WO2022158484A1 - Composition de matériau inorganique accumulateur de chaleur latente - Google Patents

Composition de matériau inorganique accumulateur de chaleur latente Download PDF

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Publication number
WO2022158484A1
WO2022158484A1 PCT/JP2022/001762 JP2022001762W WO2022158484A1 WO 2022158484 A1 WO2022158484 A1 WO 2022158484A1 JP 2022001762 W JP2022001762 W JP 2022001762W WO 2022158484 A1 WO2022158484 A1 WO 2022158484A1
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weight
composition
heat storage
benzoate
latent heat
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PCT/JP2022/001762
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English (en)
Japanese (ja)
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千秋 片野
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株式会社カネカ
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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

Definitions

  • the present invention relates to an inorganic latent heat storage material composition.
  • Temperature-controlled articles are temperature-controlled at a controlled temperature for quality maintenance. In particular, when transporting or storing a temperature-controlled article, it is preferable to keep the temperature-controlled article cool or warm for a predetermined period of time within a controlled temperature range.
  • latent heat storage material compositions (sometimes referred to as "PCM: Phase Change Materials”), mainly organic latent heat storage material compositions have been used (Patent Documents 1).
  • Patent Document 2 the main component is sodium thiosulfate pentahydrate, which is an inorganic hydrate, and sodium thiosulfate pentahydrate as a nucleating agent has a low solubility in an aqueous solution and exists as a solid.
  • An inorganic latent heat storage material composition to which benzoic acid and its derivatives are added is disclosed.
  • the conventional inorganic latent heat storage material composition as described above has a problem that the degree of supercooling is large.
  • One embodiment of the present invention has been made in view of the above-mentioned problems, and its object is to provide an inorganic latent heat storage material composition with a small degree of supercooling.
  • the present inventors have completed the present invention as a result of intensive studies to solve the above problems.
  • the inorganic latent heat storage material composition is an inorganic latent heat storage material composition, and consists of (a) calcium chloride hexahydrate and (b) bromide salt and chloride salt. (c) a cellulose derivative, and (d) 0.40% by weight or more of a strontium salt in 100% by weight of the inorganic latent heat storage material composition. , (e) 0.20% by weight or more of benzoate, and (f) (f-1) 0.5% to 0.9% by weight of oleic acid, and/or (f-2) 0.2% polyvinylpyrrolidone. % to 3.0% by weight, and the total content of the (d) strontium salt and the (e) benzoate in 100% by weight of the inorganic latent heat storage material composition is 0.90% by weight. % or more.
  • an inorganic latent heat storage material composition with a small degree of supercooling.
  • PCM Physical idea of one embodiment of the present invention
  • the purpose of PCM is to (i) stably maintain temperature-controlled articles at a predetermined temperature such as room temperature (for example, 15° C. to 30° C.), and/or (ii) maintain the living space at a predetermined temperature ( For example, the temperature is maintained at 15° C. to 30° C.).
  • a predetermined temperature such as room temperature (for example, 15° C. to 30° C.)
  • a predetermined temperature for example, at a constant temperature or a substantially constant temperature
  • transporting or storing a temperature-controlled article stably at a predetermined temperature is referred to as “constant temperature transportation”
  • the use for constant temperature transportation is called “constant temperature transportation”.
  • transportation use Sometimes referred to as “transportation use”.
  • a PCM used to maintain a temperature-controlled article and/or a living space at a temperature above 0°C is hereinafter referred to as a "heat storage material” and maintains a temperature-controlled article and/or a living space at a temperature of 0°C or lower.
  • the PCM used for this purpose is hereinafter referred to as "cold storage material”.
  • heat storage materials organic heat storage materials are mainly used, and as cold storage materials, inorganic cold storage materials (including cold insulators that change phase in a minus temperature range of 0°C or less) are mainly used. ing. Inorganic heat storage materials have been developed for a long time, but compared to organic heat storage materials, inorganic heat storage materials have unstable durability and thermal properties, making it difficult to stably control melting and solidification. Met. For this reason, conventional inorganic heat storage materials are rarely used for "constant temperature transportation applications that require strict temperature control".
  • the organic heat storage material is (i) flammable, (ii) raw materials of the heat storage material are often legally regulated hazardous materials, and (iii) the environmental load is high in the event of leakage. , and (iv) the high cost of the raw material for the heat storage material, further improvements were required for one-way constant temperature transport applications. Therefore, the inorganic system has (i) excellent environmental compatibility, safety and economic efficiency, (ii) suitable use for constant temperature transportation, and (iii) stable durability and thermal properties (supercooling suppression property). A heat storage material is desired. The present inventors have made extensive studies to obtain such an inorganic latent heat storage material composition.
  • phase separation of the inorganic latent heat storage material composition for example, (i) inorganic water (ii) precipitation of inorganic hydrates and/or inorganic salts, and (iii) precipitation of inorganic hydrates and/or inorganic salts, etc.
  • the thermal properties such as phase change temperature and latent heat amount of the inorganic latent heat storage material composition change, and as a result, the inorganic latent heat storage material composition ceases to function as a latent heat storage material.
  • Inorganic latent heat storage material compositions tend to be supercooled to a greater extent than organic latent heat storage material compositions. When the degree of supercooling is large, there is a problem that the inorganic latent heat storage material composition does not solidify within the required temperature range, and the temperature retention performance is not exhibited.
  • the inventors conducted intensive studies. As a result, the present inventors have developed an inorganic latent heat storage material containing calcium chloride hexahydrate as a main ingredient and further containing a specific amount of benzoate, a specific amount of oleic acid and/or a specific amount of polyvinylpyrrolidone. The inventors have independently found that the degree of supercooling of the composition is small, which led to the completion of the present invention.
  • the inorganic latent heat storage material composition according to one embodiment of the present invention also has the following advantages: (i) excellent environmental compatibility, safety and economy, and (ii) suitable for constant temperature transport applications. and (iii) have stable durability and thermal properties (supercooling inhibition).
  • An inorganic latent heat storage material composition according to one embodiment of the present invention is an inorganic latent heat storage material composition, and is a group consisting of (a) calcium chloride hexahydrate and (b) a bromide salt and a chloride salt.
  • An inorganic latent heat storage material composition may have the following configuration: an inorganic latent heat storage material composition containing at least all of the following (a) to (f): , (a) calcium chloride hexahydrate, (b) one or more inorganic salts selected from the group consisting of bromide salts and chloride salts; (c) a cellulose derivative, (d) a strontium salt; (e) benzoate, and (f) (f-1) oleic acid, and/or (f-2) polyvinylpyrrolidone, In 100% by weight of the inorganic latent heat storage material composition, the content of the (d) strontium salt is 0.40% by weight or more, and the content of the (e) benzoate is 0.20% by weight or more.
  • the total content of the (d) strontium salt and the (e) benzoate is 0.90% by weight or more
  • the content of the (f-1) oleic acid is 100% by weight of the inorganic latent heat storage material composition.
  • medium 0.5 wt% to 0.9 wt%
  • the content of the (f-2) polyvinylpyrrolidone is the inorganic latent heat storage material composition 100. 0.2 wt % to 3.0 wt % in the wt %.
  • the "inorganic latent heat storage material composition” is sometimes referred to as the “composition”, and the “inorganic latent heat storage material composition according to one embodiment of the present invention” is referred to as the “present composition”.
  • “(b) one or more inorganic salts selected from the group consisting of bromide salts and chloride salts” may be referred to as “(b) component”
  • “(f) (f-1) Oleic acid and/or (f-2) polyvinylpyrrolidone” may be referred to as "(f) component”.
  • the present composition has the advantage that the degree of supercooling is small because it has the configuration described above. Furthermore, the present composition has the structure described above, so that (i) the water of hydration from the inorganic hydrate (calcium chloride hexahydrate), even after long-term and/or numerous repeated uses, There is no risk of separation and precipitation and sedimentation of inorganic hydrates and/or inorganic salts (component (b)). That is, since the present composition has the above-described structure, there is no possibility that the thermal properties of the composition, such as the phase change temperature and latent heat amount, will change significantly even after long-term and/or repeated use. It also has advantages. In other words, the present composition has the above-described structure, so it also has the advantage of being excellent in durability.
  • the "degree of supercooling” may be referred to as “supercooling suppression property”. It is intended that the smaller the degree of supercooling, the better the supercooling suppression property.
  • “durability” with respect to the inorganic latent heat storage material composition means that the composition does not decrease in viscosity, deteriorate in thermal properties, and/or undergo phase separation after long-term and/or repeated use of the composition. intended nature.
  • “repeated use” with respect to the inorganic latent heat storage material composition means that the composition is repeatedly melted and solidified.
  • the smaller the degree of viscosity reduction, thermal property deterioration and/or phase separation of the composition after long-term use of the composition the more excellent the durability of the composition.
  • the longer the composition can be used without viscosity reduction, thermal property deterioration and/or phase separation the more durable the composition.
  • the smaller the degree of viscosity reduction, thermal property deterioration and/or phase separation of the composition after a number of repeated uses of the composition the more excellent the durability of the composition.
  • This composition has the advantage of being able to easily produce a composition having a melting temperature of 15°C to 30°C by using calcium chloride hexahydrate as the main ingredient.
  • the present composition containing calcium chloride hexahydrate as a main component, for example, sodium acetate trihydrate, sodium sulfate decahydrate, disodium hydrogen phosphate dodecahydrate, sodium carbonate decahydrate, etc., are used as main components.
  • An inorganic latent heat storage material composition is known. Compared to such a composition based on an inorganic salt other than calcium chloride hexahydrate, the present composition (i) is considered to be an environment in which humans live (human living environment). It can be used more preferably in the assumed temperature range, (ii) the temperature of the temperature-controlled article can be stably maintained in the vicinity of 15 ° C. to 30 ° C., and (iii) the resulting composition is more durable. It has the advantage of being superior and less odorous.
  • the content of calcium chloride hexahydrate in the present composition is not particularly limited, and can be appropriately set based on the desired melting temperature and viscosity.
  • the composition preferably contains 50.00% by weight or more, more preferably 55.00% by weight or more, and 60.00% by weight of calcium chloride hexahydrate relative to 100% by weight of the composition. More preferably, it contains 65.00% by weight or more, and particularly preferably 70.00% by weight or more.
  • the content of calcium chloride hexahydrate in the present composition is within the range described above, (i) the latent heat amount per weight increases, so that it functions efficiently as a heat storage material, and (ii) Advantages include that the composition can be used in a temperature range that simulates the environment in which humans live, and (iii) that the resulting composition has excellent durability and little odor.
  • the upper limit of the content of calcium chloride hexahydrate in the present composition is not particularly limited, and may be, for example, 95.00% by weight or less with respect to 100% by weight of the composition.
  • the (b) component may have the function of (i) adjusting the melting temperature and/or freezing temperature of the composition and/or (ii) preventing supercooling of the composition.
  • “Substances that can modulate the melting and/or freezing temperature of a composition” are sometimes referred to as “melting point modifiers” or “freezing point depressants.”
  • a “substance capable of preventing supercooling of a composition” may also be referred to as a "supercooling inhibitor", “supercooling inhibitor”, “crystal nucleating agent”, “nucleating agent” or “nucleating agent”. be.
  • the component (b) is a “melting point modifier” or “freezing point depressant”, and/or a “supercooling inhibitor”, “supercooling inhibitor”, “crystal nucleating agent”, “nucleating agent” or “ nucleating agent”.
  • (a) calcium chloride hexahydrate described above, and (c) cellulose derivatives, (d) strontium salts, (e) benzoates and (f) substances listed as components (compounds) described later ) is not included in the (b) component.
  • (a) calcium chloride hexahydrate, and (d) the strontium salts strontium bromide and strontium chloride are not considered components of (b).
  • the amounts of (a) calcium chloride hexahydrate and (d) the strontium salts strontium bromide and strontium chloride are not included in the total amount of component (b) used.
  • composition is selected from the group consisting of bromide salts and chloride salts, in addition to (a) calcium chloride hexahydrate and (d) strontium salts (e.g., strontium bromide and strontium chloride).
  • strontium salts e.g., strontium bromide and strontium chloride.
  • One or more inorganic salts are included as component (b).
  • Bromide salts are preferably water-soluble inorganic salts, such as metal bromides and ammonium bromide.
  • Water-soluble inorganic salt as used herein means an inorganic salt that has a solubility of 0.01 g/ml or more in water at 25°C.
  • metal bromides examples include lithium bromide, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, iron bromide, zinc bromide, and barium bromide.
  • bromide salt one of the compounds described above may be used alone, or two or more thereof may be used in combination.
  • the bromide salt preferably contains one or more selected from the group consisting of sodium bromide, potassium bromide and ammonium bromide, and is selected from the group consisting of sodium bromide, potassium bromide and ammonium bromide. more preferably one or more of these, more preferably sodium bromide and potassium bromide.
  • the chloride salt is preferably a water-soluble inorganic salt, such as metal chloride and ammonium chloride.
  • metal chlorides include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, iron chloride, zinc chloride, aluminum chloride, barium chloride and cobalt chloride.
  • the chloride salt one of the compounds described above may be used alone, or two or more thereof may be used in combination.
  • the chloride salt preferably contains sodium chloride, more preferably sodium chloride, because it is easily available and is widely used as a melting point adjuster.
  • Components (b) are sodium bromide, potassium bromide and sodium chloride, since the melting temperature and/or freezing temperature of the resulting composition can be adjusted to a desired temperature (for example, 15° C. to 30° C.) by using a small amount. is more preferable. It should be noted that sodium chloride can function as both a “melting point modifier" and a "supercooling inhibitor".
  • sodium bromide, potassium bromide, calcium bromide, ammonium bromide, iron bromide, zinc bromide, barium bromide, sodium chloride, potassium chloride, magnesium chloride, iron chloride, chloride Zinc and cobalt chloride can function as melting point modifiers.
  • sodium chloride and barium chloride can function as supercooling inhibitors.
  • the total content of component (b) in the present composition is not particularly limited, and can be appropriately selected according to the content of calcium chloride hexahydrate in the composition.
  • the present composition preferably contains 1.0% to 45.0% by weight, and 2.0% to 40.0% by weight, of component (b) in total with respect to 100% by weight of the composition. more preferably 3.0% to 35.0% by weight, particularly preferably 5.0% to 30.0% by weight.
  • the obtained composition when used for building materials such as wall materials, floor materials, ceiling materials, roofing materials, etc., the space near the building materials or the space covered with the building materials
  • the temperature can be maintained at an appropriate temperature (for example, 15 to 30°C) with high accuracy, and (ii) the resulting composition can stably maintain the temperature of the temperature-controlled article around 15°C to 30°C. has the advantage of
  • the composition may further contain a melting point modifier other than the component (b) that can function as a melting point modifier (hereinafter sometimes referred to as "other melting point modifier").
  • other melting point modifiers include (i) ammonium salts other than ammonium bromide and ammonium chloride, (ii) metal halides other than metal bromides and metal chlorides, (iii) metal non-halides, and (iv) urea. etc. can be mentioned.
  • Ammonium salts other than ammonium bromide and ammonium chloride, which are melting point regulators, include ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium carbamate, ammonium formate, triammonium citrate and ammonium acetate.
  • metal halides other than metal bromides and metal chlorides that are melting point adjusters include lithium iodide, sodium iodide, and potassium iodide.
  • Metal non-halides that are melting point modifiers include sodium sulfate, sodium nitrate, sodium acetate, sodium phosphate, sodium borohydride, sodium formate, sodium oxalate, sodium carbonate, sodium glutamate, sodium hydroxide, potassium sulfate, Potassium nitrate, potassium acetate, potassium phosphate, potassium borohydride, potassium formate, potassium oxalate, potassium carbonate, potassium glutamate, potassium hydroxide, calcium nitrate, calcium glutamate, aluminum sulfate, aluminum nitrate, magnesium sulfate, magnesium nitrate, carbonate Magnesium, magnesium glutamate and the like can be mentioned.
  • the other melting point modifiers mentioned above may be used singly or in combination of two or more.
  • the total content of the melting point modifier in the present composition (the total content of the component (b) that can function as a melting point modifier and other melting point modifiers) is not particularly limited, and calcium chloride in the composition It can be appropriately set according to the amount of hexahydrate.
  • the total content of the melting point modifier in the present composition is preferably 0.05 mol to 2.00 mol, more preferably 0.10 mol to 1.50 mol, per 1.0 mol of calcium chloride hexahydrate. More preferably 0.30 mol to 1.50 mol.
  • the resulting composition when used for building materials such as wall materials, floor materials, ceiling materials, roofing materials, etc., the space in the vicinity of the building material member or the space covered by the building material member
  • the temperature can be maintained at an appropriate temperature with high accuracy, and (ii) the obtained composition has the advantages of being able to stably maintain the temperature of the temperature-controlled article around 15°C to 30°C.
  • the present composition contains a melting point modifier (component (b) that can function as a melting point modifier and other melting point modifiers) in a total amount of from 0.30 mol to 1.0 mol of calcium chloride hexahydrate. A case of containing 1.50 mol will be described.
  • the temperature of the space near the building material member or the space covered with the building material member is It has the advantages of being able to stably maintain the temperature in the range of 15°C to 30°C, and (ii) that the obtained composition can stably maintain the temperature of the article to be temperature controlled at around 15°C to 30°C. have.
  • the amount of the metal halide other than the metal bromide and the metal chloride, which is a melting point modifier and contained in the composition is 1.0 mol or less per 1.0 mol of calcium chloride hexahydrate. is preferably 0.5 mol or less, and even more preferably 0.3 mol or less.
  • the obtained composition when used for building materials such as wall materials, floor materials, ceiling materials, roofing materials, etc., the space near the building material members or the space covered by the building material members.
  • the advantage is that the temperature can be maintained at an appropriate temperature with higher accuracy, and (ii) the obtained composition can stably maintain the temperature of the temperature-controlled article around 15 ° C. to 30 ° C. have
  • the content of the ammonium salt contained in the present composition is preferably small because it is easy to handle, has a small environmental load, and has little odor.
  • the content of the ammonium salt contained in the composition is preferably 1% by weight or less, more preferably 0.5% by weight or less, with respect to 100% by weight of the total weight of the composition. 0.1% by weight or less is more preferable, 0.01% by weight or less is more preferable, and 0% by weight is particularly preferable.
  • the cellulose derivative may function to increase the viscosity of the composition and/or to allow the composition to gel. "Substances that can increase the viscosity of the composition” or “substances that can gel the composition” are sometimes referred to as “thickening agents” or “gelling agents,” respectively. That is, the cellulose derivative can be said to be a “thickening agent” or a “gelling agent”.
  • this composition contains a cellulose derivative, it has the advantage that the composition remains in a gel state in a temperature environment exceeding the melting temperature.
  • Cellulose derivatives are thermosetting thickeners. Therefore, a composition containing a cellulose derivative has the advantage that it can be produced efficiently and stably.
  • Cellulose derivatives include carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose. Since (i) it is nonionic, it does not affect inorganic ions dissolved in the composition, and (ii) an aqueous solution with a high ion concentration can be made into a gel. and more preferably hydroxyethyl cellulose.
  • inorganic salt is not limited to component (b), but also includes inorganic salts belonging to other components
  • temperature changes Precipitation of inorganic salts may occur over time.
  • the composition comprises a cellulose derivative
  • the cellulose derivative not only (i) allows the composition to gel, but also (ii) effectively disperses the ions of inorganic salts dissolved in the composition. be able to. Thereby, the cellulose derivative can suppress precipitation of inorganic salts in the present composition.
  • the cellulose derivative contained in the composition does not affect the melting and/or solidification behavior of the composition and allows the composition to maintain a high latent heat of fusion.
  • the present composition contains a cellulose derivative, it has the advantage that the composition remains in a gel state even after a heat cycle test is performed under the environmental temperature at which the composition is assumed to be used.
  • the present composition contains a cellulose derivative, the shape of the composition can be kept constant even when the composition is in a molten state (gel state). As a result, even if the composition is in a molten state (gel state), it is possible to reduce the environmental load without the risk of polluting the environment.
  • the present composition preferably contains 0.3% to 7.0% by weight, more preferably 0.5% to 6.0% by weight, of the cellulose derivative relative to 100% by weight of the composition. , 1.0% to 5.0% by weight. According to this configuration, (i) aggregation and precipitation of salts (both inorganic salts and organic salts) dissolved in the composition can be prevented, (ii) the composition has good handleability, and (iii) It has the advantage that the composition is in a gel state under a temperature environment exceeding the melting temperature of the composition.
  • the composition may further contain a thickening agent other than the cellulose derivative.
  • Thickeners other than cellulose derivatives include, for example, water absorbent resins, gelatin, agar, xanthan gum, gum arabic, guar gum, carrageenan, and konjac.
  • water-absorbing resins include starch-based resins, acrylate-based resins, poval-based resins, and the like.
  • Silica includes fumed silica, precipitated silica, silica gel and the like.
  • the thickener other than the cellulose derivative may be an ionic thickener or a nonionic thickener.
  • Calcium chloride hexahydrate and component (b) contained in the composition are often dissolved in the composition to form ions. Therefore, nonionic thickeners are preferred as thickeners other than cellulose derivatives because they do not affect inorganic ions dissolved in the composition. Examples of nonionic thickeners include guar gum and dextrin.
  • the total content of the thickening agent in the present composition (the total content of the cellulose derivative and the thickening agent other than the cellulose derivative) is not particularly limited, and the amount of calcium chloride hexahydrate in the composition It can be set as appropriate.
  • the total content of the thickening agent in the present composition is preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight, per 100 parts by weight of calcium chloride hexahydrate. According to this configuration, (i) the aggregation and precipitation of salts dissolved in the composition can be prevented, (ii) the composition has good handleability, and (iii) the temperature environment exceeds the melting temperature of the composition. Underneath, it has the advantage that the composition is in a gel state.
  • strontium salt may have the function of preventing supercooling of the composition. Therefore, strontium salts can be referred to as "supercooling inhibitors”, “supercooling inhibitors”, “crystal nucleating agents”, “nucleating agents” or “nucleating agents”.
  • Strontium salts include strontium chloride and strontium chloride hexahydrate.
  • strontium salt one of the compounds described above may be used alone, or two or more of them may be used in combination.
  • the strontium salt preferably contains strontium chloride hexahydrate, more preferably strontium chloride hexahydrate, because of its excellent safety and high versatility.
  • the present composition contains 0.40% by weight or more, preferably 0.40% to 8.00% by weight, more preferably 0.48% to 8.0% by weight, based on 100% by weight of the composition, of a strontium salt.
  • a strontium salt 00 wt%, more preferably 0.50 wt% to 8.00 wt%, more preferably 0.55 wt% to 8.00 wt%, 0.60 wt% to 8
  • This configuration has the advantage of preventing overcooling of the composition without affecting salts other than the strontium salt dissolved in the composition. Further, when the upper limit of the strontium salt is 3.00% by weight or less or 1.50% by weight or less, (i) the raw material cost can be kept low, and (ii) the supersaturated composition Since the salt concentration of can be kept low, it also has the advantage that the composition has excellent stability and durability (precipitation of salt).
  • benzoate (1-5. (e) benzoate
  • benzoates can be called "supercooling inhibitors", “supercooling inhibitors”, “crystal nucleating agents”, “nucleating agents” or “nucleating agents”.
  • Benzoates may also function to prevent spoilage of the composition. Therefore, benzoate can also be called a "preservative”.
  • Benzoates include (i) metal salts of benzoic acid such as sodium benzoate, potassium benzoate, lithium benzoate and calcium benzoate, and (ii) ammonium benzoate.
  • benzoic acid such as sodium benzoate, potassium benzoate, lithium benzoate and calcium benzoate
  • ammonium benzoate As the benzoate, one of the compounds described above may be used alone, or two or more thereof may be used in combination.
  • the benzoate preferably contains one or more selected from the group consisting of a metal salt of benzoic acid and ammonium benzoate, since it has high water solubility and can reduce the degree of supercooling of the composition. It is more preferably one or more selected from the group consisting of a metal salt and ammonium benzoate, and more preferably one or more selected from the group consisting of sodium benzoate, potassium benzoate and ammonium benzoate. Preferred is sodium benzoate, particularly preferred.
  • the particle size of the benzoate in the present composition is preferably 1 ⁇ m to 1 mm, more preferably 2 ⁇ m to 900 ⁇ m, even more preferably 5 ⁇ m to 800 ⁇ m, particularly preferably 10 ⁇ m to 800 ⁇ m. .
  • This configuration has the advantage that the benzoate is dispersed in the composition so that the benzoate functions more efficiently to reduce the degree of supercooling of the composition.
  • the particle size of the benzoate in the composition can be measured with a digital scale, for example, by observing the composition using a digital microscope (model number: VHX-5000, manufactured by Keyence Corporation). . Since the components other than the benzoate are dissolved or dispersed very finely in the composition, it is very difficult to observe the components using a digital microscope. On the other hand, in the present composition, benzoate is present as a relatively large white substance compared to the ingredients other than benzoate. Therefore, the white substance observed in the composition using a digital microscope can be regarded as benzoate, and the particle size of benzoate in the composition can be determined by measuring the particle size of the white substance. Diameter can be measured.
  • the present composition contains 0.20 wt% or more, preferably 0.25 wt% to 5.00 wt%, and 0.30 wt% to 3 00% by weight, more preferably 0.30% to 2.00% by weight, particularly preferably 0.50% to 2.00% by weight, and 0.50% by weight to Most preferably it contains 1.50% by weight.
  • the composition has the advantage of a consistently low degree of supercooling, in other words a low degree of supercooling even after repeated and long-term use of the composition.
  • the upper limit of the benzoate is 3.00% by weight or less or 1.50% by weight or less, (i) the raw material cost can be kept low, and (ii) the supersaturated composition Since the salt concentration of the composition can be kept low, there is also the advantage that the stability and durability (precipitation of salt) of the composition are excellent.
  • the total content of strontium salt and benzoate in the present composition is 0.90% by weight or more, preferably 0.95% by weight or more, preferably 0.98% by weight or more. It is preferably 0.00% by weight or more, preferably 1.10% by weight or more, more preferably 1.20% by weight or more, further preferably 1.30% by weight or more. .40% by weight or more is particularly preferred. According to this configuration, the composition has the advantage of a consistently low degree of supercooling, in other words a low degree of supercooling even after repeated and long-term use of the composition.
  • the content of benzoate in the present composition may be appropriately set according to the content of strontium salt. For example, if the composition contains 0.95% or more by weight of strontium salt, based on 100% by weight of the composition, then the composition contains 0.20% or more, by weight of 100% of the composition, of 0.20% or more. It preferably contains 25% to 5.00% by weight, more preferably 0.25% to 3.00% by weight, and even more preferably 0.25% to 2.00% by weight. For example, if the composition contains 0.70% by weight or more and less than 0.95% by weight of strontium salt relative to 100% by weight of the composition, the composition contains 0.30% by weight of benzoate relative to 100% by weight of the composition.
  • the composition contains 0.40% by weight or more and less than 0.70% by weight of strontium salt relative to 100% by weight of the composition, the composition contains 0.40% by weight of benzoate relative to 100% by weight of the composition.
  • % to 5.00% by weight preferably 0.45% to 5.00% by weight, more preferably 0.50% to 5.00% by weight, 0.50% by weight More preferably, it contains up to 3.00% by weight, more preferably 0.50% by weight to 2.00% by weight.
  • the composition has the advantage of a consistently low degree of supercooling, in other words a low degree of supercooling even after repeated and long-term use of the composition.
  • the present composition further contains a supercooling inhibitor other than component (b), a strontium salt and a benzoate (hereinafter sometimes referred to as "other supercooling inhibitor") that can function as a supercooling inhibitor.
  • a supercooling inhibitor other than component (b), a strontium salt and a benzoate hereinafter sometimes referred to as "other supercooling inhibitor”
  • other supercooling inhibitors include (i) sodium pyrophosphate decahydrate, sodium tetraborate decahydrate, sodium carbonate, sodium carbonate monohydrate, sodium carbonate decahydrate, barium bromate monohydrate, calcium sulfate dihydrate, alum, disodium dihydrogen pyrophosphate hexahydrate, disodium hydrogen phosphate dodecahydrate, disodium hydrogen phosphite pentahydrate, trisodium phosphate dodecahydrate, sodium dihydrogen phosphate dihydrate, barium sulfide, calcium tartrate, strontium hydroxide oc
  • sparingly soluble salts such as barium sulfate, barium carbonate, lithium fluoride, calcium fluoride, silicon dioxide (silica), kaolinite, cryolite, fly ash, sepiolite, graphite and carbon black. organic inorganic salts, and the like. In this specification, fly ash, graphite and carbon black are also regarded as sparingly water-soluble inorganic salts.
  • the term "poorly water-soluble inorganic salt” means an inorganic salt having a solubility in water at 25°C of less than 0.01 g/ml.
  • anti-supercooling agents may be used singly or in combination of two or more.
  • the total content of the supercooling inhibitor in the present composition is particularly It is not limited and can be appropriately set according to the amount of calcium chloride hexahydrate in the composition.
  • the total content of supercooling inhibitors in the present composition is preferably 0.95% to 30.0% by weight, and 1.0% to 25.0% by weight, based on 100% by weight of the composition. % by weight is more preferred, 2.0% to 20.0% by weight is more preferred, and 3.0% to 15.0% by weight is particularly preferred. According to this configuration, the composition has the advantage of a consistently low degree of supercooling, in other words a low degree of supercooling even after repeated and long-term use of the composition.
  • the component (f) may have the function of preventing phase separation of the composition.
  • a “substance capable of preventing phase separation of a composition” may be referred to as a “phase separation inhibitor” or “phase separation inhibitor”. That is, the component (f) can be said to be a "phase separation inhibitor” or "phase separation inhibitor”.
  • the present composition may contain (f-1) oleic acid alone, (f-2) polyvinylpyrrolidone (PVP) alone, and (f-1) oleic acid and (f-2) PVP.
  • composition contains (f-1) oleic acid as the component (f)
  • the composition contains 0.5% by weight of oleic acid with respect to 100% by weight of the composition. 0.9% by weight, more preferably 0.6% to 0.8% by weight. This configuration has the advantage that a small amount of oleic acid can prevent phase separation of the composition.
  • oleic acid a mixture containing oleic acid can also be used, for example, the following commercial products can also be used: NAA (registered trademark)-34 (manufactured by NOF Corporation, oleic acid as the main component mixture), NAA (registered trademark)-35 (manufactured by NOF Corporation, a mixture containing oleic acid as the main component), extra olein (manufactured by NOF Corporation, a mixture containing oleic acid as the main component) and Nsp (manufactured by Hope Pharmaceutical Co., Ltd., fatty acid mixture) and the like.
  • NAA registered trademark
  • NAA registered trademark-35
  • extra olein manufactured by NOF Corporation, a mixture containing oleic acid as the main component
  • Nsp manufactured by Hope Pharmaceutical Co., Ltd., fatty acid mixture
  • the content of the mixture containing oleic acid in the composition is such that the content of oleic acid in the composition is 0.5% to 0.9% by weight relative to 100% by weight of the composition. It can be set appropriately depending on the concentration of oleic acid in the mixture.
  • the composition contains (f-2) polyvinylpyrrolidone (PVP) as the component (f), the composition contains 0.2% to 3.0% by weight of PVP with respect to 100% by weight of the composition. %, preferably 0.3 wt % to 2.5 wt %, more preferably 0.5 wt % to 2.0 wt %.
  • This configuration has the advantage of being able to prevent phase separation of the composition for a long period of time and maintain the gel state of the composition for a long period of time.
  • the present composition contains 3.0% by weight or less of PVP with respect to 100% by weight of the composition, (i) the amount of heat per unit weight of the composition is large, and (ii) the composition is non-uniform. It also has the advantage that there is no risk of gelation.
  • the composition contains a predetermined amount of oleic acid, or a predetermined amount of PVP, or a predetermined amount of each of oleic acid and PVP, so that even after prolonged and/or multiple repeated use of the composition, , phase separation of the composition in a molten state (gel state) (for example, separation of water of hydration from inorganic hydrate (calcium chloride hexahydrate), etc.) can be prevented.
  • gel state of the composition which is in a molten state (gel state)
  • the stability of the gel state of the composition can be improved.
  • Oleic acid and PVP have the advantage of being easily dispersed uniformly or almost uniformly in the composition. The reason for this is not clear, but is presumed as follows. Oleic acid has a polar group represented by --COOH, and PVP has polar groups represented by --CO and --CN. These polar groups have a strong affinity for the --OH group of calcium chloride hexahydrate, which is the main ingredient. As a result, it is assumed that oleic acid or PVP and the composition are compatible with each other. It should be noted that one embodiment of the present invention is not limited by such speculation.
  • PVP Compared to oleic acid, PVP has a greater effect of preventing phase separation in the composition. Specifically, compared to oleic acid, PVP is more effective in preventing phase separation over long-term and/or multiple repeated uses of the composition. The reason for this is not clear, but is presumed as follows.
  • the -CO group of PVP interacts with the -OH group of the cellulose derivative, and is presumed to easily undergo ionic cross-linking (pseudo-cross-linking) with polyvalent metal ions (calcium ions) of calcium chloride hexahydrate, which is the main ingredient. . It should be noted that one embodiment of the present invention is not limited by such speculation.
  • the present composition preferably contains PVP as the (f) component, more preferably PVP as the (f) component.
  • PVP polyvinyl sulfate
  • the composition contains PVP, it also has the advantage of a smaller difference between freezing and melting temperatures and greater durability compared to oleic acid.
  • the present composition may further contain a phase separation inhibitor other than the component (f) that can function as a phase separation inhibitor (hereinafter sometimes referred to as "other phase separation inhibitor").
  • phase separation inhibitors include, for example, fatty acids (other than oleic acid) having a melting point of 20° C. or lower, glycerin, vegetable oils, and paraffin.
  • fatty acids having a melting point of 20°C or lower examples include unsaturated fatty acids such as linoleic acid, linolenic acid, ricinoleic acid, and erucic acid.
  • unsaturated fatty acids such as linoleic acid, linolenic acid, ricinoleic acid, and erucic acid.
  • a fatty acid mixture containing 40% by weight or more of the above fatty acids may also be used.
  • Fatty acid mixtures also include some of the vegetable oils described below.
  • vegetable oil those that are liquid at room temperature and have a melting point of 10°C or less are preferable, and suitable examples include sunflower oil, corn oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, olive oil, soybean oil, linseed oil and castor oil. be able to.
  • paraffin those that are liquid at room temperature and have a melting point of 10°C or less are preferable, and suitable examples include liquid paraffin, pentadecane, tetradecane, tridecane, dodecane, undecane, and decane.
  • the other anti-phase separation agents mentioned above may be used singly or in combination of two or more.
  • an organic solvent eg, a monocyclic aromatic compound, more specifically benzene, toluene, xylene, ethylenebenzene, cumene, paracymene, dimethyl phthalate, diethyl phthalate and dipropyl phthalate
  • the content of the organic solvent having volatility at room temperature in 100 parts by weight of the total weight of the present composition is preferably 50 parts by weight or less, more preferably 10 parts by weight or less. , more preferably 5 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 parts by weight or less, and particularly preferably 0.1 parts by weight or less.
  • the content of the monocyclic aromatic compound in 100 parts by weight of the total weight of the present composition is preferably 50 parts by weight or less, more preferably 10 parts by weight or less, and preferably 5 parts by weight or less. More preferably, it is 1 part by weight or less, even more preferably 0.5 parts by weight or less, and particularly preferably 0.1 part by weight or less.
  • Total of one or more compounds selected from the group consisting of benzene, toluene, xylene, ethylenebenzene, cumene, paracymene, dimethyl phthalate, diethyl phthalate and dipropyl phthalate in 100 parts by weight of the total weight of the composition is preferably 50 parts by weight or less, more preferably 10 parts by weight or less, more preferably 5 parts by weight or less, more preferably 1 part by weight or less, and 0.5 parts by weight or less. It is more preferably 5 parts by weight or less, and particularly preferably 0.1 parts by weight or less.
  • composition may contain other components as long as they do not impair the effects of one embodiment of the present invention.
  • Other ingredients include solvents, alcohols, preservatives, fragrances, coloring agents, antifoaming agents, flame retardants, light stabilizers, UV absorbers, storage stabilizers, foam control agents, lubricants, antifungal agents, Examples include antibacterial agents, macromolecular polymers, other organic compounds, and other inorganic compounds.
  • water is preferable in order to increase the flame retardancy of the composition.
  • the alcohols include lower alcohols (e.g., methanol, ethanol, 2-propanol, ethylene glycol, glycerol, etc.) and higher alcohols (e.g., capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol, etc.). Alcohols may function to adjust the melting temperature and/or freezing temperature of the composition.
  • lower alcohols e.g., methanol, ethanol, 2-propanol, ethylene glycol, glycerol, etc.
  • higher alcohols e.g., capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol, etc.
  • Alcohols may function to adjust the melting temperature and/or freezing temperature of the composition.
  • viscosity of the inorganic latent heat storage material composition measured by a vibration viscometer at the melting temperature +10 ° C. to +35 ° C. of the inorganic latent heat storage material composition (hereinafter referred to as "viscosity of the composition"). ) will be explained.
  • the viscosity of the composition can also be said to be “the viscosity obtained by measuring the inorganic latent heat storage material composition whose melting temperature is +10°C to +35°C with a vibration viscometer".
  • the vibration viscometer includes a tuning fork vibration viscometer, a tuning fork vibration rheometer, and the like.
  • the viscosity of the composition is preferably 2 Pa ⁇ s to 25 Pa ⁇ s, more preferably 5 Pa ⁇ s to 25 Pa ⁇ s, even more preferably 5 Pa ⁇ s to 20 Pa ⁇ s, and 5 Pa ⁇ s. It is particularly preferred to be ⁇ 17 Pa ⁇ s.
  • the inorganic latent heat storage material composition has the advantage of (i) being in a gel state and (ii) having a viscosity of It has the advantage of good operability because it is not too expensive.
  • the effect of preventing phase separation (preventing water separation) by the phase separation inhibitor is likely to be exhibited, so that there is an advantage that the obtained composition is more excellent in gel state stability.
  • melting temperature In the present specification, the intermediate temperature of the temperature range exhibited by the inorganic latent heat storage material composition while the solid inorganic latent heat storage material composition melts and turns into a gel is referred to as the inorganic latent heat storage material composition. Let it be the "melting temperature” of a substance. "Melting temperature” may also be referred to as “melting point,””phase change temperature,” or “phase transition temperature.”
  • the melting temperature of this composition is not particularly limited.
  • the composition has a melting temperature between 15°C and 30°C, more preferably between 17°C and 28°C, and even more preferably between 20°C and 25°C.
  • the latent heat of the composition can be used to easily adjust the living environment to a comfortable environment, and
  • the resulting composition has the advantage of being able to stably maintain the temperature of a temperature-controlled article around 15°C to 30°C.
  • the composition preferably has a high latent heat of fusion.
  • the latent heat of fusion of the present composition is preferably 80 J/g or more, more preferably 100 J/g or more, and particularly preferably 120 J/g or more.
  • the latent heat of fusion of the inorganic latent heat storage material composition can be measured using a differential scanning calorimeter. For example, using a differential scanning calorimeter (manufactured by Seiko Instruments Inc.: SII EXSTAR6000 DSC), the temperature of the inorganic latent heat storage material composition was changed from -20°C to 50°C at a rate of 3.0°C/min. and then cooled from 50°C to -20°C at the same rate. From the DSC curve obtained at this time, the latent heat of fusion of the composition can be obtained.
  • the composition is characterized by (i) absorbing thermal energy during the phase transition of the composition from a solidified state (solid) to a molten state (gel state); It can be suitably used as a latent heat type heat storage material that releases thermal energy during the phase transition from solidified to solidified (solid).
  • the "melting state” can also be said to be the “melting state”.
  • the composition absorbs thermal energy during the phase transition from the solidified state to the molten state, thereby reducing the temperature of, for example, a room to a desired temperature below the ambient temperature, even in high temperature environments (e.g., summer). can be held.
  • the present composition releases thermal energy during the phase transition from the molten state to the solidified state, so that even in low temperature environments (e.g., winter), the temperature in a room, for example, can be raised to a desired temperature above the ambient temperature. can be held. That is, according to the inorganic latent heat storage material composition according to one embodiment of the present invention, for example, the indoor temperature can be set to a desired temperature (for example, 15 to 30 °C).
  • the inorganic latent heat storage material composition according to one embodiment of the present invention can be suitably used in various applications requiring heat storage performance, such as building materials such as wall materials, floor materials, ceiling materials, and roof materials.
  • the inorganic latent heat storage material composition according to one embodiment of the present invention can be suitably used for constant-temperature transportation of temperature-controlled articles.
  • the production method (preparation method) of the present composition is not particularly limited. Any technique known in the art of inorganic latent heat storage material compositions can be used to prepare the composition.
  • the present composition can be prepared, for example, by mixing the components (a) to (f) described above.
  • calcium chloride anhydride, calcium chloride dihydrate and/or calcium chloride tetrahydrate may be used in place of calcium chloride hexahydrate, which is the main ingredient.
  • Calcium chloride anhydrous, calcium chloride dihydrate and/or calcium chloride tetrahydrate (i) forms a hydrate (or a hydrate with a higher hydration number) on contact with water; and (ii) exothermic with the formation of the hydrate, i.e. exhibiting a positive heat of solution.
  • Calcium chloride anhydrous, calcium chloride dihydrate and/or calcium chloride tetrahydrate can form the base calcium chloride hexahydrate upon contact with water.
  • calcium chloride anhydrate, calcium chloride dihydrate and/or calcium chloride tetrahydrate can be said to be "main ingredient precursors".
  • “calcium chloride dihydrate and/or calcium chloride tetrahydrate” may be referred to as “main ingredient precursor”.
  • the present composition can be prepared, for example, by mixing (a) calcium chloride hexahydrate, (b) component, (c) cellulose derivative, (d) strontium salt, (e) benzoate and (f) component , can be prepared.
  • the present composition includes, for example, water, a main precursor (such as calcium chloride anhydride, calcium chloride dihydrate and/or calcium chloride tetrahydrate), component (b), cellulose derivative, (d) It can be prepared by mixing strontium salt, (e) benzoate and (f) component.
  • a main precursor such as calcium chloride anhydride, calcium chloride dihydrate and/or calcium chloride tetrahydrate
  • component b
  • cellulose derivative cellulose derivative
  • strontium salt strontium salt
  • benzoate and (f) component a main precursor
  • Each component mentioned above may be mixed simultaneously and may be mixed in order.
  • the order of mixing is not particularly limited, and the components may be mixed in an order in which the respective components are easily dissolved.
  • the device used for mixing each component is not particularly limited, and known devices such as a mixer such as an intensive mixer, a stirrer, and a shaker can be used as appropriate.
  • a preferred embodiment of the method for producing the present composition includes the following production method: A method for producing an inorganic latent heat storage material composition, comprising: (b) from the group consisting of a bromide salt and a chloride salt; one or more selected inorganic salts, (c) cellulose derivatives, (d) strontium salts, (e) benzoates, and (f) (f-1) oleic acid and/or (f-2) polyvinylpyrrolidone a main agent precursor addition step of adding calcium chloride anhydrate, calcium chloride dihydrate and/or calcium chloride tetrahydrate to the aqueous solution containing the inorganic latent heat storage material composition.
  • the production method has the advantage of being able to efficiently provide a gel-like inorganic latent heat storage material composition.
  • main agent precursor addition step Since one aspect of the method for producing the present composition includes a main agent precursor addition step, instead of calcium chloride hexahydrate as the main agent, calcium chloride anhydrate, calcium chloride dihydrate and /or using calcium chloride tetrahydrate.
  • the main agent precursor generates heat with the formation of hydrate, that is, exhibits positive heat of solution.
  • a mixture containing (a) calcium chloride hexahydrate, (b) component, (c) cellulose derivative, (d) strontium salt, (e) benzoate and (f) component, i.e. It can also be said to be a step of preparing an inorganic latent heat storage material composition.
  • compositions prepared using calcium chloride anhydrous, calcium chloride dihydrate and/or calcium chloride tetrahydrate may contain calcium chloride hexahydrate as the main ingredient.
  • the amount of calcium chloride anhydride, calcium chloride dihydrate and/or calcium chloride tetrahydrate used is appropriately set so that the resulting composition contains the desired amount of calcium chloride hexahydrate.
  • the method of adding the main agent precursor to the aqueous solution is not particularly limited.
  • the main precursor to be added to the aqueous solution is preferably solid, not in the form of a solution mixed with water in advance.
  • a device used for the stirring is not particularly limited, and a known device can be used as appropriate.
  • a mixer such as an intensive mixer, a stirrer, a shaker, and the like can be used.
  • Conditions for the stirring are not particularly limited.
  • the rotor rotation speed is preferably 100 rpm to 2000 rpm, more preferably 200 rpm to 1800 rpm, still more preferably 300 rpm to 1500 rpm, and particularly preferably 500 rpm to 1500 rpm.
  • the pan rotation speed is preferably 5 rpm to 40 rpm, more preferably 10 rpm to 35 rpm, and particularly preferably 15 rpm to 30 rpm.
  • the resulting mixture may be heated.
  • a device used for the heating is not particularly limited, and a known device can be used as appropriate.
  • heating means provided in the device used for stirring the mixture may be used.
  • the heating temperature of the mixture is not particularly limited, and is preferably 25° C. to 70° C., more preferably 30° C. to 70° C., more preferably 35° C. to 70° C., more preferably 40° C. to 70° C., more preferably 45° C. to 65°C is more preferred, and 50°C to 60°C is particularly preferred.
  • the temperature of the mixture obtained by adding the main precursor to the aqueous solution may rise. Therefore, the mixture need not be heated, but may be heated to improve production efficiency.
  • the temperature of the mixture obtained by adding the main agent precursor to the aqueous solution is preferably not too high in order to suppress the decomposition of the thickener by heat and to prevent the viscosity of the mixture from being excessively lowered by heat. , preferably at a temperature at which the water in the mixture is difficult to evaporate.
  • the temperature of the mixture obtained by adding the main agent precursor to the aqueous solution is preferably 100° C. or lower, more preferably 90° C. or lower, still more preferably 85° C. or lower, and particularly preferably 80° C. or lower.
  • the mixture obtained by adding the main agent precursor to the aqueous solution does not exceed the above temperature range (e.g., 100°C) by stopping stirring of the mixture, or It is preferable to finish the main agent precursor addition step by cooling the mixture.
  • calcium chloride hexahydrate which is the main ingredient
  • calcium chloride hexahydrate may be used in addition to the main ingredient precursor.
  • calcium chloride hexahydrate may be used in any step of the manufacturing process. The amounts of the main agent precursor and the main agent used are adjusted so that the total amount used together with the hydrate is the desired content of the main agent (calcium chloride hexahydrate) in the finally obtained composition. good.
  • the method for producing the present composition further includes an aqueous solution preparation step of preparing an aqueous solution prior to the main agent precursor addition step.
  • the aqueous solution preparation step preferably includes a dispersing step of dispersing the cellulose derivative, benzoate and component (f) in a mixed solution containing water, component (b) and strontium salt.
  • the aqueous solution preparing step further includes a mixed solution preparing step of preparing a mixed solution containing water, the component (b) and the strontium salt.
  • the method for producing the present composition further includes an aqueous solution preparation step, a mixture preparation step and a dispersion step in addition to the main agent precursor addition step
  • the aqueous solution preparation step and the main agent precursor addition step are carried out in this order, followed by the aqueous solution preparation.
  • the mixture preparation process and the dispersion process are performed in this order.
  • the production method of the present composition further includes an aqueous solution preparation step, a mixture preparation step and/or a dispersion step in addition to the main agent precursor addition step
  • the production method provides the composition more efficiently and stably. have the advantage of being able to
  • a specific aspect of the mixed solution preparation step is not particularly limited, and it may be an aspect of simply mixing water, the component (b), and the strontium salt. It is preferable that the component (b) and the strontium salt are completely dissolved in the mixed solution obtained in the mixed solution preparing step. In order to prepare a mixed solution in which the component (b) and the strontium salt are completely dissolved, it is preferable to stir and/or heat the mixed solution obtained by mixing water, the component (b) and the strontium salt. .
  • Examples of water include tap water, industrial water, distilled water, deionized water (water purified by ion exchange resin), and ultrapure water.
  • water ultrapure water is preferable because it has a low content of metal ions. The amount of metal ions contained in tap water does not affect the physical properties of the resulting composition.
  • the device used for stirring the mixed solution is not particularly limited, and known devices such as those listed as devices used for stirring the mixture in the main agent precursor addition step can be used as appropriate.
  • the rotor rotation speed is preferably 100 rpm to 2000 rpm, more preferably 200 rpm to 1800 rpm, still more preferably 300 rpm to 1500 rpm, and particularly preferably 500 rpm to 1500 rpm.
  • the pan rotation speed is preferably 5 rpm to 40 rpm, more preferably 10 rpm to 35 rpm, and particularly preferably 15 rpm to 30 rpm.
  • the device used for heating the mixed solution is not particularly limited, and known devices can be used as appropriate.
  • a heating means provided in the device used for stirring the mixed liquid may be used.
  • the temperature for heating the mixed liquid is not particularly limited, and is preferably 30°C to 60°C, more preferably 35°C to 55°C, and particularly preferably 40°C to 50°C.
  • the aqueous solution used in the main agent precursor addition step that is, an aqueous solution containing water, component (b), cellulose derivative, strontium salt, benzoate and component (f) can be obtained.
  • a specific aspect of the dispersing step is not particularly limited as long as an aqueous solution in which the cellulose derivative, benzoate and component (f) are dispersed can be obtained.
  • aqueous solution in which cellulose derivative, benzoate and component (f) are dispersed means that 1 L of aqueous solution is passed through a tube with a hole diameter of 50 mm from the top to the bottom of a 16-mesh sieve at a flow rate of 1 L/min. It is intended to be an aqueous solution that can pass through the sieve when run below, in other words that no solids remain on the sieve.
  • the cellulose derivative, benzoate and component (f) are added to the mixed solution, and the cellulose derivative, benzoate and component (f) are dispersed in the resulting aqueous solution.
  • a mode in which the obtained aqueous solutions are mixed may be used. It is preferable that the cellulose derivative, benzoate and component (f) are dispersed uniformly or substantially uniformly in the aqueous solution obtained in the dispersion step. In order to obtain an aqueous solution in which the cellulose derivative, benzoate and component (f) are well dispersed, it is preferable to stir the aqueous solution.
  • the device used for stirring the aqueous solution is not particularly limited, and known devices such as those listed as devices used for stirring the mixture in the main agent precursor addition step can be used as appropriate.
  • the rotor rotation speed is preferably 100 rpm to 2000 rpm, more preferably 200 rpm to 1800 rpm, still more preferably 300 rpm to 1500 rpm, and particularly preferably 500 rpm to 1500 rpm.
  • the pan rotation speed is preferably 5 rpm to 40 rpm, more preferably 10 rpm to 35 rpm, and particularly preferably 15 rpm to 30 rpm.
  • the (f) component may be colored, and the addition of the (f) component may increase the viscosity of the resulting solution. Therefore, since it is easy to visually confirm the degree of dispersion of the cellulose derivative and benzoate in the resulting solution, the cellulose derivative and benzoate are added to the mixed solution prior to component (f) in the dispersion step. preferably.
  • the component (f) is preferably added to a liquid mixture containing a cellulose derivative and a benzoate (for example, a cellulose derivative and a benzoate are dispersed).
  • the dispersion step it is preferable to mix the cellulose derivative and the benzoate in advance and add the resulting mixture to the mixed liquid.
  • the cellulose derivative and the benzoate are mixed in advance, and the obtained mixture is added to the mixed solution obtained in the mixed solution preparation step (that is, the mixed solution not containing the component (f)). is more preferred.
  • the method of mixing the cellulose derivative and the benzoate is not particularly limited, and dry blending may be used, for example.
  • the benzoate used in the production method of the present composition preferably has a particle size of 1 ⁇ m to 1 mm, more preferably 2 ⁇ m to 900 ⁇ m, even more preferably 5 ⁇ m to 800 ⁇ m, even more preferably 10 ⁇ m to 800 ⁇ m. It is particularly preferred to have According to this configuration, it is possible to easily obtain a composition containing a benzoate having a particle size within the range described above. Since the method for producing the present composition uses a benzoate having a particle size within the range described above, it is preferable to sieve the benzoate before use (for example, before adding to the mixed solution).
  • PVP When using PVP in the production of the present composition, it is preferable to mix a certain amount of water and PVP in advance to prepare an aqueous PVP solution, and then use the PVP aqueous solution.
  • an aqueous solution of PVP to the mixed liquid in the dispersion step, which contains a cellulose derivative and a benzoate (for example, a cellulose derivative and a benzoate are dispersed). It is more preferable to add the PVP aqueous solution to the mixed solution.
  • This configuration has the advantage that PVP is dispersed uniformly or substantially uniformly in the composition without the fear of lumping PVP in the resulting composition.
  • a commercially available PVP aqueous solution can also be used as the PVP aqueous solution.
  • the sparingly water-soluble inorganic salt for example, the case of using a sparingly water-soluble inorganic salt such as barium sulfate that can function as a supercooling inhibitor, will be described.
  • the sparingly water-soluble inorganic salt is preferably used (added) at the same timing and in the same manner as the cellulose derivative, benzoate and component (f).
  • the sparingly water-soluble inorganic salt is preferably added to the mixed solution obtained in the mixed solution preparation step together with the cellulose derivative, benzoate and component (f) in the dispersing step.
  • the sparingly water-soluble inorganic salt and the component (f) are added in advance in the dispersion step. It is preferable to mix and add the resulting mixture to the mixed liquid, (ii) pre-mix the cellulose derivative and the benzoate, and add the obtained mixture to the mixed liquid obtained in the mixed liquid preparation step (i.e. , (f) component-free mixed solution), the poorly water-soluble inorganic salt and (f) component are mixed in advance, and the resulting mixture is added to the mixed solution containing the cellulose derivative and benzoate. Adding is more preferable.
  • the amount of water used can be appropriately set according to the amount of the main ingredient precursor used and the amount of the main ingredient in the resulting composition.
  • the amount of water used in the mixed solution preparation step, and the amount of water contained in the aqueous solution when each component added to the mixed solution after the dispersion step is added as an aqueous solution is the amount that reacts with the total amount of the main agent precursor used to form the desired amount of the main agent (i.e., the amount that constitutes the hydrate), and the amount that does not exist as water in the composition. It is preferable that it is appropriately set so that
  • An embodiment of the present invention may have the following configuration.
  • An inorganic latent heat storage material composition comprising (a) calcium chloride hexahydrate, (b) one or more inorganic salts selected from the group consisting of bromide salts and chloride salts, and (c ) a cellulose derivative, and in 100% by weight of the inorganic latent heat storage material composition, (d) 0.40% by weight or more of a strontium salt, and (e) 0.20% by weight or more of a benzoate, (f) the inorganic The inorganic latent heat storage material composition, wherein the total content of the (d) strontium salt and the (e) benzoate is 0.90% by weight or more in 100% by weight of the latent heat storage material composition.
  • the (e) benzoate is contained in an amount of 0.20% by weight or more
  • the (d) strontium salt is 0.70% by weight or more and less than 0.95% by weight
  • the (e) benzoate is 0.30% to 3.00% by weight
  • the inorganic material according to [1] contains 0.40% by weight to 3.00% by weight of the (e) benzoate. system latent heat storage material composition.
  • [7] A method for producing the inorganic latent heat storage material composition according to any one of [1] to [6], wherein (b) one selected from the group consisting of bromide salts and chloride salts
  • An aqueous solution containing the above inorganic salt, (c) cellulose derivative, (d) strontium salt, (e) benzoate, and (f) (f-1) oleic acid and/or (f-2) polyvinylpyrrolidone is prepared.
  • an aqueous solution preparation step and a main agent precursor addition step of adding calcium chloride anhydrate, calcium chloride dihydrate and/or calcium chloride tetrahydrate to the aqueous solution prepared by the aqueous solution preparation step.
  • Measurement methods and evaluation methods in Examples and Comparative Examples are as follows.
  • the inorganic latent heat storage material compositions obtained in Examples and Comparative Examples were filled in polypropylene cryovials having a volume of 2 ml together with a thermocouple.
  • the cryovial was left in an environment of 5° C. or lower for a certain period of time to lower the temperature of the composition in the cryovial to 5° C. or lower.
  • the cryovial was allowed to stand in an ultra-low temperature thermostat (Ultra-low temperature aluminum block thermostat cryoporter (registered trademark) CS-75CP, manufactured by Synix). Then, the temperature of the constant temperature bath was raised from 5° C. to 45° C. or 50° C. at a heating rate of 1.0° C./min.
  • the temperature of the composition in the constant temperature bath was monitored with a thermocouple during the temperature rise process of the constant temperature bath, and the obtained results (temperature) were plotted against time to obtain a graph.
  • the temperature of the composition changed in the following order (1) to (3) compared to the temperature of the constant temperature bath, which increased at a constant rate: (1) from 5 ° C. to a certain temperature ( ( 2 ) changed little from temperature T1 to a certain temperature ( referred to as temperature T2) due to the latent heat of the composition; (3) temperature After T2 , the rise resumed.
  • the temperature at the midpoint between temperature T1 and temperature T2 was calculated as the melting temperature for the composition.
  • the inorganic latent heat storage material compositions obtained in Examples and Comparative Examples were filled into the cryovials having a volume of 2 ml together with a thermocouple.
  • the cryovial was left in an environment of 45° C. or higher or 50° C. or higher for a certain period of time to raise the temperature of the composition in the cryovial to 45° C. or higher or 50° C. or higher.
  • the cryovial was placed in the ultra-low temperature constant temperature bath. Then, the temperature of the constant temperature bath was lowered from 45°C or 50°C to 5°C at a temperature lowering rate of 1.0°C/min.
  • the temperature of the composition in the constant temperature bath was monitored with a thermocouple during the temperature drop process of the constant temperature bath, and the obtained results (temperature) were plotted against time to obtain a graph.
  • the temperature of the composition changed in the following order (1) to (3) compared to the temperature of the constant temperature bath: (1) from 45 ° C. or 50 ° C. ( 2 ) after a slight increase from temperature T4 to a certain temperature ( assumed to be temperature T5), the temperature was lowered from temperature T5 to a certain temperature (temperature ( 3 ) At temperature T6 , the temperature resumed decreasing.
  • the temperature difference between temperature T4 and temperature T5 was calculated as the supercooling temperature in the composition. Also, the temperature T5 was taken as the solidification temperature.
  • Examples and comparative examples are described below.
  • Calcium chloride dihydrate was used as the main agent precursor in all the examples and all the comparative examples.
  • calcium chloride dihydrate which is the main precursor, forms calcium chloride hexahydrate upon contact with water, and along with the formation of calcium chloride hexahydrate, I had a fever.
  • the inorganic latent heat storage material compositions obtained in all Examples and Comparative Examples contained calcium chloride hexahydrate as a main agent.
  • the obtained inorganic latent heat storage material composition contains calcium chloride hexahydrate as a main ingredient and does not contain water, in other words, the total amount of water used The amount of water used was adjusted so that reacts with all of the calcium chloride dihydrate to form calcium chloride hexahydrate.
  • Example 1 (Aqueous solution preparation step) (Mixed solution preparation step) 26.72 parts by weight of water, 7.6 parts by weight of sodium bromide, 3.1 parts by weight of potassium bromide and 3.2 parts by weight of sodium chloride as components (b) are placed in a 50 L intensive mixer (manufactured by Eirich Japan Co., Ltd.). and (d) 0.95 parts by weight of strontium chloride hexahydrate as a strontium salt. Subsequently, the raw materials in the intensive mixer were stirred at a rotor speed of 500 rpm and a pan speed of 15 rpm until all the raw materials were completely dissolved in water to obtain a colorless and transparent liquid mixture. A mixed liquid containing water, the component (b) and the strontium salt was obtained by this operation.
  • component (f) 0.7 parts by weight of oleic acid was added as component (f) to the mixture in the intensive mixer. Subsequently, the mixture in the intensive mixer was stirred for 30 seconds at a rotor speed of 500 rpm and a pan speed of 15 rpm. By this operation, an aqueous solution containing water, component (b) and strontium salt, in which the cellulose derivative, benzoate and component (f) are dispersed was obtained. It was also confirmed by the method described above that the cellulose derivative, benzoate and component (f) were dispersed in the aqueous solution.
  • (Main agent precursor addition step) 54.4 parts by weight of calcium chloride dihydrate was added as a main component precursor to the aqueous solution obtained in the intensive mixer. Subsequently, the mixture in the intensive mixer was stirred under conditions of a rotor speed of 1400 rpm, a pan speed of 30 rpm, and a heater set temperature of 60°C. After that, the stirring was terminated when the indicated value of the thermometer inside the intensive mixer reached 75°C. By such operation, a gel composition was obtained. Note that 54.43 parts by weight of calcium chloride dihydrate reacted with all the water in the aqueous solution to form calcium chloride hexahydrate.
  • the resulting composition contained 81.15 parts by weight of calcium chloride hexahydrate as the main ingredient.
  • the supercooling inhibition property and durability of the resulting composition were evaluated by the methods described above. Table 1 shows the results. Moreover, in Table 1, the content of each component in the composition is shown in weight %. Further, the composition obtained in Example 1 was examined using a digital microscope (model number: VHX-5000, manufactured by Keyence Corporation) as described above, and the particle size of the benzoate (sodium benzoate) in the composition was was measured and confirmed to be within the range of 1 ⁇ m to 800 ⁇ m.
  • Examples 2 to 19 Compositions of Examples 2 to 19 were produced in the same manner as in Example 1 except that the types and blending amounts of each component were changed so that compositions having the compositions shown in Tables 1 to 3 were obtained.
  • each benzoate used was sieved using a 710 ⁇ m sieve before use, and only the benzoate that passed through the sieve was used in a predetermined amount. The supercooling inhibition property and durability of the resulting composition were evaluated by the methods described above. The results are shown in Tables 1-3. Further, for the compositions obtained in Examples 2 to 19, the particle size of benzoate in the composition was measured using a digital microscope (model number: VHX-5000, manufactured by Keyence Corporation) as described above. , within the range of 1 ⁇ m to 800 ⁇ m.
  • Comparative Examples 1 to 12 Compositions of Comparative Examples 1 to 12 were produced in the same manner as in Example 1 except that the types and blending amounts of each component were changed so that compositions having the compositions shown in Tables 4 and 5 were obtained. The supercooling inhibition property and durability of the resulting composition were evaluated by the methods described above. The results are shown in Tables 4 and 5.
  • Example 2 calcium chloride dihydrate was used as the main component precursor.
  • the amount of water and the amount of calcium chloride dihydrate used in Examples 2 to 19 and Comparative Examples 1 to 12 were such that the amounts of calcium chloride hexahydrate in the resulting compositions were shown in Tables 1 to 5. was changed as appropriate.
  • the compositions of Examples 1 to 16 have a small degree of supercooling, that is, supercooling It can be seen that the cooling suppression property is excellent and the durability is also excellent.
  • Comparative Examples 1-3 do not contain benzoate and component (f). Comparative Examples 4-8 do not contain benzoate. Comparative Example 9 contains no strontium salt and Comparative Example 10 contains no strontium salt and benzoate. Comparative Examples 11 and 12 contain a strontium salt and a benzoate, but are not "the total content of the strontium salt and the benzoate is 0.90% by weight or more". As shown in Tables 4 and 5, the compositions of Comparative Examples 1 to 12 had a large degree of supercooling, that is, poor supercooling suppression properties, and were inferior in quality.
  • an inorganic latent heat storage material composition with a small degree of supercooling.
  • the inorganic latent heat storage material composition according to one embodiment of the present invention can be suitably used as a heat storage material in, for example, (i) wall materials, floor materials, ceiling materials, roof materials, base materials for floor mats, and the like. (ii) it can be suitably used for constant-temperature transportation of articles to be temperature-controlled.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne une composition de matériau inorganique d'accumulation de chaleur latente, qui présente un faible niveau de surfusion.　L'invention porte sur une composition de matériau inorganique d'accumulation de chaleur latente qui comprend du chlorure de calcium hexahydraté, au moins un sel inorganique choisi dans le groupe qui consiste en les sels bromures et les sels chlorures, et un dérivé de cellulose. La composition de matériau inorganique d'accumulation de chaleur latente comprend aussi une quantité spécifique d'un sel de strontium, une quantité spécifique d'un benzoate et (a) une quantité spécifique d'acide oléique et/ou (b) une quantité spécifique de polyvinylpyrrolidone.
PCT/JP2022/001762 2021-01-25 2022-01-19 Composition de matériau inorganique accumulateur de chaleur latente WO2022158484A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58215481A (ja) * 1982-06-09 1983-12-14 Hitachi Ltd 蓄熱材料
JP2016108535A (ja) * 2014-09-29 2016-06-20 パナソニック株式会社 蓄熱材組成物、蓄熱装置及び蓄熱方法
CN106753255A (zh) * 2016-11-25 2017-05-31 苏州安特实业有限公司 一种相变温度为‑26～‑28℃的低温相变材料
JP2018514052A (ja) * 2015-02-04 2018-05-31 グローバル ウェブ ホライズンズ，リミティド ライアビリティ カンパニー 電気化学装置の熱管理のためのシステム、構造及び材料
JP2019137854A (ja) * 2018-02-07 2019-08-22 株式会社ヤノ技研 蓄熱材組成物
WO2020203749A1 (fr) * 2019-03-29 2020-10-08 株式会社カネカ Matériau de stockage de chaleur latente

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58215481A (ja) * 1982-06-09 1983-12-14 Hitachi Ltd 蓄熱材料
JP2016108535A (ja) * 2014-09-29 2016-06-20 パナソニック株式会社 蓄熱材組成物、蓄熱装置及び蓄熱方法
JP2018514052A (ja) * 2015-02-04 2018-05-31 グローバル ウェブ ホライズンズ，リミティド ライアビリティ カンパニー 電気化学装置の熱管理のためのシステム、構造及び材料
CN106753255A (zh) * 2016-11-25 2017-05-31 苏州安特实业有限公司 一种相变温度为‑26～‑28℃的低温相变材料
JP2019137854A (ja) * 2018-02-07 2019-08-22 株式会社ヤノ技研 蓄熱材組成物
WO2020203749A1 (fr) * 2019-03-29 2020-10-08 株式会社カネカ Matériau de stockage de chaleur latente

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