyalkylene glycol, when the metal soap (B), which is insoluble in polyalkylene glycol, is directly added to the polyalkylene glycol, the metal soap (B) is uniform in the polyalkylene glycol. not distributed to As a result, there is also the problem that the physical properties of the obtained heat storage agent composition are not stable.
• the metal soap (A) soluble in polyalkylene glycol is uniformly dispersed in the polyalkylene glycol, and then the metal soap (A) is converted to the metal soap (B). . Therefore, there is an advantage that the obtained heat storage agent composition retains its shape at 40° C. and also has stable physical properties. That is, in one embodiment of the present invention, among many metal soaps, a metal soap (A) that is soluble in polyalkylene glycol is used.
• a method for producing a heat storage agent composition comprises a polyalkylene glycol solution (I) containing a polyalkylene glycol and a metal soap (A) soluble in the polyalkylene glycol; and mixing.
• the metal ion (C) is an ion that changes the metal soap (A) into the polyalkylene glycol-insoluble metal soap (B).
• the "method for producing a heat storage agent composition according to one embodiment of the present invention” may be referred to as “this production method”.
• the “step of mixing the polyalkylene glycol solution (I) and the metal ions (C)” may also be referred to as the “metal ion (C) mixing step”.
• “polyalkylene glycol solution (I)” may be simply referred to as “solution (I)”.
• the heat storage agent composition obtained by this production method can maintain the temperature of the temperature-controlled article in various controlled temperature ranges (eg, 1°C to 40°C). Therefore, the heat storage agent composition obtained by the present production method can be used to treat temperature-controlled articles whose controlled temperature is in the range of 1° C. to 40° C. in a specific environment within the controlled temperature of each temperature-controlled article. allow storage or transportation; In addition, since this production method has the above-described configuration, the heat storage agent composition obtained by this production method is judged not to fall under the category of dangerous goods under the Fire Service Act of Japan, and restrictions on handling are relaxed. have advantages.
• the heat storage agent composition obtained by this production method does not undergo solid-liquid separation even after multiple uses, and thus has the advantage of being able to withstand long-term use.
• the heat storage agent composition obtained by this production method is safe, can withstand long-term use, and can suppress the amount of diffusion by retaining its shape (gelation) in the unlikely event of leakage. Therefore, it can be said that the heat storage agent composition is more environmentally friendly than the conventional heat storage agent composition. Therefore, one embodiment of the present invention can contribute to achieving the Sustainable Development Goals (SDGs).
• SDGs Sustainable Development Goals
• the heat storage agent composition according to one embodiment of the present invention stores thermal energy applied from the outside while the heat storage agent composition undergoes a phase transition from a solidified state (solid) to a molten state (in other words, during melting). It can be used as a latent heat type heat storage material. Therefore, the heat storage agent composition according to one embodiment of the present invention can also be said to be a "melting-type latent heat storage agent composition". In addition, the heat storage agent composition according to one embodiment of the present invention releases thermal energy to the outside during the phase transition of the heat storage agent composition from the molten state to the solidified state (solid) (in other words, during solidification). It can be used as a latent heat type heat storage material. Therefore, the heat storage agent composition according to one embodiment of the present invention can also be said to be a "solidifying latent heat storage agent composition".
• Polyalkylene glycol is not particularly limited.
• polyalkylene glycols include polyalkylene glycols having 2 to 4 carbon atoms in the alkylene group.
• Specific examples of polyalkylene glycol include polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol. As the polyalkylene glycol, one of these may be used alone, or two or more thereof may be used in combination.
• the polyalkylene glycol preferably contains any one of polyethylene glycol and polypropylene glycol, in which the alkylene group has 2 to 3 carbon atoms, and includes polyethylene glycol. is more preferred, and polyethylene glycol is even more preferred.
• the number average molecular weight of polyalkylene glycol is not particularly limited. Polyalkylene glycols have different melting points depending on the number average molecular weight. Therefore, by changing the number average molecular weight of the polyalkylene glycol used in the production method of the present invention and/or by using a plurality of polyalkylene glycols with different number average molecular weights, the heat storage agent composition obtained Solidification start temperature can be adjusted.
• the melting point of polyethylene glycol having a number average molecular weight of 200 is -65°C to -50°C
• the melting point of polyethylene glycol having a number average molecular weight of 400 is 4°C to 8°C
• the melting point of polyethylene glycol having a number average molecular weight of 600 is -65°C to -50°C.
• the melting point of some polyethylene glycol is 15°C to 25°C
• the melting point of polyethylene glycol with a number average molecular weight of 1000 is 30°C to 40°C.
• the number average molecular weight of the polyalkylene glycol is preferably from 200 to 20,000, more preferably from 400 to 10,000, even more preferably from 400 to 1,000.
• This configuration has the advantage of being able to adjust the solidification start temperature of the heat storage agent composition to a temperature range suitable for constant temperature transportation of pharmaceuticals, medical devices, cells, specimens, organs, chemical substances, foods, and the like.
• only a single number-average molecular weight polyalkylene glycol may be used, or two or more different number-average molecular weight polyalkylene glycols may be used in combination.
• the heat storage agent composition contains polyalkylene glycol with a number average molecular weight of 400 and polyalkylene glycol with a number average molecular weight of 600
• the weight ratio of the polyalkylene glycol having a number average molecular weight of 400 to the polyalkylene glycol having a number average molecular weight of 600 in the heat storage agent composition is preferably 0.20 to 2.00, more preferably 0.30 to 1.50, still more preferably 0.40 to 1.20, and particularly preferably 0.50 to 1.00.
• This configuration has the advantage of being able to adjust the solidification start temperature of the heat storage agent composition to a temperature range suitable for constant temperature transportation of pharmaceuticals, medical devices, cells, specimens, organs, chemical substances, foods, and the like.
• the heat storage agent composition contains polyalkylene glycol with a number average molecular weight of 400, polyalkylene glycol with a number average molecular weight of 600, and polyalkylene glycol with a number average molecular weight of 1000 will be described. .
• the weight ratio of the polyalkylene glycol having a number average molecular weight of 400 to the polyalkylene glycol having a number average molecular weight of 600 in the heat storage agent composition is , is preferably 0.20 to 2.00, more preferably 0.25 to 1.50, even more preferably 0.30 to 1.00, and particularly preferably 0.35 to 0.80.
• the weight ratio of the polyalkylene glycol having a number average molecular weight of 1000 to the polyalkylene glycol having a number average molecular weight of 400 in the heat storage agent composition is preferably 0.01 to 2.00, more preferably 0.03 to 1.50, even more preferably 0.03 to 1.00, and particularly preferably 0.05 to 0.50.
• the weight ratio of the polyalkylene glycol with a number average molecular weight of 1000 to the polyalkylene glycol with a number average molecular weight of 600 in the heat storage agent composition is preferably 0.010 to 0.5000, more preferably 0.015 to 0.3000, more preferably 0.020 to 0.250, more preferably 0.025 to 0.100, and 0.030 to 0.080 is particularly preferred.
• the heat storage agent composition contains polyalkylene glycol with a number average molecular weight of 600 and polyalkylene glycol with a number average molecular weight of 1000
• the weight ratio of polyalkylene glycol with a number average molecular weight of 1000 to polyalkylene glycol with a number average molecular weight of 600 in the heat storage agent composition is preferably 0.040 to 1.000, more preferably 0.080 to 0.750, even more preferably 0.120 to 0.500, and particularly preferably 0.150 to 0.350.
• This configuration has the advantage of being able to adjust the solidification start temperature of the heat storage agent composition to a temperature range suitable for constant temperature transportation of pharmaceuticals, medical devices, cells, specimens, organs, chemical substances, foods, and the like.
• the number average molecular weight of polyalkylene glycol is a value obtained by measuring by SEC method (Size Exclusion Chromatography).
• the polyalkylene glycol may be the main ingredient.
• the polyalkylene glycol may account for 50% by weight or more in 100% by weight of the heat storage agent composition obtained by this production method.
• the heat storage agent composition obtained by this production method when polyalkylene glycol is the main ingredient, the heat storage agent composition has an advantage of being excellent in safety.
• the amount of polyalkylene glycol in the heat storage agent composition obtained by this production method is not particularly limited.
• the amount of polyalkylene glycol in the heat storage agent composition is preferably 60% by weight or more, more preferably 70% by weight or more, and 80% by weight or more in 100% by weight of the heat storage agent composition. is more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
• This configuration has the advantage of stabilizing thermal properties such as the melting point, freezing point and/or solidification start temperature of the heat storage agent composition.
• metal soap As used herein, the term "metal soap” is intended as a general term for metal salts of fatty acids, and specifically, an anion (anion) derived from a fatty acid and a cation (cation), which is a metal ion. Bound substances are intended. Therefore, “metal soap” herein also includes sodium salts of fatty acids and potassium salts of fatty acids. In this specification, the metal ions contained in the metal soap (A) may be referred to as metal ions (D).
• the metal ion (D) is preferably potassium ion.
• Metal soaps containing potassium ions as metal ions (D) are often soluble in polyalkylene glycol. Therefore, by using the metal soap (A) containing potassium ions as the metal ions (D), the anions derived from the fatty acid (that is, the metal ions (D)) can be uniformly dissolved in the polyalkylene glycol. It has the advantage of being easy.
• the metal soap (A) is preferably composed of anions derived from fatty acids having 6 to 18 carbon atoms, more preferably composed of anions derived from fatty acids having 12 to 18 carbon atoms.
• the fatty acid may be a saturated fatty acid or an unsaturated fatty acid.
• the metal soap (A) is more preferably composed of an anion derived from at least one fatty acid selected from the group consisting of lauric acid, stearic acid, myristic acid, palmitic acid and oleic acid.
• the resulting heat storage agent composition has stable shape retention performance at 40° C. and does not undergo solid-liquid separation even during long-term storage. It has the advantage of having properties.
• the metal soap (A) is not particularly limited as long as it is soluble in polyalkylene glycol.
• the metal soap (A) is preferably at least one selected from the group consisting of potassium laurate, potassium stearate, potassium myristate, potassium palmitate and potassium oleate. According to this configuration, the obtained heat storage agent composition has the advantage of having stable shape retention performance at 40° C. and having the property of not causing solid-liquid separation even during long-term storage.
• the metal ion (C) is not particularly limited as long as it is an ion capable of converting the metal soap (A) into the polyalkylene glycol-insoluble metal soap (B). From the viewpoint that the metal soap (A) is easily changed to the metal soap (B) insoluble in the polyalkylene glycol, the metal ion (C) includes the metal ion (D) contained in the metal soap (A) to be used. Ions with a low ionization tendency are preferred.
• metal ions (C) are preferably sodium ions.
• the metal ion (D) contained in the metal soap (A) is a potassium ion and the metal ion (C) is a sodium ion
• the potassium ion has a higher ionization tendency than the sodium ion and exists as an ion in the solution.
• Potassium soaps are easily converted to sodium soaps by ion exchange.
• metal soap (B) Since the metal soap (B) is insoluble in polyalkylene glycol, the metal soap (B) produced by mixing the solution (I) and the metal ion (C) is partly or entirely Precipitation may occur.
• the heat storage agent composition obtained by this production method retains its shape at 40° C. due to the formation of the metal soap (B). Therefore, metal soap (B) can also be called a gelling agent or a thickening agent.
• the metal soap (B) contained in the heat storage agent composition does not necessarily have to be entirely precipitated, and part or all of it may be dissolved in the heat storage agent composition.
• the metal soap (B) is preferably composed of anions derived from fatty acids having 6 to 18 carbon atoms, more preferably composed of anions derived from fatty acids having 12 to 18 carbon atoms.
• the fatty acid may be a saturated fatty acid or an unsaturated fatty acid.
• the metal soap (B) is more preferably composed of an anion derived from at least one fatty acid selected from the group consisting of lauric acid, stearic acid, myristic acid, palmitic acid and oleic acid.
• the resulting heat storage agent composition has stable shape retention performance at 40° C. and does not undergo solid-liquid separation even during long-term storage. It has the advantage of having properties.
• the metal soap (B) is not particularly limited as long as it is insoluble in polyalkylene glycol.
• Metal soap (B) is preferably at least one selected from the group consisting of sodium laurate, sodium stearate, sodium myristate, sodium palmitate and sodium oleate. According to this configuration, the obtained heat storage agent composition has the advantage of having stable shape retention performance at 40° C. and having the property of not causing solid-liquid separation even during long-term storage.
• the heat storage agent composition according to one embodiment of the present invention may contain other components in addition to the polyalkylene glycol and the metal soap (B).
• Other components include, for example, water, corrosion inhibitors, antioxidants, antistatic agents, colorants, antifungal agents, and the like.
• the heat storage agent composition according to one embodiment of the present invention preferably contains water.
• water it is preferable to use water in this production method.
• This configuration has the advantage that it is possible to reliably uniformly disperse the metal ions (C) in the solution (1).
• water is cheap and safe. Therefore, using water in this production method to obtain a heat storage agent composition containing water is preferable not only from the above-mentioned advantages, but also from the viewpoint of cost and safety.
• Water is not particularly limited, and examples include tap water, industrial water, RO water (water purified by reverse osmosis membrane method), distilled water, pure water (e.g., deionized water (purified water), etc.), and ultrapure water.
• Water is preferably RO water, distilled water, pure water (for example, deionized water) and/or ultrapure water in terms of stable production of the heat storage agent composition.
• the amount of water in the heat storage agent composition obtained by this production method is not particularly limited.
• the amount of water in the heat storage agent composition is preferably 1.0% by weight to 10.0% by weight, more preferably 1.3% by weight to 9.0% by weight, based on 100% by weight of the heat storage agent composition. more preferably 1.5 wt% to 8.0 wt%, even more preferably 1.8 wt% to 7.0 wt%, and 2.0 wt% to 6.0 wt%. 0% by weight is particularly preferred.
• the amount of water used in the production method for example, the amount of aqueous solution containing metal ions (C) used can be adjusted so that the amount of water in the obtained heat storage agent composition is within the above range. preferable.
• This configuration has the advantage that the metal ions (C) can be uniformly dispersed in the solution (I) without impairing the thermal properties of the polyalkylene glycol.
• This production method comprises a metal ion (C) mixing step of mixing a polyalkylene glycol solution (I) containing a polyalkylene glycol and a metal soap (A) soluble in the polyalkylene glycol with a metal ion (C).
• the polyalkylene glycol solution (I) is a solution containing polyalkylene glycol as a solvent, metal soap (A) as a solute, and 50% by weight or more of 100% by weight of the solvent being polyalkylene glycol.
• the amount (content) of polyalkylene glycol in the solvent of solution (I) or in solution (I) is not particularly limited.
• the amount of the polyalkylene glycol in the solvent of the solution (I) or in the solution (I) is within the above-mentioned preferred range in consideration of the following points. (i) the amount of solution (I) used, (ii) the amount of polyalkylene glycol in solution (I) and the amount of polyalkylene glycol used other than solution (I), etc. .
• the amount (content) of the polyalkylene glycol in the solution (I) is, for example, preferably 60% by weight or more, more preferably 70% by weight or more, based on 100% by weight of the solution (I). It is more preferably at least 90% by weight, particularly preferably at least 95% by weight.
• the number average molecular weight of the polyalkylene glycol in the solvent of solution (I) or in solution (I) is not particularly limited.
• the number average molecular weight of the polyalkylene glycol in the solvent of the solution (I) or in the solution (I) is determined so that the solidification initiation temperature of the obtained heat storage agent composition has a desired value, taking into consideration the following points. , can be set as appropriate: (i) the amount of solution (I) used, the number average molecular weight and amount of polyalkylene glycol in solution (I), (ii) the number of polyalkylene glycols used other than solution (I) average molecular weight and quantity, etc.
• the amount (content) of the metal soap (A) in the solution (I) is not particularly limited.
• the amount of metal soap (A) in solution (I) can be appropriately set in consideration of the amount of solution (I) used and the amount of metal ion (C) used.
• the amount of metal soap (A) in 100% by weight of solution (I) is preferably 0.1% to 10.0% by weight, preferably 0.2% to 5% by weight. 0% by weight, more preferably 0.3% to 3.0% by weight, and particularly preferably 0.4% to 1.8% by weight. According to this configuration, there is no possibility that the metal soap (A) will be precipitated due to temperature changes in the solution (I), and the obtained heat storage agent composition has the advantage that it does not undergo solid-liquid separation even during long-term storage. .
• a method for preparing the polyalkylene glycol solution (I) is not particularly limited, but an example thereof includes a method of mixing the polyalkylene glycol and the metal soap (A).
• a) polyalkylene glycol is mixed with a solution of metal soap (A) dissolved in any solvent (for example, water or a small amount of polyalkylene glycol solution).
• any solvent for example, water or a small amount of polyalkylene glycol solution.
• the polyalkylene glycol and the solid metal soap (A) may be mixed.
• the mixture obtained by mixing the polyalkylene glycol and the metal soap (A) (or the solution of the metal soap (A)) may be (a) heated to an arbitrary temperature (for example, 50° C.), (b ) may be maintained (warmed) at an arbitrary temperature (eg, 50° C.) for a certain period of time (eg, until the metal soap (A) is dissolved), and/or (c) may be stirred.
• an arbitrary temperature for example, 50° C.
• b may be maintained (warmed) at an arbitrary temperature (eg, 50° C.) for a certain period of time (eg, until the metal soap (A) is dissolved)
• c) may be stirred.
• the metal soap (A) can be easily dissolved in the polyalkylene glycol solution and/or the metal soap (A) can be reliably uniformly dispersed in the solution (I).
• Each of the device for mixing the polyalkylene glycol and the metallic soap (A) (or the solution of the metallic soap (A)), the device for heating the mixture obtained by such mixing, and the device for stirring the mixture is particularly There is no limitation, and known devices can be used.
• the metal ion (C) mixing step may include a step of mixing (a) the polyalkylene glycol solution (I) and a metal salt containing the metal ion (C), and (b) the polyalkylene glycol solution ( A step of mixing I) with a solution containing metal ions (C) may be included.
• the metal ion (C) mixing step includes mixing the polyalkylene glycol solution (I) and the solution containing the metal ions (C). It is preferable to include a step (hereinafter sometimes referred to as a “metal ion (C)-containing solution mixing step”).
• the solution containing the metal ion (C) may be a polyalkylene glycol solution containing polyalkylene glycol and the metal ion (C), and contains the metal ion (C). It may be an aqueous solution.
• the polyalkylene glycol and the polyalkylene glycol solution containing the metal ion (C) in the metal ion (C) mixing step are referred to as "polyalkylene glycol solution (II)" or simply “solution (II)". In some cases.
• aqueous solution (IV) containing metal ions (C) in the metal ion (C) mixing step
• aqueous solution (IV) containing metal ions (C) or simply “aqueous solution (IV)”. In some cases.
• the polyalkylene glycol solution (I) is mixed with the polyalkylene glycol solution (II) containing the polyalkylene glycol and the metal ion (C).
• the polyalkylene glycol solution (II) in which the metal ions (C) are uniformly dispersed in the solution and the solution (I) can be mixed.
• the obtained heat storage agent composition can retain its shape uniformly over the entire heat storage agent composition even at 40° C. (in other words, it can be a uniform gel). That is, the obtained heat storage agent composition has the advantage that it is judged not to fall under the category of dangerous substances under the Japanese Fire Service Law even after long-term use, and the concern of solid-liquid separation can be avoided.
• the polyalkylene glycol solution (II) is a solution containing polyalkylene glycol as a solvent, metal ions (C) as a solute, and 50% by weight or more of 100% by weight of the solvent being polyalkylene glycol.
• the polyalkylene glycol in the solution (II) may be the same polyalkylene glycol as the polyalkylene glycol in the solution (I) (for example, a polyalkylene glycol having the same number of carbon atoms in the alkylene group and/or the number average molecular weight), Different polyalkylene glycols (eg, polyalkylene glycols having different carbon numbers and/or number average molecular weights in the alkylene group) may be used.
• the amount (content) of polyalkylene glycol in the solvent of solution (II) or in solution (II) is not particularly limited.
• the amount of the polyalkylene glycol in the solvent of the solution (II) or in the solution (II) is within the preferred range described above, taking into consideration the following points. It can be set appropriately so that: the amount of solution (II) used, the amount of polyalkylene glycol in solution (II), and the amount of polyalkylene glycol used in other than solution (II) (for example, solution (I)) etc.
• the amount (content) of the polyalkylene glycol in the solution (II) is, for example, preferably 60% by weight or more, more preferably 70% by weight or more, in 100% by weight of the solution (II). It is more preferably at least 90% by weight, particularly preferably at least 95% by weight.
• the number average molecular weight of the polyalkylene glycol in the solvent of solution (II) or in solution (II) is not particularly limited.
• the number-average molecular weight of the polyalkylene glycol in the solvent of the solution (II) or in the solution (II) is determined so that the solidification initiation temperature of the obtained heat storage agent composition becomes a desired value, taking into consideration the following points. , can be set as appropriate: the amount of solution (II) used, the number average molecular weight and amount of polyalkylene glycol in solution (II), and the polyalkylene glycol used in solution (II) other than (e.g., solution (I)) number average molecular weight and amount of
• the amount (content) of the metal ion (C) in the solution (II) is not particularly limited.
• the relationship between the amount of metal ion (C) in solution (II) and the amount of metal soap (A) is ⁇ (molar amount of metal ion (C)) ⁇ (valence of metal ion (C)) ⁇ is excessive with respect to ⁇ (molar amount of metal ion (D) contained in metal soap (A)) ⁇ (valence of metal ion (D) contained in metal soap (A)) ⁇ is preferably
• ⁇ (metal ion ( The ratio of the value of (molar amount of C)) ⁇ (valence of metal ion (C)) ⁇ is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, 5 or more is particularly preferred. According to this configuration, all of the metal soap (A) is replaced with the metal soap (B), so solid-liquid separation of the gel caused by the metal soap (A) remaining in the heat storage agent composition is reduced or
• the method for preparing solution (II) is not particularly limited.
• Examples of the method for preparing the solution (II) include (a) a method of mixing a polyalkylene glycol and a metal salt containing a metal ion (C), and (b) a method of mixing a polyalkylene glycol and a metal ion (C). and a method of mixing with a solution.
• the solution containing metal ion (C) may be polyalkylene glycol and a polyalkylene glycol solution containing metal ion (C), or an aqueous solution containing metal ion (C).
• aqueous solution containing the metal ion (C) in the preparation of the solution (II) may be referred to as "aqueous solution (III) containing metal ion (C)" or simply “aqueous solution (III)”. .
• the solution (II) is preferably prepared by mixing the polyalkylene glycol and the aqueous solution (III) containing the metal ion (C), in other words, the polyalkylene glycol solution (II) is , polyalkylene glycol and the aqueous solution (III) containing the metal ion (C). According to this configuration, it is possible to obtain the polyalkylene glycol solution (II) in which the metal ions (C) are uniformly dispersed in the solution.
• the obtained heat storage agent composition can retain its shape uniformly over the entire heat storage agent composition even at 40° C. (in other words, it can be a uniform gel). That is, the obtained heat storage agent composition has the advantage that it is judged not to fall under the category of dangerous substances under the Japanese Fire Service Law even after long-term use, and the concern of solid-liquid separation can be avoided.
• the aqueous solution (III) containing metal ions (C) is a solution containing water as a solvent, metal ions (C) as a solute, and 50% by weight or more of 100% by weight of the solvent being water.
• the solvent of the aqueous solution (III) may be water only.
• the aqueous solution (III) can be prepared by mixing water and a metal salt containing the metal ion (C).
• the metal salt containing the metal ion (C) is not particularly limited, and examples thereof include sodium compounds such as sodium chloride, sodium bromide, sodium sulfate, sodium nitrate, sodium acetate, sodium carbonate and sodium formate.
• the metal salt containing the metal ion (C) one of these may be used alone, or two or more thereof may be used in combination.
• a case of adopting a method of mixing polyalkylene glycol and an aqueous solution (III) containing a metal ion (C) as a method for preparing the solution (II) will be described.
• a water-soluble metal salt that is insoluble in polyalkylene glycol can be used as the metal salt containing the metal ion (C).
• Such metal salts are not particularly limited and include, for example, the above-mentioned sodium compounds.
• sodium chloride, sodium bromide, sodium sulfate, and sodium nitrate are metal salts that are odorless, safe, and have few restrictions on handling.
• acetate, sodium carbonate and sodium formate more preferably at least one selected from the group consisting of sodium chloride, sodium sulfate and sodium nitrate
• the resulting heat storage agent composition may contain water.
• the advantages of including water in the heat storage agent composition are as described above.
• the polyalkylene glycols contained in the heat storage agent composition as the amount of polyalkylene glycol dissolved in water increases, the latent heat amount of the heat storage agent composition may decrease. Therefore, it is preferable that the amount of polyalkylene glycol dissolved in water in the heat storage agent composition is small. Therefore, the higher the concentration of the metal ion (C) (or the metal salt containing the metal ion (C)) in the aqueous solution (III), the better, and the closer to the saturation concentration the better.
• the saturation concentration of sodium chloride with respect to water at 20°C is 26.5 (weight/weight%).
• the concentration of the metal ions (C) in the aqueous solution (III) can be adjusted.
• the mixture obtained by mixing water and the metal salt containing the metal ion (C) may be (a) heated to an arbitrary temperature (for example, 25 ° C.), (b ) may be maintained (warmed) at an arbitrary temperature (eg, 20° C.) for a certain period of time (eg, until the metal salt containing the metal ion (C) is dissolved), and/or (c) stirred.
• an arbitrary temperature for example, 25 ° C.
• b may be maintained (warmed) at an arbitrary temperature (eg, 20° C.) for a certain period of time (eg, until the metal salt containing the metal ion (C) is dissolved)
• c stirred.
• each of the device for mixing water and the metal salt containing the metal ion (C), the device for heating the mixture obtained by such mixing, and the device for stirring the mixture especially There is no limitation, and known devices can be used.
• solution (II) a mixture obtained by mixing polyalkylene glycol and a solution containing metal ions (C) (for example, aqueous solution (III)) may be stirred.
• This configuration has the advantage that the metal ions (C) can be reliably uniformly dispersed in the solution (II).
• an apparatus for mixing polyalkylene glycol and a solution containing metal ions (C) e.g., aqueous solution (III)
• Each device for stirring is not particularly limited, and known devices can be used.
• the metal ion (C) mixing step preferably includes a step of mixing the polyalkylene glycol solution (I) with an aqueous solution (IV) containing the metal ion (C) as the metal ion (C) solution mixing step.
• the process of dispersing the metal ions (C) in the polyalkylene glycol in advance can be omitted, so that there is an advantage that the working efficiency is improved.
• the step of mixing the polyalkylene glycol solution (I) and the aqueous solution (IV) containing the metal ions (C) may be referred to as "aqueous solution (IV) mixing step".
• the aqueous solution (IV) containing metal ions (C) is a solution containing water as a solvent, metal ions (C) as a solute, and 50% by weight or more of 100% by weight of the solvent being water.
• the solvent of the aqueous solution (IV) may be water only.
• the aqueous solution (IV) can be said to be the same aqueous solution as the aqueous solution (III) described above, although the steps used in this production method and the purpose of use are different. Therefore, for the aqueous solution (IV), the description in the above section (Aqueous solution (III) containing metal ions (C)) can be used as appropriate.
• the metal salt containing the metal ion (C) used in the preparation of the aqueous solution (IV) includes the metal salts described in the above section (Aqueous solution (III) containing the metal ion (C)). .
• the method for preparing the aqueous solution (IV) may also include the metal salt described in the above section (Aqueous solution (III) containing metal ion (C)). can.
• sodium chloride, sodium bromide, sodium sulfate, and sodium nitrate are metal salts that are odorless, safe, and have few restrictions on handling.
• acetate, sodium carbonate and sodium formate more preferably at least one selected from the group consisting of sodium chloride, sodium sulfate and sodium nitrate
• the amount (content) of the metal ion (C) in the solution (IV) is not particularly limited.
• the relationship between the amount of metal ion (C) in solution (IV) and the amount of metal soap (A) is ⁇ (molar amount of metal ion (C)) ⁇ (valence of metal ion (C)) ⁇ is excessive with respect to ⁇ (molar amount of metal ion (D) contained in metal soap (A)) ⁇ (valence of metal ion (D) contained in metal soap (A)) ⁇ is preferably
• ⁇ (metal ion ( The ratio of the value of (molar amount of C)) ⁇ (valence of metal ion (C)) ⁇ is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, 5 or more is particularly preferred. According to this configuration, all of the metal soap (A) is replaced with the metal soap (B), so solid-liquid separation of the gel caused by the metal soap (A) remaining in the heat storage agent composition is reduced or prevented.
• the metal ion (C) mixing step may include (a) a step of simultaneously mixing the solution (I) and the metal ion (C), and (b) adding the metal ion (C) to the solution (I). or (c) adding the solution (I) to the metal ions (C).
• the step of mixing the metal ions (C) includes (a) mixing the solution (I) and the metal ions (C) simultaneously, or (b) adding the metal ions (C) to the solution (I). It is preferable to include steps.
• the metal salt containing the metal ion (C) (for example, the sodium compound described above) is combined with the metal soap (A) (for example, potassium laurate, potassium stearate, potassium myristate, potassium palmitate, potassium oleate).
• the metal soap (A) for example, potassium laurate, potassium stearate, potassium myristate, potassium palmitate, potassium oleate.
• the solution (II) or aqueous solution (IV) containing the metal ion (C) generally tends to have a higher specific gravity than the solution (I).
• a solution with a relatively high specific gravity is added to a solution with a relatively low specific gravity, and the mixture is mixed. preferably.
• the metal ion (C) mixing step is performed as the solution (II) mixing step or the aqueous solution (IV) mixing step ( a) simultaneously mixing a solution (I) containing a metal soap (A) and a solution (II) or an aqueous solution (IV) containing a metal ion (C), or (b) a metal soap (A ) to the solution (I) containing the metal ion (C), the step of adding the solution (II) or the aqueous solution (IV) containing the metal ion (C).
• the metal ion (C) mixing step is, for example, a solution (II) mixing step or an aqueous solution (IV) mixing step, in which (a) a solution (I) at a relatively high temperature (e.g., 50°C) and a room temperature (e.g., 25°C) ) with a solution (II) or an aqueous solution (IV) of (b) relatively high temperature (e.g. 50 ° C.) solution (I) at about room temperature (e.g.
• the amounts of solution (I), solution (II) and aqueous solution (IV) used in the metal ion (C) mixing step are not particularly limited.
• Each of the amounts of solution (I), solution (II) and aqueous solution (IV) used in the metal ion (C) mixing step is the amount of metal soap (A) in solution (I), The amount of metal ion (C) (metal salt), the amount of metal ion (C) (metal salt) in solution (IV), and the amount of polyalkylene glycol in solution (I) and solution (II), etc.
• the solidification start temperature of the resulting heat storage agent composition can be appropriately set to a desired temperature.
• the amount (used amount) of the metal ion (C) is not particularly limited.
• the relationship between the amount of the metal ion (C) and the amount of the metal soap (A) in the metal ion (C) mixing step is ⁇ (molar amount of metal ion (C)) x (valence of metal ion (C) number) ⁇ is the value of ⁇ (molar amount of metal ion (D) contained in metal soap (A)) ⁇ (valence of metal ion (D) contained in metal soap (A)) ⁇ preferably in excess.
• ⁇ (metal ion ( The ratio of the value of (molar amount of C)) ⁇ (valence of metal ion (C)) ⁇ is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, 5 or more is particularly preferred. According to this configuration, all of the metal soap (A) is replaced with the metal soap (B), so solid-liquid separation of the gel caused by the metal soap (A) remaining in the heat storage agent composition is reduced or prevented. be able to.
• a case of preparing a heat storage material containing the heat storage agent composition by storing the heat storage agent composition in a container will be described.
• the production of the heat storage agent composition and the preparation of the heat storage material may be performed at the same time.
• a blow container made of HDPE is filled with the solution (I) at a relatively high temperature (for example, 50°C) and then filled with the solution (II) or the aqueous solution (IV) at about room temperature (for example, 25°C).
• the production of the heat storage agent composition and the preparation of the heat storage material may be performed simultaneously.
• the solution (I) at a relatively high temperature (eg, 50°C) and the solution (II) or aqueous solution (IV) at about room temperature (eg, 25°C) are mixed in an HDPE blow container.
• the production of the heat storage agent composition and the preparation of the heat storage material may be performed at the same time by a method of simultaneous filling.
• a case of preparing a heat storage material containing the heat storage agent composition by storing the obtained heat storage agent composition in an airtight container after manufacturing the heat storage agent composition will be described.
• the heat storage agent composition retains its shape at 40.degree. Therefore, after heating the heat storage agent composition obtained after production to a temperature higher than 40° C. (for example, 60° C.) to obtain a fluid heat storage agent composition, the heat storage agent composition is placed, for example, in a 500 mL HDPE blow container.
• a heat storage material can be prepared by filling the heat storage agent composition.
• a heat storage agent composition according to one embodiment of the present invention contains a polyalkylene glycol and a metal soap (B) insoluble in the polyalkylene glycol, and retains its shape at 40°C.
• the heat storage agent composition according to one embodiment of the present invention has the above configuration, (i) in various controlled temperature ranges (for example, 1° C. to 40° C.), pharmaceuticals, medical devices, cells, specimens, organs, It is possible to maintain the temperature of temperature-controlled articles such as chemical substances or food, to enable the storage or transportation of such temperature-controlled articles, and , has the advantage that handling constraints are relaxed.
• the heat storage agent composition according to one embodiment of the present invention retains its shape at 40°C.
• the fact that the heat storage agent composition retains its shape at 40°C means that the heat storage agent composition does not have fluidity at 40°C.
• the heat storage agent composition is in a molten state at 40°C, the heat storage agent composition does not have fluidity at 40°C, so it can be said that the heat storage agent composition is not liquid but gel at 40°C.
• a heat storage agent composition (sample) is placed in a flat-bottomed transparent glass tube having an inner diameter of 30 mm and a height of 120 mm to a height of 55 mm from the bottom.
• the glass tube is provided with a marked line at 85 mm from the bottom; (2) Leave the glass tube upright for 10 minutes in a constant temperature water bath adjusted to 40°C; (3) After 10 minutes, remove the glass tube from the constant temperature water bath and lay it horizontally; (4) Measure the time from laying the glass tube horizontally until the sample in the glass tube exceeds the 85 mm marked line; (5) If the obtained time is within 90 seconds, it is determined that the heat storage agent composition retains its shape at 40° C. (in other words, it does not have fluidity).
• This test is the same as the test based on the Class 4 and Designated Combustible Judgment Flowchart stipulated by the Fire and Disaster Management Agency of the Ministry of Internal Affairs and Communications in accordance with the government ordinance on the regulation of dangerous substances in Japan.
• the heat storage agent composition according to one embodiment of the present invention retains its shape at 40°C.
• the heat storage agent composition according to one embodiment of the present invention is: It does not contain substances listed in items 1 to 9 of the same category, and (b) has a flash point of 40° C. or higher as measured by a seta closed flash point tester. Therefore, it is determined that the heat storage agent composition according to one embodiment of the present invention does not fall under the category of hazardous materials under the Fire Service Act of Japan.
• the solidification start temperature of the present heat storage agent composition is preferably 1.0°C to 40.0°C, more preferably 1.0°C to 30.0°C, more preferably 1.0°C to 20.0°C. 0°C to 15.0°C is more preferred, 3.0°C to 15.0°C is more preferred, 5.0°C to 15.0°C is even more preferred, and 6.0°C to 12.0°C is particularly preferred. .
• This configuration has the advantage that it can be suitably used as a heat storage agent composition when the article to be temperature-controlled is a biopharmaceutical, a pharmaceutical intermediate, a vaccine, or the like.
• the “solidification initiation temperature” of the heat storage agent composition means “the temperature exhibited by the heat storage agent composition when the gelled heat storage agent composition begins to solidify, in other words, to solidify”. intended to be
• the solidification initiation temperature of the heat storage agent composition can be measured by the following method using a constant temperature bath having a temperature control unit and a thermocouple: (1) A heat storage agent composition is placed in a test tube, and a thermocouple is inserted in the center of the heat storage agent composition; (2) The test tube is placed in a constant temperature bath having a temperature control unit; (3) While monitoring the temperature of the heat storage agent composition, the temperature in the constant temperature bath is lowered from a high temperature (eg, 50°C) to a low temperature (eg, -50°C) at a constant cooling rate (eg, a rate of 1°C/min).
• a high temperature eg, 50°C
• a low temperature eg, -50°C
• a constant cooling rate eg, a rate of 1°C/min
• the temperature is lowered, and the temperature change of the heat storage agent composition is plotted against time and graphed; (3)
• the temperature of the heat storage agent composition in the test tube changes in the following order (i) to (iii) as compared with the temperature of the constant temperature bath that decreases at a constant rate: (i (ii) after a slight increase from temperature T1 to temperature T2, there is little change from temperature T2 to temperature T3 due to the latent heat of the heat storage agent composition; (3) At temperature T3 , the temperature begins to drop significantly.
• Temperature T1 is referred to herein as the "solidification initiation temperature”.
• the heat storage agent composition according to one embodiment of the present invention can be used as a heat storage material by being stored (filled) in a container, bag, or the like.
• a heat storage material containing the heat storage agent composition according to one embodiment of the present invention in other words, a heat storage material containing the heat storage agent composition according to one embodiment of the present invention is also one embodiment of the present invention. .
• the container or bag is mainly made of resin (for example, synthetic resin).
• resin for example, synthetic resin.
• the resin include polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate, polystyrene, nylon and polyester.
• One of these materials may be used alone, or two or more of these materials may be used in combination in order to improve heat resistance and barrier properties (for example, a multi-layer structure is used). etc.) can also be done. From the point of view of handling and cost, it is preferable to use a container or bag made of polyethylene.
• the shape of the container or bag is not particularly limited, but from the viewpoint of efficient heat exchange between the cold storage material composition and the temperature-controlled article or its surrounding space through the container or bag, the thickness is A shape that is thin and can secure a large surface area is preferable.
• the container for example, an HDPE blown container having an internal capacity of 500 mL is suitable.
• the heat storage agent composition according to one embodiment of the present invention is suitably used for storing and transporting various articles such as cells, pharmaceuticals, medical devices, cells, specimens, organs, chemical substances, and foods that require temperature control. can.
• the heat storage agent composition according to one embodiment of the present invention or the heat storage material according to one embodiment of the present invention can also be used as various heat retaining tools.
• the heat storage agent composition according to one embodiment of the present invention or the heat storage material according to one embodiment of the present invention can be used as a heat storage material in various heat storage devices such as air conditioners and heat recovery systems.
• the heat storage agent composition according to one embodiment of the present invention or the heat storage material according to one embodiment of the present invention can be applied to various devices as a heat storage material. can.
• An embodiment of the present invention may have the following configuration.
• a heat storage agent composition that contains a polyalkylene glycol and a metal soap (B) that is insoluble in the polyalkylene glycol, and retains its shape at 40°C.
• An embodiment of the present invention may have the following configuration.
• step includes mixing the polyalkylene glycol solution (I) with a polyalkylene glycol solution (II) containing the polyalkylene glycol and the metal ion (C).
• a method for producing a heat storage agent composition includes mixing the polyalkylene glycol solution (I) with a polyalkylene glycol solution (II) containing the polyalkylene glycol and the metal ion (C).
• the metal soap (A) is at least one selected from the group consisting of potassium laurate, potassium stearate, potassium myristate, potassium palmitate and potassium oleate [Y1] to [Y4] A method for producing a heat storage agent composition according to any one of .
• [Y6] of [Y1] to [Y5], wherein the metal soap (B) is at least one selected from the group consisting of sodium laurate, sodium stearate, sodium myristate, sodium palmitate and sodium oleate A method for producing the heat storage agent composition according to any one of the above.
• Raw materials used in Examples and Comparative Examples are as follows. ⁇ Main agent> ⁇ Polyethylene glycol 400 (PEG400) (number average molecular weight 400, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ Polyethylene glycol 600 (PEG600) (number average molecular weight 600, manufactured by Sanyo Chemical Industries, Ltd.) ⁇ Polyethylene glycol 1000 (PEG1000) (number average molecular weight 1000, manufactured by Sanyo Chemical Industries, Ltd.) The ratios of PEG400, PEG600, and PEG1000 described in the table all represent the amount (% by weight) of each PEG used when the heat storage agent composition is taken as 100% by weight.
• Example 1 Method for preparing polyalkylene glycol solution (I-1)
• Example 2 Method for preparing polyalkylene glycol solution (I-1)
• 4.0 g of potassium laurate was added to 272.5 g of polyethylene glycol 600 to form a mixture.
• the mixture was heated and kept at 50° C., and potassium laurate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-1).
• a blown container made of HDPE (High Density PolyEthylene) having a content of 500 mL was filled with the polyethylene glycol solution (I-1) and then with the polyethylene glycol solution (II-1). After closing the cap of the HDPE blow container, the HDPE blow container was shaken up and down 10 times and allowed to stand still for 10 minutes to obtain a heat storage material (a-1) in which the heat storage agent composition was solidified.
• HDPE High Density PolyEthylene
• Example 2 (Method for preparing polyalkylene glycol solutions (I-1) and (II-1)) Polyalkylene glycol solutions (I-1) and (II-1) were prepared in the same manner as in Example 1.
• Example 3 (Method for producing polyalkylene glycol solution (I-2)) 4.0 g of potassium laurate was added to a mixture of 198.5 g of polyethylene glycol 400 and 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium laurate was dissolved in the mixture of polyethylene glycols to prepare a polyalkylene glycol solution (I-2).
• Example 4 (Method for preparing polyalkylene glycol solution (I-3)) To 272.5 g of polyethylene glycol 600 was added 4.0 g of potassium stearate to form a mixture. The mixture was heated and kept at 50° C., and potassium stearate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-3).
• Polyalkylene glycol solution (II-1) was prepared in the same manner as in Example 1.
• Example 5 (Method for producing polyalkylene glycol solution (I-4)) 4.0 g of potassium stearate was added to a mixture of 198.5 g of polyethylene glycol 400 and 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C. to dissolve potassium stearate to prepare a polyalkylene glycol solution (I-4).
• an aqueous sodium chloride solution (IV-1) was prepared by dissolving 5.5 g of purified salt in 19.5 g of water at room temperature.
• the polyethylene glycol solution (I-4) was filled into an HDPE blown container having a content of 500 mL, and then the sodium chloride aqueous solution (IV-1) was filled.
• the HDPE blow container was shaken up and down 10 times and allowed to stand still for 10 minutes to obtain a heat storage material (a-5) in which the heat storage agent composition was solidified.
• the moles of sodium ions (sodium chloride) and potassium ions (potassium laurate) present in all the liquids in the manufacturing process of the heat storage materials (a-1, a-2, a-3) of Examples 1 to 3 The ratio was 0.0188 mol:0.0034 mol, with a large excess of sodium ions.
• the molar ratio of sodium ions (sodium chloride) and potassium ions (potassium stearate) present in the entire liquid during the manufacturing process of the heat storage materials (a-4, a-5) of Examples 4 and 5 was 0.019. mol: 0.0025 mol, a large excess of sodium ions.
• Example 6 (Method for preparing polyalkylene glycol solution (I-5)) 4.0 g of potassium laurate was added to a mixture of 331.0 g of polyethylene glycol 600 and 15.0 g of polyethylene glycol 1000 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium laurate was dissolved in the mixture of polyethylene glycols to prepare a polyalkylene glycol solution (I-5).
• Example 7 (Method for preparing polyalkylene glycol solutions (I-5) and (II-2)) Polyalkylene glycol solution (I-5) and polyalkylene glycol solution (II-2) were prepared by the same method as in Example 6.
• Example 8 (Method for producing polyalkylene glycol solution (I-6)) To a mixture of 135.0 g of polyethylene glycol 400, 331.0 g of polyethylene glycol 600 and 15.0 g of polyethylene glycol 1000, 4.0 g of potassium laurate was added to prepare a mixture. The mixture was heated and kept at 50° C., and potassium laurate was dissolved in the mixed solution of polyethylene glycol to prepare a polyalkylene glycol solution (I-6).
• Example 9 (Method for preparing polyalkylene glycol solution (I-7)) 4.0 g of potassium stearate was added to a mixture of 331.0 g of polyethylene glycol 600 and 15.0 g of polyethylene glycol 1000 to form a mixture. The mixture was heated and kept at 50° C., and potassium stearate was dissolved in the mixed solution of polyethylene glycol to prepare a polyalkylene glycol solution (I-7).
• Example 10 (Method for producing polyalkylene glycol solution (I-8)) 4.0 g of potassium stearate was added to a mixture of 135.0 g of polyethylene glycol 400, 331.0 g of polyethylene glycol 600 and 15.0 g of polyethylene glycol 1000 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium stearate was dissolved in the mixed solution of polyethylene glycol to prepare a polyalkylene glycol solution (I-8).
• the moles of sodium ions (sodium chloride) and potassium ions (potassium laurate) present in all liquids in the manufacturing process of the heat storage materials (b-1, b-2, b-3) of Examples 6 to 8 The ratio was 0.0113 mol:0.0034 mol, indicating a large excess of sodium ions.
• the molar ratio of sodium ions (sodium chloride) and potassium ions (potassium stearate) present in the entire liquid in the manufacturing process of the heat storage materials (b-4, b-5) of Examples 9 and 10 was 0.0113. mol: 0.0025 mol, a large excess of sodium ions.
• Example 11 (Method for preparing polyalkylene glycol solution (I-9)) A mixture was prepared by adding 4.0 g of potassium laurate to 250.0 g of polyethylene glycol 600. The mixture was heated and kept at 50° C., and potassium laurate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-9).
• Example 12 (Method for preparing polyalkylene glycol solutions (I-9) and (II-3)) Polyalkylene glycol solution (I-9) and polyalkylene glycol solution (II-3) were prepared in the same manner as in Example 11.
• Example 13 (Method for producing polyalkylene glycol solution (I-10)) 4.0 g of potassium laurate was added to a mixture of 337.5 g of polyethylene glycol 600 and 93.5 g of polyethylene glycol 1000 at 50° C. to prepare a mixture. While the mixture was kept at 50° C., potassium laurate was dissolved in the mixed solution of polyethylene glycol to prepare a polyalkylene glycol solution (I-10).
• Example 14 (Method for preparing polyalkylene glycol solution (I-11)) To 250.0 g of polyethylene glycol 600 was added 4.0 g of potassium stearate to form a mixture. The mixture was heated and kept at 50° C., and potassium stearate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-11).
• Example 15 (Method for producing polyalkylene glycol solution (I-12)) 4.0 g of potassium stearate was added to a mixture of 337.5 g of polyethylene glycol 600 and 93.5 g of polyethylene glycol 1000 at 50° C. to prepare a mixture. While the mixture was kept at 50° C., potassium stearate was dissolved in the mixture of polyethylene glycols to prepare a polyalkylene glycol solution (I-12).
• the moles of sodium ions (sodium chloride) and potassium ions (potassium laurate) present in all liquids in the manufacturing process of the heat storage materials (c-1, c-2, c-3) of Examples 11 to 13 The ratio was 0.0188 mol:0.0034 mol, with a large excess of sodium ions.
• the molar ratio of sodium ions (sodium chloride) and potassium ions (potassium stearate) present in the entire liquid in the manufacturing process of the heat storage materials (c-4, c-5) of Examples 14 and 15 was 0.019. mol: 0.0025 mol, a large excess of sodium ions.
• Example 16 (Method for preparing polyalkylene glycol solution (I-13)) 4.0 g of potassium myristate was added to 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium myristate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-13).
• Polyalkylene glycol solution (II-1) was prepared in the same manner as in Example 1.
• Example 17 (Method for producing polyalkylene glycol solution (I-14)) 4.0 g of potassium myristate was added to a mixture of 198.5 g of polyethylene glycol 400 and 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C. to dissolve potassium myristate to prepare a polyalkylene glycol solution (I-14).
• an aqueous sodium chloride solution (IV-1) was prepared by dissolving 5.5 g of purified salt in 19.5 g of water at room temperature.
• a polyethylene glycol solution (I-14) was filled into a 500 mL HDPE blown container, and then the sodium chloride aqueous solution (IV-1) was filled.
• the HDPE blow container was shaken up and down 10 times and allowed to stand still for 10 minutes to obtain a heat storage material (a-8) in which the heat storage agent composition was solidified.
• Example 18 (Method for preparing polyalkylene glycol solution (I-15)) 4.0 g of potassium palmitate was added to 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium palmitate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-7).
• Polyalkylene glycol solution (II-1) was prepared in the same manner as in Example 1.
• Example 19 (Method for producing polyalkylene glycol solution (I-16)) 4.0 g of potassium palmitate was added to a mixture of 198.5 g of polyethylene glycol 400 and 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C. to dissolve potassium palmitate to prepare a polyalkylene glycol solution (I-16).
• an aqueous sodium chloride solution (IV-1) was prepared by dissolving 5.5 g of purified salt in 19.5 g of water at room temperature.
• a polyethylene glycol solution (I-16) was filled into a 500 mL HDPE blown container, and then the sodium chloride aqueous solution (IV-1) was filled.
• the HDPE blow container was shaken up and down 10 times and allowed to stand still for 10 minutes to obtain a heat storage material (a-10) in which the heat storage agent composition was solidified.
• Example 20 (Method for preparing polyalkylene glycol solution (I-17)) 4.0 g of potassium oleate was added to 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C., and potassium oleate was dissolved in polyethylene glycol 600 to prepare a polyalkylene glycol solution (I-17).
• Polyalkylene glycol solution (II-1) was prepared in the same manner as in Example 1.
• Example 21 (Method for producing polyalkylene glycol solution (I-18)) 4.0 g of potassium oleate was added to a mixture of 198.5 g of polyethylene glycol 400 and 272.5 g of polyethylene glycol 600 to prepare a mixture. The mixture was heated and kept at 50° C. to dissolve potassium oleate to prepare a polyalkylene glycol solution (I-18).
• an aqueous sodium chloride solution (IV-1) was prepared by dissolving 5.5 g of purified salt in 19.5 g of water at room temperature.
• a polyethylene glycol solution (I-18) was filled into an HDPE blown container having a content of 500 mL, and then the sodium chloride aqueous solution (IV-1) was filled.
• the HDPE blow container was shaken up and down 10 times and allowed to stand still for 10 minutes to obtain a heat storage material (a-12) in which the heat storage agent composition was solidified.
• the molar ratio of sodium ions (sodium chloride) and potassium ions (potassium myristate) present in all liquids in the manufacturing process of the heat storage materials (a-7 and a-8) of Examples 16 and 17 was 0.00. 0188 mol: 0.0030 mol, and sodium ions (sodium chloride and potassium ions (potassium palmitate) present in all liquids in the manufacturing process of the heat storage materials (a-9, a-10) of Examples 18 to 19 is 0.0188 mol:0.0027 mol, and sodium ions (sodium chloride and The molar ratio with potassium ions (potassium oleate) was 0.0188 mol:0.0025 mol, and sodium ions were in large excess in all cases.
• examples include lithium stearate, lithium laurate, lithium montanate, sodium 12-hydroxystearate, sodium behenate, sodium montanate, potassium 12-hydroxystearate, potassium montanate, calcium laurate , calcium 12-hydroxystearate, calcium montanate, barium laurate, zinc laurate, zinc 12-hydroxystearate, aluminum stearate, aluminum 12-hydroxystearate or aluminum 2-ethylhexanoate, and polyalkylene Although added directly to the glycol, it was not possible to force the polyalkylene glycol to retain its shape at 40°C.
• the polyalkylene glycol could be kept in shape at 40° C., but sodium laurate or sodium stearate was not present in the polyalkylene glycol. Due to the uniformity, the physical properties of the resulting heat storage agent composition were unstable. That is, in one embodiment of the present invention, the step of using a metal soap (A) that is soluble in polyalkylene glycol and converting the metal soap (A) into the metal soap (B) in the polyalkylene glycol is important. We were able to prove that
• compositions of the heat storage agent compositions contained in the heat storage materials (a-1) to (a-12), (b-1) to (b-6) and (c-1) to (c-6) are shown in Table 1. and Table 2.
• a heat storage agent composition is taken out from each of the heat storage materials (a-1) to (a-12), (b-1) to (b-6) and (c-1) to (c-6), and each heat storage agent Each physical property of the composition was measured and evaluated by the following methods.
• the solidification initiation temperature of each heat storage agent composition was measured by the following method using a constant temperature bath having a temperature control unit and a thermocouple: (1) A heat storage agent composition was placed in a test tube, and a thermocouple was inserted in the center of the heat storage agent composition; (2) the test tube was placed in a constant temperature bath having a temperature control unit; (3) While monitoring the temperature of the heat storage agent composition, the temperature in the constant temperature bath is lowered from 50° C. to ⁇ 50° C. at a rate of 1° C./min, and the temperature change of the heat storage agent composition is measured against time.
• the temperature of the heat storage agent composition in the test tube changed in the following order (i) to (iii) as compared with the temperature of the constant temperature bath, which decreased at a constant rate: (i ( ii ) after a slight increase from temperature T1 to temperature T2 , from temperature T2 to temperature T3 , there is little change due to the latent heat of the heat storage agent composition; (3) After the temperature T3 , the temperature began to decrease significantly.
• the temperature T1 is defined as the "solidification initiation temperature”.
• the glass tube was provided with a marked line at 85 mm from the bottom; (2) The glass tube was left upright for 10 minutes in a constant temperature water bath adjusted to 20°C; (3) After 10 minutes, the glass tube was taken out of the constant temperature water bath and placed horizontally; (4) The time from laying down the glass tube horizontally until the sample in the glass tube crossed the 85 mm marked line was measured; (5) Based on the measurement results, whether or not the heat storage agent composition retains its shape at 20° C. (in other words, whether or not it has fluidity) was determined according to the following criteria. Within 90 seconds: The heat storage agent composition retains its shape at 20°C (has fluidity).
• the heat storage agent composition does not retain its shape at 20°C (has no fluidity) (denoted as "No” in the table). It should be noted that the heat storage agent composition determined to retain its shape at 20°C by the above test was judged to be "not liquid at 20°C" by a test based on the Class 4 and Designated Combustible Judgment Flowchart stipulated by the Fire and Disaster Management Agency of the Ministry of Internal Affairs and Communications. be judged.
• the glass tube was provided with a marked line at 85 mm from the bottom; (2) The glass tube was left upright for 10 minutes in a constant temperature water bath adjusted to 40°C; (3) After 10 minutes, the glass tube was taken out of the constant temperature water bath and placed horizontally; (4) The time from laying down the glass tube horizontally until the sample in the glass tube crossed the 85 mm marked line was measured; (5) Based on the measurement results, whether or not the heat storage agent composition retains its shape at 40° C. (in other words, whether or not it has fluidity) was determined according to the following criteria. Within 90 seconds: The heat storage agent composition retains its shape at 40°C (has fluidity).
• the heat storage agent composition does not retain its shape at 40°C (has no fluidity) (denoted as "No” in the table). It should be noted that the heat storage agent composition determined to retain its shape at 40°C by the above test was judged to be "non-liquid at 40°C" by a test based on the Class 4 and Designated Combustible Judgment Flow Chart stipulated by the Fire and Disaster Management Agency of the Ministry of Internal Affairs and Communications. be judged. Therefore, the heat storage agent composition determined to retain its shape at 40.degree.
• (iv) Hazardous material determination Table 2 shows the results of the shape retention test at 20°C, the shape retention test at 40°C, and the flash point measurement test. As shown in Table 2, the heat storage agent compositions of Examples 1 to 15 retain their shape at 40°C, ie they are not liquid at 40°C. In addition, the heat storage agent compositions of Examples 1 to 15 did not contain the substances listed in Items 1 to 9 of Appendix 1, Group 2 of the Fire Service Act, and the flash points measured by the Seta closed flash point measurement test were is above 40°C. Therefore, it is determined that the heat storage agent compositions of Examples 1 to 15 do not fall under the second category of hazardous materials under the Japanese Fire Service Law. The heat storage agent compositions of Examples 1 to 15 do not correspond to either Category 2 or Category 4 hazardous materials under the Fire Service Act of Japan. non-dangerous goods".
• the heat storage agent compositions of Comparative Examples 1, 5 and 9 do not retain their shape at 40°C, that is, they are liquid at 40°C.
• the heat storage agent compositions of Comparative Examples 1, 5 and 9 are "not ignitable" in the measurement result obtained by the closed ceta flash point measurement test.
• the heat storage agent compositions of Comparative Examples 1, 5 and 9 were measured for Cleveland open flash point by a Cleveland open flash point measurement test. °C or higher. Therefore, the heat storage agent compositions of Comparative Examples 1 and 5 are determined to be "dangerous materials" in the hazardous material determination under the Japanese Fire Service Law.
• the heat storage agent composition of Comparative Example 9 is determined as a "designated combustible material" in the hazardous material determination under the Fire Service Act of Japan.
• Heat cycle test For each heat storage agent composition, a test (heat cycle test) was conducted in which the temperature of the heat storage agent composition was repeatedly raised and lowered multiple times. The results of the heat cycle test indicate physical properties of the heat storage agent composition (heat storage material) after multiple uses.
• the heat cycle test was specifically carried out by the following method: (1) A heat storage agent composition was placed in a test tube, and a thermocouple was inserted into the center of the heat storage agent composition; The test tube was placed in a constant temperature bath with (3) After holding the temperature in the constant temperature bath at 50°C for 1 hour, the temperature was lowered from 50°C to 2°C over 1 hour, held at 2°C for 1 hour, and then raised from 2°C to 50°C over 1 hour. was repeated 50 times; (4) After performing the variable temperature cycle, the state of the heat storage agent composition was observed. Specifically, it was visually determined whether or not the heat storage agent composition was solid-liquid separated.
• Tables 3 and 4 show the measurement and evaluation results of each physical property.
• the heat storage agent composition or heat storage material according to one embodiment of the present invention can maintain the temperature of a temperature-controlled article in various controlled temperature ranges (for example, 1°C to 40°C), and meets the requirements of the Japanese Fire Service Law. It does not correspond to dangerous goods in Therefore, one embodiment of the present invention can be suitably used for storing and transporting various articles such as pharmaceuticals, medical devices, cells, specimens, organs, chemical substances or foods. Moreover, one embodiment of the present invention can be suitably used as various heat-retaining tools. Furthermore, the heat storage agent composition according to one embodiment of the present invention can be suitably used as a heat storage material in various heat storage devices such as air conditioners and heat recovery systems.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Combustion & Propulsion (AREA)
• Thermal Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84323214

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (4)

• 2022
  • 2022-05-30 JP JP2023525804A patent/JPWO2022255281A1/ja active Pending
  • 2022-05-30 WO PCT/JP2022/021854 patent/WO2022255281A1/ja not_active Ceased

Patent Citations (4)

Also Published As

Similar Documents

Legal Events