JP2006097001A - Heat storage material-microencapsulated solid material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat storage material-microencapsulated solid material including a latent heat storage material, causing no damage of microcapsules in making the solid material and usable over a long period without declining in heat storage effect even if temperature change is applied repeatedly in the temperature range including the phase change temperature. <P>SOLUTION: The heat storage material-microencapsulated solid material is such that microcapsules including a heat storage material are made to adhere to one another together with a binder, wherein the hardness of the binder is lower than that of a resin constituting the film of the microcapsules. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a microcapsule solid that contains a heat storage material, and specifically relates to a microcapsule solid that has excellent temperature buffering properties near the melting point of the heat storage material.

  In recent years, it has been required to save energy by effectively using thermal energy. As an effective method, a method of storing heat by using latent heat accompanying a phase change of a substance has been considered. Compared to the method using only sensible heat without phase change, it can store a large amount of heat energy in a narrow temperature range including the melting point, thus not only reducing the capacity of the heat storage material but also reducing the amount of heat storage. There is an advantage that heat loss can be suppressed to a small amount because a large temperature difference does not occur for a large amount.

  In order to increase the heat exchange efficiency of the heat storage material, a method of encapsulating the heat storage material has been proposed. In general, as a method for microencapsulating a heat storage material, an encapsulation method by a composite emulsion method (for example, see Patent Document 1), a method for forming a thermoplastic resin in a liquid on the surface of the heat storage material particles (for example, Patent Document 2) And a method of polymerizing and coating the monomer on the surface of the heat storage material particles (for example, see Patent Document 3), a method for producing a polyamide-coated microcapsule by an interfacial polycondensation reaction (for example, see Patent Document 4), and the like. Can do.

  In many cases, the above-described microencapsulation method obtains the heat storage material microcapsules in a state of being dispersed in a medium such as water. By drying it and taking it out as a solid matter, the solid state can always be maintained regardless of the phase state of the contained latent heat storage material. Therefore, it can be used in a wider range of applications. The solid material of the heat storage material microcapsule is not a microcapsule alone, which is simply a dried medium used to make the microcapsule, but a binder is used in combination to maintain a state in which a plurality of microcapsules are fixed. It is customary (see, for example, Patent Document 5).

However, when the heat storage material microcapsules are solidified, there is a problem that cannot be seen when dispersed in the medium. That is, when a solid is produced, the microcapsule is damaged by external pressure or internal stress at the time of molding, or the temperature is repeatedly stored in the temperature range where the phase change temperature is sandwiched in the heat storage material microcapsule solid. There was a problem that the effect was reduced.
Japanese Patent Laid-Open No. 62-1452 Japanese Patent Laid-Open No. 62-149334 JP-A-62-2225241 Japanese Patent Laid-Open No. 2-258052 JP-A-2-222483

  An object of the present invention is to provide a microcapsule solid material containing a latent heat storage material without causing damage to the microcapsule during the production of the solid material, and repeatedly applying a temperature change in a temperature range sandwiching the phase change temperature. Another object is to provide a heat storage material microcapsule solid that can be used for a long period of time without reducing the heat storage effect.

As a result of intensive studies, the present inventors have found the following invention.
(1) In the heat storage material microcapsule solid body in which the heat storage material microcapsules enclosing the heat storage material are fixed together with the binder, the hardness of the binder is higher than the hardness of the capsule film constituting resin forming the heat storage material microcapsule. A heat storage material microcapsule solid, characterized by using a binder having a small value,
(2) When the form of the heat storage material microcapsule solid is powder or solid, the hardness value of the binder is 0.01 or more and 95 or less when the hardness value of the capsule film constituent resin is 100 The heat storage material microcapsule solid according to the above (1),
(3) When the shape of the heat storage material microcapsule solid is a granulated body, the hardness value of the binder is 0.1 or more and 90 or less when the hardness value of the capsule film constituent resin is 100. The heat storage material microcapsule solid according to (1) above,
(4) The heat storage material microcapsule solid according to any one of (1) to (3) above, wherein the volume average particle diameter of the heat storage material microcapsules enclosing the heat storage material is in the range of 0.5 to 50 μm,
(5) The heat storage material microcapsule solid according to any one of (1) to (4), wherein the volume average diameter of the heat storage material microcapsule solid is in the range of 10 μm to 100 mm.

  The solid material of the heat storage material microcapsule shown in the present invention has a hardness smaller than the hardness of the capsule film constituting resin that forms the heat storage material microcapsule, when the hardness of the binder used when fixing a plurality of heat storage material microcapsules is fixed. By using a resin, the microcapsules are not destroyed during the production of solids, and even if temperature changes are repeatedly applied in the temperature range sandwiching the phase change temperature, the heat storage effect is not reduced and the performance is maintained over a long period of time. It became possible to maintain. That is, by appropriately setting the hardness of the capsule film constituent resin forming the heat storage material microcapsule and the hardness of the binder existing around the heat storage material microcapsule, desired performance and durability in the initial stage are set. It was possible to improve the performance.

  In the production of solid matter, a solid matter is produced from a mixture containing heat storage material microcapsules and a binder wetted with water as main components using a drying device or a granulating device. In the drying step, moisture is removed from the binder and the binder shrinks in volume. At this time, if the hardness of the binder is greater than the hardness of the capsule film constituting resin forming the heat storage material microcapsules, the capsule film may be stressed by the binder and may be damaged. On the other hand, by using a binder having a value smaller than the hardness of the resin constituting the capsule film, the capsule film is less susceptible to stress from the binder, and the capsule film can be prevented from being damaged. .

  When the temperature change is repeatedly applied in the temperature range sandwiching the phase change temperature, the heat storage material that is a phase change compound existing inside the heat storage material microcapsule repeats melting and solidification, but these heat storage materials are in a solid state. When changing to the molten state, the volume increases. Conversely, when changing from the molten state to the solidified state, the volume decreases. In conjunction with this, the heat storage material microcapsules enclosing the heat storage material also expand when the heat storage material changes from the solidified state to the molten state, and conversely contract when the heat storage material changes from the molten state to the solidified state. The volume variation due to the expansion and contraction of the heat storage material microcapsules is absorbed by the medium in a state where it is dispersed in the medium, so that no damage is caused to the capsule film. On the other hand, in the case of a microcapsule solid, if the binder present around the microcapsule does not absorb the displacement of the volume variation well, the capsule film is stressed by both the heat storage material inside the capsule and the binder outside the capsule. If the expansion and contraction are repeated, the capsule film is damaged, and the heat storage material inside the capsule gradually leaks to the outside, and the heat storage effect is reduced.

  On the other hand, by using a binder having a value smaller than the hardness of the capsule film constituent resin forming the heat storage material microcapsule, the hardness of the binder used when fixing a plurality of heat storage material microcapsules is fixed. The displacement of the volume fluctuation due to expansion and contraction is absorbed by the binder present around the microcapsule, and the capsule film is not damaged. In other words, even if the temperature change is repeatedly applied in the temperature range sandwiching the phase change temperature, it has been possible to maintain the usable performance over a long period without reducing the heat storage effect.

  The latent heat storage material contained in the microcapsules according to the present invention is used for the purpose of storing heat using latent heat accompanying phase transition, and any compound having a melting point or a freezing point can be used. Specific heat storage materials include aliphatic hydrocarbon compounds (paraffin compounds) such as tetradecane, hexadecane, octadecane, and paraffin wax, inorganic eutectics and inorganic hydrates, and fatty acids such as palmitic acid and myristic acid. , Aromatic hydrocarbon compounds such as benzene and p-xylene, ester compounds such as isopropyl palmitate and butyl stearate, and compounds such as alcohols such as stearyl alcohol, preferably having a heat of fusion of about 80 kJ / kg or more. Compounds that are chemically and physically stable and inexpensive are used. These may be used as a mixture, and a supercooling preventing material, a specific gravity adjusting material, a deterioration preventing agent and the like may be added as necessary. It is also possible to use a mixture of two or more microcapsules having different melting points.

  A physical method and a chemical method are known as a method for producing a microcapsule according to the present invention. In particular, as a method for microencapsulating a latent heat storage material, an encapsulation method by a composite emulsion method (Japanese Patent Laid-Open No. 62-1452). No.), a method of spraying a thermoplastic resin on the surface of the heat storage material particles (Japanese Patent Laid-Open No. 62-45680), and a method of forming a thermoplastic resin in the liquid on the surface of the heat storage material particles (Japanese Patent Laid-Open No. Sho 62- 149334), a method of polymerizing and coating monomers on the surface of the heat storage material particles (Japanese Patent Laid-Open No. 62-225241), a method for producing a polyamide-coated microcapsule by interfacial polycondensation reaction (Japanese Patent Laid-Open No. 2-258052) Is used.

  Examples of the capsule film constituting resin for forming the heat storage material microcapsules according to the present invention include polystyrenes, polyacrylonitriles, poly (poly (nitrides) obtained by techniques such as interfacial polymerization, in-situ polymerization, and radical polymerization. A (meth) acrylate, polyamide, polyacrylamide, ethyl cellulose, polyurethane, aminoplast resin, or a synthetic or natural resin using a coacervation method between gelatin and carboxymethyl cellulose or gum arabic is used. In particular, melamine formalin resins and urea formalin resins by in situ polymerization method, polyamides by interfacial polymerization method, polyureas, polyurethane ureas and polyurethanes, and polymethacrylates by radical polymerization method can be preferably used.

  The volume average particle diameter of the heat storage material microcapsules according to the present invention is preferably in the range of 0.5 to 50 μm, more preferably in the range of 1 to 20 μm. When the particle diameter is larger than this range, the mechanical shearing force may be extremely weak. When the particle diameter is smaller than this range, the fracture may be suppressed, but the film thickness may be reduced and the heat resistance may be poor. The volume average particle diameter described in the present invention represents the average particle diameter of the microcapsule particles in terms of volume, and in principle, particles having a fixed volume are sieved in order from the smallest, and the particles corresponding to 50% of the volume. Means the particle size at the time of separation. The volume average particle diameter can be calculated by actual measurement by microscopic observation, but it can be automatically measured by using a commercially available electrical and optical particle diameter measuring apparatus. Measurement was carried out using a particle size measuring device, Multisizer II, manufactured by the company.

  As a method of obtaining the heat storage material microcapsule solid material of the present invention, a binder is added to the microcapsule dispersion liquid prepared in the state of an aqueous dispersion, and various types such as a spray dryer, a drum dryer, a freeze dryer, a filter press, etc. Examples thereof include a method of evaporating and dewatering the water of the medium using a drying apparatus / dehydrating apparatus to form a powder or solid form. Also, after adding or binding agent to form powder or solid with the above device, add binder, various types of granulation such as extrusion granulation, rolling granulation, stirring granulation, etc. It is also possible to increase the particle size by granulating using the method, and to make it easy to handle. In the present invention, these powders, solid bodies, and granulated bodies are collectively referred to as solid bodies. The shape of the solid material may be any shape such as a sphere, an ellipse, a cube, a rectangular parallelepiped, a cylinder, a cone, a bowl, a bowl, a regular polyhedron, a star, and a cylinder.

  The volume average diameter of the heat storage material microcapsule solid according to the present invention is preferably in the range of 10 μm to 100 mm, more preferably in the range of 20 μm to 50 mm. When the average diameter is smaller than this range, the solid matter is likely to be scattered, so-called dusting is likely to occur, and the handling property may be deteriorated. When the average diameter is larger than this range, the ratio of the surface area becomes smaller than the volume, and the efficiency of heat exchange with the outside may be reduced. The volume average diameter described in the present invention represents the average diameter of the microcapsule solids in terms of volume, and in principle, a fixed volume of solids is sieved in ascending order, and the solid corresponding to 50% of the volume. It means the object diameter at the time when an object is separated. Measurement of volume average diameter in the case of powder can be calculated by sieving method or actual measurement by microscopic observation, but it can also be measured automatically by using commercially available electrical and optical particle size measuring devices. . The measurement of the volume average diameter in the case of a granulated body or a solid body can be calculated by actual measurement using a sieving method or industrial calipers. When measuring granulates and solids with industrial calipers, measure the shortest and longest diameters of 20 or more randomly extracted granulates and solids, and use these average values to determine the volume average It is good also as a diameter.

  The blending ratio of the binder used in the heat storage material microcapsule solid of the present invention to the microcapsule component is slightly different in the preferred range depending on the form of the heat storage material microcapsule solid. That is, when the form of the heat storage material microcapsule solid is powder or solid, the blending ratio of the binder is preferably in the range of 0.2 to 50% by mass with respect to the microcapsule component, A range of 0.5 to 30% is more preferable. When the form of the heat storage material microcapsule solid is a granulated body, the compounding ratio of the binder is preferably in the range of 1 to 80% by mass ratio with respect to the microcapsule component, and further in the range of 3 to 50%. Is more preferable. If it is above this range, the heat storage performance may be lowered. If the amount is below this range, the binding ability may be lowered, or the volume displacement may not be sufficiently absorbed when the microcapsules contract or expand. The term “microcapsule component” as used herein refers to a combination of a microcapsule inclusion and a capsule film.

  The hardness according to the present invention is the degree of hardness of an object and is also called hardness. Since hardness is difficult to give a clear and uniform definition to itself, values measured by various test methods are used. Typical test methods include the following. (1) Brinell hardness: Hardness defined by the ratio of the load and the surface area of the depression when a steel ball having a diameter of 5 mm or 10 mm is pushed into the sample. (2) Vickers hardness: Hardness defined by the ratio between the load and the surface area of the indentation when a diamond indenter of a regular square pyramid is pushed into the sample. When rhombus diamond indenters with different diagonal lengths are used, it is called Knoop hardness. The micro Vickers hardness tester can take a very small load and examine the hardness of each minute portion or structure. (3) Rockwell hardness: First, a reference load is applied using a steel ball or diamond conical indenter with a specified shape, and then the load is increased to the test load and then returned to the reference load. Hardness defined from the difference in depth of the dent at the time of two reference loads before and after this. There are various types of hardness depending on the combination of the shape, dimensions, and both load values of the indenter. In JIS, B hardness and C hardness are defined, and E scale, L scale, M scale, R scale, etc. are also used. (4) Shore hardness: Hardness obtained by dropping a hammer with a substantially spherical diamond at the tip so that it hits the sample surface vertically from a certain height and measuring the height at which the hammer rebounds. (5) Mohs hardness: Hardness used in relation to minerals. Ten types of minerals are selected, and if they are scratched sequentially and scratched, the hardness is assumed to be lower than that mineral. (6) Barcol hardness: This is a method in which a penetration gauge is read with a dial gauge when a needle-like indenter is pressed against the material surface under a certain condition using a hardness meter. Hardness test methods used for plastics are generally Barcoll hardness specified by JIS, Rockwell hardness and Vickers hardness specified by foreign standards such as ASTM. For rubber, durometers are widely used. (The above is a physics and chemistry encyclopedia (4th edition, published by Iwanami Shoten, 1987) and a new edition polymer dictionary (published by Asakura Shoten, 1988)). In the present invention, the above-mentioned various hardnesses will be collectively referred to as hardness, but as the hardness according to the present invention, in particular, from the viewpoint of preventing microcapsule damage during solid preparation and improving durability during repeated use. Rockwell hardness, Shore hardness, Vickers hardness or Barcol hardness can be adopted as a suitable standard. The hardness of the resin for forming the capsule film and the hardness of the binder can be derived from a handbook containing the hardness of each material, or can be calculated by actual measurement using various hardness testers. Test standards are established for JIS-K7202 and ASTM-D785 for Rockwell hardness and ASTM-D2240 for Shore hardness, respectively.

  In the heat storage material microcapsule solid according to the present invention, as described above, a binder is used in the pulverization and solidification step and / or the granulation step. As the binder, the heat storage material microcapsule is used. The object of the present invention can be achieved by using a binder having a hardness value smaller than the hardness of the resin for forming the capsule film that forms the capsule. The relationship between the hardness of the capsule film constituting resin and the hardness of the binder is that the object of the present invention is achieved if the value of the binder hardness is less than the hardness value of the capsule film constituting resin. The preferred range varies slightly depending on the form of the capsule solid. That is, when the form of the heat storage material microcapsule solid is a powder or solid, the hardness value of the binder is 0.01 or more and 95 or less when the hardness value of the capsule film constituent resin is 100. It is preferable. When the form of the solid material of the heat storage material microcapsule is a granulated body, it is preferable that the hardness value of the binder is 0.1 or more and 90 or less when the hardness value of the capsule film constituent resin is 100. The preferred range varies slightly depending on the blending ratio of the binder to the microcapsule component. That is, when the heat storage material microcapsule solid is in the form of powder or solid, the above range is preferable when the blending ratio of the binder to the microcapsule component is less than 20%, and the blending ratio of the binder is 20%. In the above, the hardness value of the binder is preferably 0.01 or more and 90 or less when the hardness value of the capsule film-constituting resin is 100. When the form of the heat storage material microcapsule solid is a granulated body, the above range is preferable when the blending ratio of the binder to the microcapsule component is less than 35%, and when the blending ratio of the binder is 35% or more, the capsule When the hardness value of the film-forming resin is 100, the hardness value of the binder is preferably 0.1 or more and 80 or less. When the hardness of the binder is larger than this range, there is a case where the displacement due to volume fluctuation due to expansion and contraction is not sufficiently absorbed. If the hardness of the binder is smaller than this range, the heat storage material microcapsule solids may be inadvertently fixed (so-called blocking).

  When melamine formalin resins or urea formalin resins obtained by in situ polymerization are used as the capsule film constituent resin for forming the heat storage material microcapsules, the hardness of these film constituent resins is 110 to 10 in terms of Rockwell hardness (M scale). Since it is 120, if a hardness is in the range of said ratio, a binder can be used conveniently. Since the hardness of these film-constituting resins is relatively high, the range of choice of binder is wide. On the other hand, when polyamides, polyureas, polyurethaneureas and polyurethanes by interfacial polymerization are used as capsule film constituent resins, and polymethacrylates by radical polymerization are used, the hardness of these film constituent resins is Rockwell hardness (M scale). ) Is often 70 to 100 MPa. Therefore, it is necessary to select a binder having a hardness within the above range for the binder to be suitably used. When using these film constituting resins, it is necessary to select the binder to be used in consideration of the hardness of the binder more carefully than when using melamine formalin resins or urea formalin resins. When two or more kinds of binders having different hardnesses are used, the object of the present invention can be achieved if the hardness of the binder mixture satisfies the above ratio range.

  The binder used for the solid material of the heat storage material microcapsule of the present invention is also a component that also brings about an effect of increasing the cohesive strength, water resistance, and strength between the microcapsules. As the binder used in the present invention, any binder can be used singly or in combination of two or more as long as it satisfies the above-mentioned hardness conditions. In addition, a conventionally known natural polymer having a film-forming ability, a natural polymer modified product (semi-synthetic product), a synthetic polymer and an inorganic compound can be selected and used in consideration of hardness.

  Examples of natural polymer substances include polysaccharides such as oxidized starch and phosphated starch, and proteins such as gelatin, casein, glue and collagen. Semi-synthetic products include propylene glycol alginate, viscose, methylcellulose, ethylcellulose, methylethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, carboxymethylhydroxyethylcellulose, and hydroxypropylmethylcellulose. Fibrin derivatives such as phthalate are used.

  Synthetic polymers include polyvinyl alcohol, partially acetalized polyvinyl alcohol, allyl-modified polyvinyl alcohol, modified polyvinyl alcohols such as polyvinyl methyl ether, polyvinyl ethyl ether, and polyvinyl isobutyl ether, poly (meth) acrylic acid esters, poly ( Hydrophilic polymers of (meth) acrylic acid ester partial saponification products, poly (meth) acrylic acid derivatives such as poly (meth) acrylic amide, polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, and vinyl pyrrolidone vinyl acetate copolymers, Polyvinyl acetate, polyurethane, styrene butadiene copolymer, carboxy-modified styrene butadiene copolymer, acrylonitrile butadiene copolymer, methyl acrylate acrylate copolymer Body, and latexes such as ethylene-vinyl acetate copolymer, melamine-formaldehyde resin (precondensate), urea-formalin resin (precondensate), thermoplastic elastomers, and the like.

  The heat storage material microcapsule solid of the present invention can be used alone, but is dispersed, mixed, impregnated in fiber, resin, inorganic material, etc., coated or pasted on the surface thereof, Alternatively, it can be used in combination with an adsorbent or a heat generating material or filled in a packaging material.

  Utilizing the heat storage material microcapsule solid material of the present invention as a heat insulating material that heats and stores heat by microwave irradiation is an example of use that can effectively exhibit the effects of the present invention. The heat insulating material that heats and stores heat by microwave irradiation using the heat storage material microcapsule solid material referred to here is, for example, silica gel or the like, as described in JP-A-2001-303032 and JP-A-2005-179458. A water-absorbing compound or a compound having a polar structure and a heat storage material microcapsule solid are filled alone or in a suitable packaging material. By irradiating with microwaves, the water-absorbing compound or the compound having a polar structure generates heat, and the heat is transferred to the solid material of the heat storage material microcapsule which is in direct or indirect contact, thereby enabling heat storage. By setting the magnitude relationship between the hardness of the capsule film constituent resin forming the heat storage material microcapsule in the heat storage material microcapsule solid and the hardness of the binder existing around the heat storage material microcapsule within an appropriate range, Suppresses the destruction of the microcapsule during solid preparation, suppresses the destruction of the microcapsule due to the pressure received from the human body during use, and repeats heating (heat storage) and use (heat dissipation)-that is, the temperature across the phase change temperature It is possible to prevent destruction and deterioration of the microcapsules in the solid material of the heat storage material microcapsules when the temperature change is repeatedly applied in the region, and to maintain a high heat storage performance over a long period of time.

  Utilizing the heat storage material microcapsule solid of the present invention for bedding is an example of use that can effectively demonstrate the effects of the present invention. The bedding using the heat storage material microcapsule solid material mentioned here includes pillows, bed pads, sheets, futons, blankets, etc., and those using a single fabric made of natural fibers or synthetic fibers, or cotton inside. , Filled with synthetic or natural materials such as wool, feathers, urethane foam, sponges, gel cushions, buckwheat husks, plastic beads. The heat storage material microcapsule solid is used by being filled alone in the fabric or filled together with the filler. By setting the magnitude relationship between the hardness of the capsule film constituent resin forming the heat storage material microcapsule in the heat storage material microcapsule solid and the hardness of the binder existing around the heat storage material microcapsule within an appropriate range, Suppresses destruction of microcapsules during solid production, suppresses destruction of microcapsules due to pressure received from the human body during use, and repeats use (endothermic) and standing (cooling)-that is, sandwiching a phase change temperature It is possible to prevent destruction and deterioration of the microcapsules in the solid material of the heat storage material microcapsule when the temperature change is repeatedly applied in the temperature range, and to maintain a high heat storage performance over a long period of time.

  Utilization of the heat storage material microcapsule solid of the present invention as a building material is an example of use that can effectively exhibit the effects of the present invention. Heat storage material microcapsule building material that uses solid material here refers to concrete, cement board, gypsum board, resin board, fiber board using wood fiber, mineral fiber, synthetic resin fiber, etc. Solids are mixed and coated. By using these for the frame, ceiling, wall, floor, etc., it becomes possible to create an environment in which the indoor temperature is hardly raised or lowered. Moreover, it can also be used as a heating and / or cooling system in combination with a heater or a cooler. By setting the magnitude relationship between the hardness of the capsule film constituent resin forming the heat storage material microcapsule in the heat storage material microcapsule solid and the hardness of the binder existing around the heat storage material microcapsule within an appropriate range, Suppressing the destruction of the microcapsule during the production of solids, or suppressing the destruction of the microcapsules due to the pressure during molding when manufacturing building materials using solids, Heat dissipation)-In other words, when the temperature change is repeatedly applied in the temperature range across the phase change temperature, the microcapsule in the solid material of the heat storage material is prevented from being destroyed or deteriorated, and the heat storage performance with a high heat quantity is maintained over a long period of time. It becomes possible to do.

  Utilizing the heat storage material microcapsule solid of the present invention as a gas adsorbent is an example of use that can effectively demonstrate the effects of the present invention. The gas adsorbent using the heat storage material microcapsule solid material referred to here is, for example, an adsorbent such as activated carbon, zeolite, alumina, silica gel, organometallic complex, and the heat storage material as described in JP-A No. 2001-145832. It is a composite of microcapsule solids. Gases to be adsorbed include natural gas such as methane, petroleum gas such as propane and butane, hydrogen, carbon monoxide and carbon dioxide, oxygen, nitrogen, odorous gas, acid gas, basic gas, and organic solvent gas. Etc. The heat (adsorption heat) generated when these gases are adsorbed by the adsorbent can be stored and absorbed in the heat storage material microcapsule solids to suppress the temperature rise, and the decrease in adsorption efficiency can be suppressed. In addition, the heat absorbed when desorbing gas from the adsorbent (desorption heat) is radiated from the heat stored in the heat storage material microcapsule solids to suppress the temperature drop and suppress the decrease in desorption efficiency. can do. By setting the magnitude relationship between the hardness of the capsule film constituent resin forming the heat storage material microcapsule in the heat storage material microcapsule solid and the hardness of the binder existing around the heat storage material microcapsule within an appropriate range, Suppresses destruction of microcapsules during solid production, suppresses destruction of microcapsules due to mechanical pressure during use, and repeats use (heat storage and heat dissipation)-that is, temperature changes in the temperature range sandwiching the phase change temperature It is possible to prevent the microcapsules in the solid material of the heat storage material microcapsules from being broken or deteriorated when repeatedly applied, and maintain a high heat storage performance over a long period of time.

Hereinafter, the present invention will be described in more detail with reference to examples. The parts and percentages in the examples are based on mass unless otherwise specified.
<Heat history durability>
Put the heat storage capsule solid in a thermostatic chamber capable of temperature control, change the temperature from −10 ° C. to 60 ° C. as the temperature range sandwiching the phase change temperature, and hold (temperature increase for 1 hour, 60 ° C. for 30 minutes, Measures the amount of heat stored after applying a temperature change of 1000 times, and the ratio with the amount of heat before giving the temperature change is the heat history durability. It was sex. It shows that it is excellent in the heat retention property after giving a temperature change, so that a numerical value is large. The amount of heat stored was determined by the amount of heat of fusion measured with a differential scanning calorimeter (Perkin Elmer, DSC7, USA).
<Solvent extraction rate>
After 1 g of the produced heat storage capsule solid was shaken and extracted with 50 mL of n-hexane for 5 minutes, the hexane phase was measured by gas chromatography, and the amount of the detected heat storage agent component was charged into the heat storage capsule solid as the amount of heat storage agent component. The value obtained by dividing was taken as the solvent extraction rate (percentage), which was a measure of the degree of film destruction. It shows that the smaller the solvent extraction rate is, the less the film is broken.

  Preparation of heat storage material microcapsule dispersion: In a sodium salt aqueous solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5, 80 g of n-hexadecane having a melting point of 16 ° C. was added as a latent heat storage material. The mixture was added with vigorous stirring and emulsified. Next, 6 g of melamine, 9 g of 37% formaldehyde aqueous solution and 15 g of water were mixed, adjusted to pH 8, and a melamine-formalin initial condensate aqueous solution was prepared at about 80 ° C. The total amount was added to the above emulsion and heated and stirred at 70 ° C. for 2 hours to carry out an encapsulation reaction. Then, the pH of this dispersion was adjusted to 9 to complete the encapsulation, and the heat storage material microcapsule dispersion Got. The volume average particle size of the obtained microcapsules was 2.5 μm. The capsule film-forming resin forming the heat storage material microcapsule was a melamine-formalin resin, and the Rockwell hardness (M scale) was 120.

  Preparation of powdered heat storage material microcapsule solid: In the above heat storage material microcapsule dispersion, polymethyl methacrylate latex as a binder (polymethyl methacrylate Rockwell hardness (M scale) was 95) Is added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder is 100: 15, and then heated and dried with a drum dryer to obtain a powder having a volume average diameter of 500 μm. A solid heat storage material microcapsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 79.

  The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 0.9%, and the heat history durability was 90%.

  The process until the production of the heat storage material microcapsule dispersion was performed in the same manner as in Example 1. The obtained heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder.

  Preparation of granulated heat storage material microcapsule solids: The heat storage material microcapsule powder obtained above was coated with an ethylene-vinyl acetate copolymer latex (ethylene-vinyl acetate copolymer as a binder). Rockwell hardness (M scale) was 35) was added and mixed so that the mass ratio of the heat storage material microcapsule component to the solid content of the binder was 100: 8, and then extruded. Extrusion molding was carried out using a granulating apparatus, and drying was carried out at 100 ° C. to obtain a granulated heat storage material microcapsule solid having a volume average diameter of 2 mm. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29.

  The obtained granulated heat storage material microcapsule solid had a solvent extraction rate of 0.3% and a heat history durability of 98%.

  Preparation of heat storage material microcapsule dispersion: 80 g of dodecyl decanoate having a melting point of 23 ° C. as a latent heat storage material, dicyclohexylmethane 4,4-diisocyanate (aliphatic isocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd. W) A solution in which 15 g was dissolved was added to 100 g of an aqueous solution of 5% polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name POVAL 117), and stirred and emulsified at room temperature until the average particle size became 3 μm. Next, after adding 60 g of 3% polyether aqueous solution (polyether manufactured by Asahi Denka Kogyo Co., Ltd., trade name Adeka Polyether EDP-450) to this emulsion, heating and stirring were performed at 60 ° C. A heat storage material microcapsule dispersion having low viscosity and good dispersion stability was obtained. The volume average particle size of the obtained microcapsules was 3.2 μm. The capsule film-forming resin forming the heat storage material microcapsules was polyurethane urea, and the Rockwell hardness (M scale) was 70.

  Preparation of powder-like heat storage material microcapsule solid: In the above heat storage material microcapsule dispersion, a silicone resin dispersion (the Rockwell hardness (M scale) of the silicone resin was 20) as a binder was stored. After adding and mixing so that the mass ratio of the material microcapsule component and the solid content of the binder becomes a ratio of 100: 10, it is dried by heating with a spray dryer, and is stored in the form of a powder having a volume average diameter of 120 μm A material microcapsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29.

  The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 0.8%, and the heat history durability was 93%.

  The process until the production of the heat storage material microcapsule dispersion was performed in the same manner as in Example 3. The obtained heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a powder of the heat storage material microcapsule.

  Preparation of granulated heat storage material microcapsule solids: The heat storage material microcapsule powder obtained above was coated with an ethylene-vinyl acetate copolymer latex (ethylene-vinyl acetate copolymer as a binder). Rockwell hardness (M scale was 35) was added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder would be a ratio of 100: 12. Extrusion molding was carried out using a granulating apparatus, and drying was performed at 100 ° C. to obtain a granulated heat storage material microcapsule solid having a volume average diameter of 1 mm. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 50.

  The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 0.7% and a heat history durability of 96%.

  Production of heat storage material microcapsule dispersion: 10 g of methyl methacrylate was dissolved in 80 g of n-hexadecane having a melting point of 16 ° C. as a latent heat storage material, and this was put into 300 g of 1% polyvinyl alcohol aqueous solution at 75 ° C. and emulsified by vigorous stirring. It was. Next, the inside of the polymerization vessel containing the emulsified liquid was kept in a nitrogen atmosphere while maintaining at 75 ° C., and then 2,2′-azobis {2- [1- (2-hydroxyethyl) − dissolved in 15 g of ion-exchanged water. 0.3 g of 2-imidazolin-2-yl] propane} dihydrochloride was added. After 7 hours, the polymerization was completed, the inside of the polymerization vessel was cooled to room temperature, and the encapsulation was completed. The volume average particle diameter of the obtained microcapsules was 2.3 μm. The capsule film constituting resin forming this heat storage material microcapsule was polymethyl methacrylate, and the Rockwell hardness (M scale) was 95.

  Preparation of powdered heat storage material microcapsule solid: In the above heat storage material microcapsule dispersion, polystyrene latex (polystyrene Rockwell hardness (M scale) was 75) as a binder was added to the heat storage material microcapsule. After adding and mixing so that the mass ratio of the capsule component and the solid content of the binder becomes a ratio of 100: 8, the mixture is heated and dried by a spray dryer, and the powdered heat storage material micro having a volume average diameter of 100 μm A capsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 79.

  The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 2.1%, and the heat history durability was 82%.

  The production of the heat storage material microcapsule dispersion was performed in the same manner as in Example 5, and the obtained heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder.

  Preparation of granulated heat storage material microcapsule solids: The heat storage material microcapsule powder obtained above was coated with an ethylene-vinyl acetate copolymer latex (ethylene-vinyl acetate copolymer as a binder). The Rockwell hardness (M scale) was 35) was added and mixed so that the mass ratio of the heat storage material microcapsule component to the solid content of the binder was 100: 10, and then extruded. Extrusion molding was carried out using a granulating apparatus, and drying was performed at 100 ° C. to obtain a granulated heat storage material microcapsule solid having a volume average diameter of 1 mm. The ratio between the hardness of the capsule film constituent resin and the hardness of the binder is 100: 37.

  The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 0.6% and a heat history durability of 94%.

  In Example 1, the powdery heat storage material of Example 7 was prepared in the same manner as in Example 1 except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to 100: 30. A microcapsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 79, which is the same as in Example 1. The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 0.6%, and the heat history durability was 91%.

  In Example 2, the granulated body-like heat storage of Example 8 was carried out in the same manner as in Example 2 except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to a ratio of 100: 38. A material microcapsule solid was obtained. In addition, the ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29, which is the same as in Example 2. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 0.1% and a heat history durability of 99%.

  In Example 3, the powdery heat storage material of Example 9 was prepared in the same manner as in Example 3 except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to 100: 25. A microcapsule solid was obtained. Note that the ratio of the hardness of the capsule film-constituting resin to the hardness of the binder is 100: 29, which is the same as in Example 3. The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 0.4%, and the heat history durability was 95%.

  In Example 4, the granulated body-like heat storage of Example 10 was performed in the same manner as in Example 4 except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to a ratio of 100: 45. A material microcapsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 50, which is the same as in Example 4. The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 0.2% and a heat history durability of 98%.

  In Example 5, the powdery heat storage material of Example 11 was prepared in the same manner as in Example 5 except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to a ratio of 100: 23. A microcapsule solid was obtained. Note that the ratio of the hardness of the capsule film-constituting resin to the hardness of the binder is 100: 79, which is the same as in Example 5. The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 1.4%, and the heat history durability was 78%.

  In Example 6, the granulated body-like heat storage of Example 12 was carried out in the same manner as in Example 6, except that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was changed to a ratio of 100: 40. A material microcapsule solid was obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 37, which is the same as in Example 6. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 0.4% and a heat history durability of 96%.

(Comparative Example 1)
In Example 2, a melamine-formalin resin initial condensate aqueous solution (a melamine-formalin resin Rockwell instead of an ethylene-vinyl acetate copolymer latex as a binder at the time of production of a granular heat storage material microcapsule solid A granulated heat storage material microcapsule solid in Comparative Example 1 was obtained in the same manner as in Example 2 except that the hardness (M scale) was 120). The ratio between the hardness of the capsule film constituent resin and the hardness of the binder is 100: 100. The solvent extraction rate of the obtained granulated heat storage material microcapsule solid was 4.1%, and the heat history durability was 66%.

(Comparative Example 2)
In Example 4, an aqueous urea formalin resin condensate aqueous solution (the Rockwell hardness of urea formalin resin (Rockwell hardness ( M scale) was 115), and a granulated heat storage material microcapsule solid of Comparative Example 2 was obtained in the same manner as in Example 4. The ratio between the hardness of the capsule film constituent resin and the hardness of the binder is 100: 160. The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 6.2% and a thermal history durability of 37%.

(Comparative Example 3)
In Example 6, Example 6 was used except that an aqueous urea formalin resin condensate aqueous solution was used in place of the ethylene-vinyl acetate copolymer latex as a binder during the production of the granular heat storage material microcapsule solid. By the same operation, a granulated heat storage material microcapsule solid of Comparative Example 3 was obtained. The ratio between the hardness of the capsule film constituent resin and the hardness of the binder is 100: 120. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 6.9% and a thermal history durability of 35%.

(Comparative Example 4)
In Example 2, a melamine-formalin resin initial condensate aqueous solution was used in place of the ethylene-vinyl acetate copolymer latex as a binder at the time of production of the granulated heat storage material microcapsule solid, and the heat storage material The granulated heat storage material microcapsule solid of Comparative Example 4 was obtained in the same manner as in Example 2 except that the mass ratio of the microcapsule component and the solid content of the binder was set to 100: 38. Obtained. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 100, which is the same as in Comparative Example 1. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 2.9% and a heat history durability of 59%.

(Comparative Example 5)
In Example 4, a urea formalin resin initial condensate aqueous solution was used in place of the ethylene-vinyl acetate copolymer latex as a binder when preparing the granulated heat storage material microcapsule solid, and the heat storage material micro The granulated heat storage material microcapsule solid material of Comparative Example 5 is obtained in the same manner as in Example 4 except that the mass ratio of the capsule component and the solid content of the binder is 100: 45. It was. Note that the ratio of the hardness of the capsule film-constituting resin to the hardness of the binder is 100: 160, which is the same as in Comparative Example 2. The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 4.1% and a heat history durability of 32%.

(Comparative Example 6)
In Example 6, the urea-formalin resin initial condensate aqueous solution was used in place of the ethylene-vinyl acetate copolymer latex as a binder when preparing the granulated heat storage material microcapsule solid, and the heat storage material micro The granulated body heat storage material microcapsule solid of Comparative Example 6 is obtained in the same manner as in Example 6 except that the mass ratio of the capsule component and the solid content of the binder is 100: 40. It was. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 120, which is the same as in Comparative Example 3. The solvent extraction rate of the obtained granulated heat storage material microcapsule solid was 4.7%, and the heat history durability was 29%.

  Preparation of granulated heat storage material microcapsule solid: In the preparation of the heat storage material microcapsule dispersion of Example 1, paraffin wax having a melting point of 55 ° C. was used instead of n-hexadecane as the latent heat storage material. A heat storage material microcapsule dispersion was prepared in exactly the same manner as in Example 1. Next, the same operation as in Example 2 is performed, and the heat storage material microcapsule powder of Example 13 is obtained from the heat storage material microcapsule dispersion via the heat storage material microcapsule powder. It was. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29. The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 0.2% and a heat history durability of 98%.

  Preparation of heat insulating material to be heated and stored by microwave irradiation: 33 parts by mass of the granulated heat storage material microcapsule solid obtained in Example 13 and 67 parts by mass of silica gel particles having a particle diameter of 2 mm were mixed, and cotton A bag made of 600 g was filled. When heating was performed using a microwave oven for 2 minutes, a comfortable temperature range of 43 ° C. or higher lasted for 70 minutes, and a heat insulating material that maintained warmth for a long time was obtained. Moreover, even if this operation was repeated 200 times, the heat storage component did not ooze out from the granulated solid heat storage material microcapsule solid, and the time for maintaining the temperature of 43 ° C. or higher did not change.

  Preparation of granulated heat storage material microcapsule solid: In the preparation of the heat storage material microcapsule dispersion of Example 1, n-octadecane having a melting point of 28 ° C. was used instead of n-hexadecane as the latent heat storage material Prepared a dispersion liquid of heat storage material microcapsules by the same operation as in Example 1. Next, the same operation as in Example 2 is performed to obtain a granulated heat storage material microcapsule solid in Example 14 from this heat storage material microcapsule dispersion via the heat storage material microcapsule powder. It was. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29. The obtained granulated heat storage material microcapsule solid had a solvent extraction rate of 0.3% and a heat history durability of 98%.

  Preparation of pillow: After mixing 100 parts by mass of the granulated heat storage material microcapsule solid material obtained in Example 14 and 100 parts by mass of buckwheat husk, 1.5 kg of this mixture was added to a cotton fabric to a length of 45 cm × A pillow having heat storage properties was obtained by filling a bag that was sewn in a horizontal 65 cm bag. When this pillow was left in a room at room temperature of 25 ° C. for 6 hours, when it was used, a comfortable cooling sensation lasted for 1 hour. Further, even when this operation was repeated 200 times, the heat storage component did not ooze out from the granulated solid heat storage material microcapsule solids, and the time for maintaining a comfortable cool feeling did not change.

  Preparation of granulated heat storage material microcapsule solid: In the preparation of the heat storage material microcapsule dispersion of Example 1, n-octadecane having a melting point of 28 ° C. was used instead of n-hexadecane as the latent heat storage material Prepared a dispersion liquid of heat storage material microcapsules by the same operation as in Example 1. Next, the same operation as in Example 2 was performed except that the volume average diameter of the granulated body heat storage material microcapsule solids was set to 1 mm in Example 2, and this heat storage material microcapsule dispersion was used as a heat storage material. The granulated body heat storage material microcapsule solid of Example 15 was obtained via the microcapsule powder. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 0.5% and a heat history durability of 97%.

  Production of wood board: 30 parts of granulated solid heat storage material microcapsule solid material obtained in Example 15, 70 parts of wood powder having a major axis of 3 mm or less as a filling material, and 30% concentration urea formalin resin initial condensate After thoroughly mixing 30 parts of the aqueous solution, pressurization and thermoforming were performed under conditions of a pressure of 3 MPa and a temperature of 160 ° C. to obtain a wooden board having a heat storage property of 40 mm square and 5 mm thick. A cube-shaped box was prepared by combining six of these plate-shaped compacts, left in a large constant temperature chamber with an internal temperature of 15 ° C for 6 hours, and then the internal temperature was switched to 33 ° C. The air temperature of the part was maintained at 28 ° C. or lower for 3 hours. Moreover, when the operation of switching the internal temperature of the large constant temperature chamber alternately between 10 ° C. and 35 ° C. every 2 hours was repeated 10 times, the air temperature in the central part of the box was in a relatively narrow range of 19 to 28 ° C. The thermal storage performance was excellent, and excellent heat storage performance was confirmed. Furthermore, even when this operation was repeated 200 times, the heat storage component did not ooze out from the granulated solid material of the heat storage material microcapsule, and the change range of the air temperature at the center inside the box did not change.

  Preparation of granulated heat storage material microcapsule solid: In the preparation of the heat storage material microcapsule dispersion of Example 1, paraffin wax having a melting point of 36 ° C. was used instead of n-hexadecane as the latent heat storage material. A heat storage material microcapsule dispersion was prepared in exactly the same manner as in Example 1. Next, the same operation as in Example 2 was performed except that the volume average diameter of the granulated body heat storage material microcapsule solids was set to 1 mm in Example 2, and this heat storage material microcapsule dispersion was used as a heat storage material. A granulated heat storage material microcapsule solid in Example 16 was obtained via the microcapsule powder. The ratio of the hardness of the capsule film constituent resin to the hardness of the binder is 100: 29. The resulting granulated heat storage material microcapsule solid had a solvent extraction rate of 0.6% and a heat history durability of 97%.

  Preparation of gas adsorbent: 35 parts of the granulated heat storage material microcapsule solid obtained in Example 16 and 100 parts of activated carbon having an average particle diameter of 1.2 mm were mixed to obtain a heat storage material composite adsorbent. . When the adsorption amount of methane gas (supply gas temperature = 25 ° C.) was measured using this heat storage material composite adsorbent, the gas adsorption amount at a pressure of 1 MPa was 43 mg per 1 g of the heat storage material composite adsorbent. In addition, when gas adsorption and desorption were repeated 50 times by alternately repeating the gas pressure of 1 MPa and 0.1 MPa, the temperature around 36 ° C. near the melting point lasted for a long time, and the temperature of the heat storage material composite adsorbent There was hardly any increase, and the gas adsorption amount was hardly lowered to 41 mg per 1 g of the heat storage material composite adsorbent, and an excellent heat storage effect was confirmed. Furthermore, even when this operation was repeated 200 times, the heat storage component did not ooze out from the granulated solid heat storage material microcapsule solid, and the gas adsorption amount did not change.

  The heat-storing material microcapsule solid material according to the present invention includes a heat-retaining material, bedding, building material, and gas adsorbent that are heated and stored by microwave irradiation, as well as fiber processed products such as clothing materials, and overheat-suppressing materials such as electronic parts and / or Or supercooling suppression materials, building heat storage / space-filling air conditioning for buildings, floor heating, air conditioning, civil engineering materials such as roads and bridges, waste heat utilization equipment such as fuel cells and incinerators, hot water storage and storage, industrial It can be applied to various fields of use such as thermal insulation materials for agriculture, thermal insulation materials for agriculture, household goods, health supplies, and medical materials.

Claims (5)

  In the heat storage material microcapsule solid material in which the heat storage material microcapsules enclosing the heat storage material are fixed together with the binder, the hardness of the binder is smaller than the hardness of the capsule film constituting resin forming the heat storage material microcapsule. A heat storage material microcapsule solid, characterized by using a binder having   When the form of the heat storage material microcapsule solid is powder or solid, the hardness value of the binder is 0.01 or more and 95 or less when the hardness value of the capsule film constituting resin is 100 Item 1. The heat storage material microcapsule solid according to Item 1.   2. When the form of the heat storage material microcapsule solid is a granulated body, the hardness value of the binder is 0.1 or more and 90 or less when the hardness value of the capsule film constituting resin is 100. The heat storage material microcapsule solid as described.   The heat storage material microcapsule solid material according to any one of claims 1 to 3, wherein the heat storage material microcapsule enclosing the heat storage material has a volume average particle diameter in a range of 0.5 to 50 µm.   The heat storage material microcapsule solid material according to any one of claims 1 to 4, wherein a volume average diameter of the heat storage material microcapsule solid material is in a range of 10 µm to 100 mm.