JP2006097000A - 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 coefficient of thermal expansion of the binder is greater 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 a heat storage material microcapsule solid body in which a heat storage material microcapsule enclosing the heat storage material is fixed together with a binder, the thermal expansion coefficient of the binder is a capsule film constituting resin that forms the heat storage material microcapsule. A heat storage material microcapsule solid, characterized by using a binder having a value larger than the thermal expansion coefficient;
(2) When the form of the heat storage material microcapsule solid is powder or solid, the value of the thermal expansion coefficient of the binder is 1. The heat storage material microcapsule solid according to the above (1), which is from 05 to 50,
(3) When the form of the heat storage material microcapsule solid is a granulated body, the value of the thermal expansion coefficient of the binder is 1.1 or more when the value of the thermal expansion coefficient of the capsule film-forming resin is 1. The heat storage material microcapsule solid according to the above (1), which is 30 or less,
(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 coefficient of thermal expansion of a binder used when a plurality of heat storage material microcapsules are fixed, from the coefficient of thermal expansion of the capsule film constituent resin that forms the heat storage material microcapsule. By using a resin having a large value, the microcapsules are not destroyed during solid production, and the heat storage effect is not reduced even if temperature changes are repeatedly applied in the temperature range sandwiching the phase change temperature. It became possible to maintain performance over a period of time. That is, by appropriately setting the thermal expansion coefficient of the capsule film constituting resin forming the heat storage material microcapsule and the thermal expansion coefficient of the binder existing around the heat storage material microcapsule, a desired value in the initial stage can be obtained. Performance and durability could be improved.

  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, the binder after moisture is removed undergoes volume expansion due to heat, and the capsule film also undergoes volume expansion due to heat. At this time, if the thermal expansion coefficient of the binder is smaller than the thermal expansion coefficient of the capsule film constituent resin that forms the heat storage material microcapsule, the capsule film receives stress from the binder and damages the capsule film. Can receive. On the other hand, by using a binder having a value larger than the thermal expansion coefficient of the capsule film constituent resin, the capsule film becomes less susceptible to stress from the binder and can suppress damage to the capsule film. did it.

  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, the binder having a value larger than the thermal expansion coefficient of the capsule film constituting resin forming the heat storage material microcapsule is used when the heat storage material microcapsules are fixed to each other. By using, volumetric displacement 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 coefficient of thermal expansion according to the present invention represents the rate at which the volume V (or length L) of the substance increases as the temperature T increases, and is defined as ∂lnV / ∂T or ∂lnL / ∂T. The former is called body thermal expansion coefficient, and the latter is called linear thermal expansion coefficient. For isotropic materials, ∂lnV / ∂T = 3∂lnL / ∂T, but for anisotropic materials such as crystals, the coefficient of linear thermal expansion varies depending on the direction (the above is a new version of the Dictionary of Polymers (published by Asakura Shoten, 1988). Issue year)). In the present invention, the above-described body thermal expansion coefficient and linear thermal expansion coefficient are collectively referred to as a thermal expansion coefficient. From the viewpoint of improving durability during use, both the body thermal expansion coefficient and the linear thermal expansion coefficient can be adopted as suitable standards. The thermal expansion coefficient of the capsule film constituting resin and the thermal expansion coefficient of the binder can be derived from a handbook containing the thermal expansion coefficient of each material, or can be calculated by actual measurement using various measuring devices. Note that the test standard for linear thermal expansion coefficient is established in ASTM-D696.

  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 thermal expansion coefficient larger than that of the capsule film-constituting resin that forms the capsule. The relationship between the thermal expansion coefficient of the capsule film constituent resin and the thermal expansion coefficient of the binder is such that the object of the present invention can be achieved if the value of the thermal expansion coefficient of the binder exceeds the value of the thermal expansion coefficient of the capsule film constituent resin. However, the preferred range varies slightly 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 value of the thermal expansion coefficient of the binder is 1.05 or more when the value of the thermal expansion coefficient of the capsule film constituent resin is 1. It is preferable that it is 50 or less. When the shape of the heat storage material microcapsule solid is a granulated body, the value of the thermal expansion coefficient of the binder is 1.1 or more and 30 or less when the value of the coefficient of thermal expansion of the capsule film constituent resin is 1. It is preferable. 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, it is preferable that the value of the coefficient of thermal expansion of the binder is 1.05 or more and 30 or less when the value of the coefficient of thermal expansion of the capsule film constituent resin is 1. 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 The value of the thermal expansion coefficient of the binder is preferably from 1.1 to 20 when the value of the thermal expansion coefficient of the film-constituting resin is 1. If the thermal expansion coefficient of the binder is smaller than this range, the volume variation due to expansion and contraction may not be sufficiently absorbed. If the thermal expansion coefficient of the binder is larger than this range, inadvertent fixation (so-called blocking) between the heat storage material microcapsule solids may occur.

When melamine formalin resins or urea formalin resins obtained by in situ polymerization are used as the capsule film constituent resin forming the heat storage material microcapsules, the thermal expansion coefficient of these film constituent resins is 3 × 10 in terms of linear thermal expansion coefficient. ^{Since it is −5} to 4 × 10 ⁻⁵ / K, the binder can be suitably used as long as its thermal expansion coefficient is within the above range. Since the thermal expansion coefficients of these film-constituting resins are relatively low, the selection range of the 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 thermal expansion coefficient of these film constituent resins is the linear thermal expansion coefficient. 7 × 10 ⁻⁵ to 15 × 10 ⁻⁵ / K in many cases, it is necessary to select a binder whose thermal expansion coefficient is within the above-mentioned range in order to use it suitably. There is. When using these film-constituting resins, it is necessary to select the binder to be used in consideration of the thermal expansion coefficient of the binder more carefully than when using melamine formalin resins or urea formalin resins. . Further, when two or more kinds of binders having different thermal expansion coefficients are used, the object of the present invention can be achieved if the thermal expansion coefficients of the binder mixture satisfy 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 alone or in combination of two or more as long as it satisfies the above conditions of thermal expansion coefficient. It is possible to select and use a conventionally known natural polymer having a wearing ability and a film forming ability, a natural polymer modified product (semi-synthetic product), a synthetic polymer and an inorganic compound in consideration of the thermal expansion coefficient. it can.

  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 saponified 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. Heat storage material microcapsule Solid relationship between the thermal expansion coefficient of the capsule film constituent resin that forms the microcapsule and the thermal expansion coefficient of the binder existing around the heat storage material microcapsule within an appropriate range By doing so, the destruction of the microcapsules during solid preparation is suppressed, the destruction of the microcapsules due to the pressure received from the human body during use, or repeated heating (heat storage) and use (heat dissipation)-that is, phase change 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 sandwiching the temperature, 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. Heat storage material microcapsule Solid relationship between the thermal expansion coefficient of the capsule film constituent resin that forms the microcapsule and the thermal expansion coefficient of the binder existing around the heat storage material microcapsule within an appropriate range By doing so, the destruction of the microcapsules at the time of solid preparation is suppressed, the destruction of the microcapsules due to the pressure received from the human body at the time of use, or the repeated use (endothermic) and leaving (cooling) -that is, the phase 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 given in the temperature range sandwiching the change temperature, 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. Heat storage material microcapsule Solid relationship between the thermal expansion coefficient of the capsule film constituent resin that forms the microcapsule and the thermal expansion coefficient of the binder existing around the heat storage material microcapsule within an appropriate range By suppressing the destruction of the microcapsule during the production of the solid material, or suppressing the destruction of the microcapsule due to the pressure at the time of molding when manufacturing the building material using the solid material, use (endothermic and cooling) Or heat storage and heat dissipation)-that is, when the temperature change is repeatedly applied in the temperature range sandwiching the phase change temperature, the microcapsules in the solid material of the heat storage material microcapsules are prevented from being destroyed and deteriorated, and the heat quantity is high over a long period of time. It becomes possible to maintain heat storage performance.

  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. Heat storage material microcapsule Solid relationship between the thermal expansion coefficient of the capsule film constituent resin that forms the microcapsule and the thermal expansion coefficient of the binder existing around the heat storage material microcapsule within an appropriate range To suppress the destruction of the microcapsule during solid preparation, to suppress the destruction of the microcapsule due to mechanical pressure during use, or to repeatedly use (heat storage and heat dissipation)-that is, the temperature that sandwiches 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.

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-constituting resin forming the heat storage material microcapsule was melamine-formalin resin, and the linear thermal expansion coefficient was 4.0 × 10 ⁻⁵ / K.

Preparation of powdered heat storage material microcapsule solid: In the above heat storage material microcapsule dispersion, polymethyl methacrylate latex as a binder (the linear thermal expansion coefficient of polymethyl methacrylate is 7.0 × 10 ⁻⁵ / K) was added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was 100: 15, and then heated and dried with a drum dryer to obtain a volume average. A powdery heat storage material microcapsule solid having a diameter of 500 μm was obtained. The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 1.8.

  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). Linear thermal expansion coefficient was 18 × 10 ⁻⁵ / K), and added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was 100: 8, Extrusion molding was performed with an extrusion granulator and dried at 100 ° C. to obtain a granulated heat storage material microcapsule solid having a volume average diameter of 2 mm. The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 4.5.

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

Production 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 linear thermal expansion coefficient was 15 × 10 ⁻⁵ / K.

Production of powder-like heat storage material microcapsule solids: Silicone resin dispersion as binder in the heat storage material microcapsule dispersion (linear thermal expansion coefficient of silicone resin was 19 × 10 ⁻⁵ / K) 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: 10, and then heated and dried by a spray dryer to obtain a powder having a volume average diameter of 120 μm. A heat storage material microcapsule solid was obtained. The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 1.3.

  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). Linear thermal expansion coefficient was 18 × 10 ⁻⁵ / K), and added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was 100: 12, Extrusion molding was performed using an extrusion granulator, 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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 1.2.

  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 the heat storage material microcapsule was polymethyl methacrylate, and the linear thermal expansion coefficient was 7.0 × 10 ⁻⁵ / K.

Production of powder-like heat storage material microcapsule solids: Silicone resin dispersion as binder in the heat storage material microcapsule dispersion (linear thermal expansion coefficient of silicone resin was 19 × 10 ⁻⁵ / K) Is added and mixed so that the mass ratio of the heat storage material microcapsule component to the solid content of the binder is 100: 8, and then heated and dried with a spray dryer to obtain a powder having a volume average diameter of 100 μm. A heat storage material microcapsule solid was obtained. In addition, the ratio of the thermal expansion coefficient of the capsule film constituent resin and the thermal expansion coefficient of the binder is 1: 2.7.

  The resulting powdery heat storage material microcapsule solid had a solvent extraction rate of 1.1% and a heat history durability of 92%.

  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). Linear thermal expansion coefficient was 18 × 10 ⁻⁵ / K), and added and mixed so that the mass ratio of the heat storage material microcapsule component and the solid content of the binder was 100: 10, Extrusion molding was performed using an extrusion granulator, 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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 2.6.

  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 thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 1.8, 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. The ratio of the thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 4.5, 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. The ratio of the thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 1.3, 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 thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 1.2, 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. The ratio of the thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 2.7, which is the same as in Example 5. The solvent extraction rate of the obtained powdery heat storage material microcapsule solid was 0.8%, and the heat history durability was 94%.

  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 thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 2.6, 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 (linear heat of melamine-formalin resin instead of ethylene-vinyl acetate copolymer latex as a binder at the time of production of granulated heat storage material microcapsule solids The granulated heat storage material microcapsule solid of Comparative Example 1 was obtained in the same manner as in Example 2 except that the expansion coefficient was 4.0 × 10 ⁻⁵ / K). The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 1. 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, instead of the ethylene-vinyl acetate copolymer latex as a binder for the production of the granular heat storage material microcapsule solid, an aqueous urea formalin resin condensate aqueous solution (linear thermal expansion coefficient of urea formalin resin) in the same manner as in example 4 except for using which was) a 2.9 × 10 ^-5 / K, to obtain a granule form of the heat storage material microcapsule solids of Comparative example 2. The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 0.19. 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, a melamine-formalin resin initial condensate aqueous solution (linear heat of melamine-formalin resin instead of ethylene-vinyl acetate copolymer latex as a binder at the time of preparation of granulated body heat storage material microcapsule solids The granulated heat storage material microcapsule solid of Comparative Example 3 was obtained in the same manner as in Example 6 except that the expansion coefficient was 4.0 × 10 ⁻⁵ / K). The ratio of the thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 0.57. The obtained granular heat storage material microcapsule solid had a solvent extraction rate of 4.5% and a heat history durability of 59%.

(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 thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 1, 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. The ratio of the thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 0.19, 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, 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 preparation of the granulated body heat storage material microcapsule solid, and the heat storage material The granulated heat storage material microcapsule solid material of Comparative Example 6 was obtained in the same manner as in Example 6 except that the mass ratio of the microcapsule component and the solid content of the binder was set to 100: 40. Obtained. The ratio of the thermal expansion coefficient of the capsule film-constituting resin to the thermal expansion coefficient of the binder is 1: 0.57, which is the same as in Comparative Example 3. The obtained granulated heat storage material microcapsule solid had a solvent extraction rate of 3.4% and a heat history durability of 48%.

  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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 4.5. 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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 4.5. 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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 4.5. 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 thermal expansion coefficient of the capsule film constituent resin to the thermal expansion coefficient of the binder is 1: 4.5. 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 a heat storage material microcapsule solid body in which a heat storage material microcapsule encapsulating the heat storage material is fixed together with a binder, the thermal expansion coefficient of the binder is a thermal expansion coefficient of the capsule film constituting resin forming the heat storage material microcapsule. A heat storage material microcapsule solid, wherein a binder having a larger value is used.   When the shape of the heat storage material microcapsule solid is powder or solid, the value of the thermal expansion coefficient of the binder is 1 to 50 when the value of the thermal expansion coefficient of the capsule film constituent resin is 1. The heat storage material microcapsule solid according to claim 1, which is:   When the form of the heat storage material microcapsule solid is a granulated body, the value of the thermal expansion coefficient of the binder film resin when the value of the thermal expansion coefficient of the capsule film constituting resin is 1 is 1.1 or more and 30 or less. The heat storage material microcapsule solid according to claim 1.   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.