JP2006213914A - Thermal storage material microcapsule granule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal storage material microcapsule granule that can be used for a long period of time without the decrease of the thermal storage effect even when it is used in an environment where an outer pressure is applied to a packed material or a processed product of the microcapsule granule containing a latent heat storaging material. <P>SOLUTION: The thermal storage material microcapsule granule is formed by combining a plurality of thermal storage material microcapsules containing a heat storaging material together with a binder, and a value obtained by dividing a press-crashing strength of the thermal storage material microcapsule granule measured by the JIS Z 8841 by a projection cross-sectional area of the thermal storage material microcapsule granule is set within the range of 0.2-50 N/mm<SP>2</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a microcapsule granulated product containing a 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. Since a large temperature difference does not occur for a large amount, there is an advantage that heat loss can be suppressed to a small 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 heat storage material microcapsules in a state of being dispersed in a medium. By drying it and taking it out as a solid material, the solid state can 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 likely to be scattered in the powdered state just by drying the medium used to make the microcapsule and may be restricted in handling, so the heat storage material microcapsule together with the binder A heat storage material microcapsule granulated product in which a plurality of particles are fixed and granulated to a size that is difficult to scatter is proposed (see, for example, Patent Documents 5 and 6).

  However, some of the heat storage material microcapsule granulated products may cause a so-called pulverization phenomenon in which a part of the granulated material collapses and pulverizes. There are problems in using the capsule for a long period of time, such as the capsule falling off or the durability of the processed product of the heat storage material microcapsule granulated product being lowered.

On the other hand, in microcapsules other than the heat storage material microcapsule, a proposal example in which the crushing strength, breaking strength, compressive strength, etc. of the microcapsule itself are defined in order to control pressure sensitivity, sustained release properties, etc. 9)), but there is no example that defines the crushing strength of the whole microcapsule granulated product in which a plurality of microcapsules are fixed together with a binder.
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 JP 2001-303032 A JP-A-8-325117 Japanese Examined Patent Publication No. 7-121850 JP-A-6-3209

  The object of the present invention is to provide a microcapsule granulated product containing a latent heat storage material, which is resistant to scratching even when the heat storage material microcapsule granulated product is used in an environment where external force is applied. An object of the present invention is to provide a heat storage material microcapsule granulated product that is excellent in resistance to dust and has a high heat storage performance and can be used for a long period of time.

As a result of intensive studies, the present inventors have found the following invention.
(1) In a heat storage material microcapsule granulated product in which a plurality of heat storage material microcapsules encapsulating the heat storage material are fixed together with a binder, the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granulated material is divided by the projected cross-sectional area of the thermal storage material microcapsule granules are thermal storage material microcapsule granules, characterized in that in the range of 0.2~50N / mm ^2,
(2) The heat storage material microcapsule granulated product according to the above (1), wherein the addition ratio of the binder in the heat storage material microcapsule granulated product is in the range of 0.1 to 20% by mass,
(3) The heat storage material microcapsule granulated product according to (1) or (2) above, wherein the average diameter in the minor axis direction of the heat storage material microcapsule granulated product is in the range of 0.1 to 100 mm,
(4) The heat storage material microcapsule granulated product according to any one of (1) to (3) above, wherein the binder is a polyamide epihalohydrin resin.

The heat storage material microcapsule granulated product shown in the present invention has a value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granulated product by the projected cross-sectional area of the heat storage material microcapsule granulated product. By setting the range of ^{2 to} 50 N / mm ² , even if the heat storage material microcapsule granulated filler or processed material is used in an environment where external force is applied, it has excellent scratch resistance and is difficult to dust. In addition, it has become possible to maintain a high heat storage performance over a long period of time.

  In the heat storage material microcapsule granulated product as in the present invention, the strength of the entire heat storage material microcapsule granule is important as well as the strength of each single heat storage material microcapsule. By setting the strength of the material within an appropriate range, a part of the granulated material collapses and pulverizes, so-called powder falling phenomenon is suppressed, and the heat storage material microcapsule is filled with the heat storage material microcapsule. It can be prevented from falling off, and the durability of the heat storage material microcapsule granulated product can be prevented from being lowered. did it.

  The latent heat storage material included in the microcapsule of 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, butyl stearate and stearyl stearate, and alcohols such as stearyl alcohol, preferably having a heat of fusion of about 80 kJ / Kg or more of a compound that is chemically and physically stable and inexpensive. 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.

  As a method for producing the microcapsules of the present invention, a physical method and a chemical method are known. 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. Sho 62-1452). Gazette), a method of spraying a thermoplastic resin on the surface of the heat storage material particles (Japanese Patent Laid-Open No. 62-45680), 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 the monomer 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), etc. Is used.

  As the membrane material of the microcapsule according to the present invention, polystyrene, polyacrylonitrile, poly (meth) acrylate, polyamide, polyacrylamide, which are obtained by a method such as an interfacial polymerization method, an in-situ method, or a radical polymerization method, Ethyl cellulose, polyurethane, aminoplast resin, or synthetic or natural resin using a coacervation method of gelatin and carboxymethyl cellulose or gum arabic is used. Melamine formalin resin, urea formalin resin, polyamide, polyurea, polyurethane urea are used. It is particularly preferable to use a microcapsule using a melamine formalin resin film or a urea formalin resin film by a physically and chemically stable in situ method.

  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 50 μm, the mechanical shearing force may be extremely weak, and when the particle diameter is smaller than 0.5 μm, the fracture is suppressed, but the film thickness becomes thin 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 for obtaining the heat storage material microcapsule granulated product of the present invention, a spray dryer, drum dryer, freeze dryer, filter with or without a binder added to the microcapsule dispersion prepared in the state of an aqueous dispersion Various types of drying equipment such as presses are used to evaporate and dehydrate the water of the medium to form a powder or solid, and then add a binder to the various types such as extrusion granulation, tumbling granulation, stirring granulation, etc. A granulated product can be produced by granulating using a granulation method. Alternatively, a granulated product can be prepared by adding a thickener or a dehydrating agent to the microcapsule dispersion and adding a binder, followed by granulation using the same various granulation methods. Furthermore, an antioxidant, a VOC adsorbent, activated carbon, a photocatalyst, an organic or inorganic pigment, an incombustible material, a flame retardant powder, and the like can be added during drying or granulation. The shape of the heat storage material microcapsule granule 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, a cylinder, and the like.

  The average diameter in the minor axis direction of the heat storage material microcapsule granulated product according to the present invention is preferably in the range of 0.1 to 100 mm, and more preferably in the range of 0.5 to 50 mm. When the average diameter is less than 0.1 mm, the granulated product is likely to be scattered, so-called dusting is likely to occur, and handling properties may be deteriorated. When the average diameter is larger than 100 mm, the ratio of the surface area is smaller than the volume, and the efficiency of heat exchange with the outside may be reduced. The short diameter direction average diameter described in the present invention represents the average diameter in the shortest diameter direction of the microcapsule granulated product, and the short diameter direction average diameter can be measured with industrial calipers or the like, as well as commercially available optical It is also possible to measure automatically by using an automatic particle size measuring device or the like.

  The crushing strength of the granulated product according to the present invention is a strength representing the resistance against fracture of the granulated product, and is measured by a test method defined in JIS Z 8841 (granulated product-strength test method). The unit of crushing strength according to JIS Z 8841 is represented by N (Newton). However, when the unit of the crushing strength is handled as N, when the size of the granulated material is large, a large value of the crushing strength is obtained, and when the size of the granulated material is small, the value of the crushing strength tends to be small. Therefore, in the present invention, in order to correct the factor of the size of the granulated product, the value obtained by dividing the crushing strength by the projected cross-sectional area in the compression direction of the granulated product to be measured is a strength value. It was decided to treat it as an indicator. The compression direction at the time of crushing strength measurement in the present invention was set to the shortest diameter direction of the granulated material to be measured. The projected cross-sectional area of the granulated product in the compression direction is obtained as an area when the granulated product to be measured is projected onto a plane perpendicular to the compression direction. The crushing strength can be measured using various commercially available material strength testers.

The heat storage material microcapsule granulated product of the present invention has a value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granulated product by the projected cross-sectional area of the heat storage material microcapsule granulated product. Maintaining high heat storage performance over a long period of time even if the heat storage material microcapsule granulated filler or processed product is used in an environment where external force is applied by setting the range to -50 N / mm ² Is possible. More preferably, it is more preferably in the range of 0.5 to 20 N / mm ² . If the numerical value obtained by dividing the crushing strength by the projected cross-sectional area is less than 0.2 N / mm ² , the strength becomes insufficient, and a part of the granulated material may collapse and cause a pulverization phenomenon in which the powder falls. The capsule may be broken and the heat storage component may ooze out to the outside, making it difficult to maintain the heat storage performance over a long period of time. In addition, when the numerical value is larger than 50 N / mm ² , the strength is sufficient, but expansion and contraction when the temperature change is repeatedly applied to the heat storage material microcapsule granulated material in the temperature range sandwiching the phase change temperature. The volume fluctuation of the microcapsule due to the above may not be absorbed by the binder present around the microcapsule, resulting in damage to the capsule film and gradually reducing the heat storage effect. It becomes difficult to maintain heat storage performance with a large amount of heat over a long period of time. In addition, the amount of heat storage may become small because the amount of the binder in the heat storage material microcapsule granulated product becomes too large.

To obtain a value obtained by dividing the crushing strength of the heat storage material microcapsule granulated material according to JIS Z 8841 by the projected cross-sectional area of the heat storage material microcapsule granulated material, within a range of 0.2 to 50 N / mm ² , This was achieved for the first time by adjusting the following factors in a balanced manner. In other words, when obtaining a granulated product via the state of the powder or solid, the water absorption amount of the powder or solid, the type and addition form of the binder, the addition amount, and the amount of added water are optimal. Turned into. Alternatively, when adding a thickener or dehydrating agent to a microcapsule dispersion and adding a binder to obtain a granulated product without going through a powder or solid, the type and addition of the thickener or dehydrating agent The form and addition amount, the kind of binder, the addition form and addition amount were optimized, respectively. Furthermore, the order of addition of each material, the addition method, and the mixing method were also optimized. In various granulation methods such as extrusion granulation, rolling granulation and stirring granulation, optimum extrusion method, extrusion condition, rolling method and rolling condition, stirring method and stirring condition were set respectively. The drying method after granulation and the drying conditions were also optimized. By optimizing all of these in a well-balanced manner, a value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granulated product by the projected cross-sectional area of the heat storage material microcapsule granulated product is 0.2 to A range of 50 N / mm ² could be achieved.

  The binder used in the heat storage material microcapsule granulated product of the present invention is a component that also brings the action of enhancing the cohesive force, fusion power, and water resistance between the microcapsules, and the heat storage material microcapsule and the binder are integrated. Thus, the strength of the heat storage material microcapsule granulated product of the present invention is expressed. As the binder used in the present invention, any binder can be used as long as the above-mentioned strength can be obtained. Specific examples thereof include conventionally known binding ability and film forming ability. Natural polymers, natural polymer modified products (semi-synthetic products), synthetic polymers and inorganic compounds can be used.

  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 alcohol such as polyvinyl methyl ether, polyvinyl ethyl ether, and polyvinyl isobutyl ether, poly (meth) acrylic acid and esters thereof. , Poly (meth) acrylic acid ester partial saponification products, and poly (meth) acrylic acid derivatives such as poly (meth) acrylic amide, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, and vinylpyrrolidone vinyl acetate Molecules, polyvinyl acetate, polyurethane, styrene-butadiene copolymer, carboxy-modified styrene-butadiene copolymer, poly (meth) acrylates, acrylonitrile butane Latexes such as ene copolymers, methyl butadiene acrylate copolymers, ethylene vinyl acetate copolymers, polyurethane elastomer dispersions, polysiloxane acrylic graft polymer dispersions, silicone polymers, melamine formaldehyde precondensates, urea formalin Examples include initial condensates, polyamide epihalohydrins, polyamine epihalohydrins, and thermoplastic elastomers. In particular, polyamide epihalohydrin resins and polyamine epihalohydrin resins, and more preferably polyamide epichlorohydrin resin, exhibit sufficient crushing strength even with a small amount of addition, and also have excellent solvent resistance in the heat storage material microcapsule granulated product. Since it can be given, it can be used particularly preferably.

  The addition ratio of the binder in the heat storage material microcapsule granulated product is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 15% by mass with respect to the mass of the microcapsule solid content. . When the amount is 20% by mass or more, the amount of stored heat may decrease, and when the amount is 0.1% by mass or less, the binding ability may decrease.

  Although the heat storage material microcapsule granulated product of the present invention can be used alone, it can be dispersed and mixed in fibers, resins, etc., combined with an adsorbent or a heat generating material, or filled in a packaging material. Can be used.

Utilizing the heat storage material microcapsule granulated product 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 granulated material mentioned here includes pillows, bed pads, sheets, futons, blankets, etc., using fabrics made of natural fibers or synthetic fibers alone, or inside thereof Filled with synthetic or natural materials such as cotton, urethane foam, sponge, gel cushion, buckwheat husk, plastic beads, etc. It is used by being filled or filled with the above filling. Here, by setting the strength of the heat storage material microcapsule granulated product to an appropriate range, a part of the granulated product will collapse during use or washing, and the powder falling phenomenon that does not occur will not occur. It is possible to maintain a heat storage performance with a large amount of heat and use it comfortably. In this application, when the value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granule by the projected cross-sectional area of the heat storage material microcapsule granulation is lower than 0.2 N / mm ² , the strength is insufficient. Therefore, it is not preferable because it may cause powder fall or powder at the time of use or washing, resulting in a decrease in heat storage amount or asthma. On the other hand, if the value obtained by dividing the crushing strength by the projected cross-sectional area is higher than 50 N / mm ^2, it is not preferable because there are too many binders and the heat storage amount is insufficient.

Moreover, utilization of the heat storage material microcapsule granulated product 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 granulated material referred to here is, for example, silica gel or the like as described in JP-A-2001-303032 and JP-A-2005-179458. The water-absorbing compound or the compound having the polar structure and the heat storage material microcapsule granulated product are filled alone or in a suitable packaging material, and the microwave is irradiated to generate the water-absorbing compound or the compound having the polar structure. The heat is transferred to the heat storage material microcapsule granulated product that is in direct or indirect contact, and heat storage is possible. Here, by setting the strength of the heat-storing material microcapsule granules to an appropriate range, the heat-storing material microcapsule granules can be prevented from being destroyed or deteriorated during heating or use, and the heat storage performance has a high calorific value over a long period of time. Can be maintained. In this application, when the value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granule by the projected cross-sectional area of the heat storage material microcapsule granulation is lower than 0.2 N / mm ² , It is not preferable because it is rubbed with a water-absorbing compound such as silica gel or a compound having a polar structure and powdered, and causes powdery asthma and a decrease in heat storage. On the other hand, if the value obtained by dividing the crushing strength by the projected cross-sectional area is higher than 50 N / mm ^{2, the} amount of heat storage becomes insufficient due to too much binder, which is not preferable.

Furthermore, utilization of the heat storage material microcapsule granulated material of the present invention as a building material is an example of use that can effectively exhibit the effects of the present invention. The building material using the heat storage material microcapsule granulated material here refers to concrete, cement board, gypsum board, resin board, fiber board using wood fiber, mineral fiber, synthetic resin fiber, etc. It is a mixture of capsule granulated products, and by using these for a casing, ceiling, wall, floor, etc., it becomes possible to create an environment in which the indoor temperature is hardly raised or lowered. Here, by setting the strength of the heat storage material microcapsule granulated product to an appropriate range, the heat storage material microcapsule can be prevented from being destroyed or deteriorated during molding or subsequent use, and a high heat storage performance can be obtained over a long period of time. Can be maintained. In this application, when the value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granule by the projected cross-sectional area of the heat storage material microcapsule granulation is lower than 0.2 N / mm ² , the heat storage material Since the microcapsules are not sufficiently protected, they are destroyed during molding, and the durability when repeatedly used is not preferable. Further, if the value obtained by dividing the crushing strength by the projected cross-sectional area is higher than 50 N / mm ^{2, the} amount of heat storage is insufficient due to too much binder, and the expansion of the heat storage material microcapsules accompanying the melting and solidification of the heat storage material Displacement of volume fluctuation due to shrinkage is not sufficiently absorbed, and it is not preferable because the capsule film is damaged when it is used repeatedly, and durability is lowered. The mass ratio of the heat storage material microcapsule granules in the heat storage building material is preferably set in the range of 5 to 70% by mass, and preferably 10 to 50% by mass. If it is 70% by mass or more, the strength as a building material may be poor, and if it is 5% by mass or less, the heat storage performance may be poor.

In addition, utilizing the heat storage material microcapsule granulated product of the present invention for space-filling air conditioning is an example of use that can effectively demonstrate the effects of the present invention. The space-filling type air conditioner using the heat storage material microcapsule granulated material as referred to herein is an idle space other than a living space such as a wall in a building, under a floor, or a ceiling, as described in, for example, JP-A-2001-81447. A heat storage material microcapsule granulated product is disposed and used in the space. Here, by setting the strength of the heat storage material microcapsule granules to an appropriate range, the heat storage material microcapsules are prevented from being destroyed or deteriorated during construction or subsequent use, and a high heat storage performance is achieved over a long period of time. Can be maintained. In this application, when the value obtained by dividing the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granule by the projected cross-sectional area of the heat storage material microcapsule granulation is lower than 0.2 N / mm ² , It is not preferable because it is damaged at the time of use and does not exhibit sufficient heat storage performance or causes powdering. On the other hand, if the value obtained by dividing the crushing strength by the projected cross-sectional area is higher than 50 N / mm ^{2, the} amount of heat storage becomes insufficient due to too much binder, which is not preferable.

(Example)
Hereinafter, the present invention will be described in more detail by way of examples. In addition, as long as there is no notice in particular, the number of parts and percentage in an Example are mass references | standards.
<Crushing strength>
The crushing strength was measured at a compression rate of 0.2 mm / sec using a desktop material testing machine (STA-1150, manufactured by Orientec Co., Ltd.).
<Heat history durability>
The heat storage material microcapsule granulated material is put in a thermostat capable of temperature control, and the temperature is changed from −10 ° C. to 60 ° C. as a temperature range sandwiching the phase change temperature. Measure the amount of heat stored after giving a temperature change 1000 times, and determine the ratio of the amount of heat before giving the temperature change. Thermal history durability. It shows that it is excellent in the heat retention property after giving a temperature change, so that a numerical value is large. The heat storage amount was determined by the heat of fusion measured with a differential scanning calorimeter (DSC7, manufactured by Perkin Elmer, USA).

  Preparation of heat storage material microcapsule dispersion: 100 g of sodium salt aqueous solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5 was charged with 80 g of n-octadecane having a melting point of 28 ° C. as a latent heat storage material. The mixture was added with vigorous stirring and emulsified. Next, 6 g of melamine, 12 g of 37% formaldehyde aqueous solution and 20 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 diameter of the obtained microcapsules was 1.7 μm.

  The heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder. To 100 parts by mass of the obtained heat storage material microcapsule powder, 17 parts by mass of urethane elastomer dispersion (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Superflex 200, solid content concentration 30% by mass) as a binder and an appropriate amount After adding and mixing the added water, extrusion molding is performed by an extrusion granulator, and drying is performed at 100 ° C., and a heat storage material microcapsule having a minor axis direction average diameter of 1.9 mm and a major axis direction average diameter of 5.3 mm A granulated product was obtained.

When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 3.0 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 96%.

  The heat storage material microcapsule dispersion prepared in exactly the same manner as in Example 1 was spray-dried by spray drying to obtain a heat storage material microcapsule powder. To 100 parts by mass of the obtained heat storage material microcapsule powder, 17 parts by mass of a urethane elastomer dispersion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 200, solid content concentration: 30% by mass) as a binder and an aqueous polyamide epichlorohydrin solution (Made by Sumitomo Chemical Co., Ltd., Sumires Resin 675A, solid content concentration 25% by mass) 4 parts by mass and an appropriate amount of added water were added and mixed, and then extrusion molding was performed with an extrusion granulator, 100 ° C. To obtain a heat storage material microcapsule granulated product having a minor axis direction average diameter of 1.9 mm and a major axis direction average diameter of 5.3 mm.

When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 12.5 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 91%.

  Preparation of heat storage material microcapsule dispersion: Into 100 g of sodium salt aqueous solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5, 80 g of paraffin wax having a melting point of 52 ° C. was vigorously added as a latent heat storage material. The mixture was added with stirring and emulsified. Next, 8 g of melamine, 12 g of 37% aqueous formaldehyde solution and 20 g of water were mixed, adjusted to pH 8, and an aqueous solution of melamine-formalin initial condensate 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 diameter of the obtained microcapsules was 2.7 μm.

  The heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder. 10 parts by mass of an aqueous urethane dispersion (manufactured by Dainippon Ink & Chemicals, Ltd., Hydran HW-920, solid content concentration 50% by mass) as a binder is appropriately added to 100 parts by mass of the obtained heat storage material microcapsule powder. After adding an amount of added water and mixing, extrusion molding is performed with an extrusion granulator and dried at 100 ° C., and the heat storage material has a minor axis direction average diameter of 2.1 mm and a major axis direction average diameter of 4.2 mm. A microcapsule granulated product was obtained.

When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 3.6 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 96%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. Heat storage material microcapsule granulation in the same manner as in Example 3 except that 100 parts by weight of the obtained heat storage material microcapsule powder was changed to 2 parts by weight of the aqueous urethane dispersion as a binder. I got a thing. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.8 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 94%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. Other than using 2 parts by mass of polyamide epichlorohydrin aqueous solution (Sumitomo Chemical Co., Ltd., Sumire's Resin 675A, solid content concentration 25% by mass) as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder. Was similar to Example 3 to obtain a heat storage material microcapsule granulated product. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 1.7 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 95%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. With respect to 100 parts by mass of the obtained heat storage material microcapsule powder, 2 parts by mass of a polyamide epichlorohydrin aqueous solution (manufactured by Sumitomo Chemical Co., Ltd., Sumires Resin 675A, solid content concentration 25% by mass) as a binder and aqueous urethane dispersion A heat storage material microcapsule granulated product was obtained in the same manner as in Example 3 except that 10 parts by mass of liquid (Dainippon Ink and Chemicals, Hydran HW-920, solid content concentration 50% by mass) was used. . When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area of the heat storage material microcapsule granulation was 8.2 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 96%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. Heat storage material microcapsule granulation in the same manner as in Example 3 except that the amount of aqueous urethane dispersion added as a binder was 20 parts by weight with respect to 100 parts by weight of the obtained heat storage material microcapsule powder. I got a thing. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 15 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 90%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. In the same manner as in Example 3, except that 5 parts by mass of a carboxymethyl cellulose aqueous solution (solid content concentration: 10% by mass) was used as a binder with respect to 100 parts by mass of the obtained heat storage material microcapsule powder. Capsule granules were obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.3 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 92%.

The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. Implemented except that 100 parts by mass of polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., PVA-235, solid content concentration 20% by mass) was used as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder. In the same manner as in Example 3, a heat storage material microcapsule granulated product was obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 34 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 85%.

  Preparation of heat storage material microcapsule dispersion liquid: 100 g of sodium salt aqueous solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5 was charged with 80 g of n-heptadecane having a melting point of 22 ° C. as a latent heat storage material. The mixture was added with vigorous stirring and emulsified. Next, 8 g of melamine, 16 g of 37% formaldehyde aqueous solution and 30 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 diameter of the obtained microcapsules was 1.7 μm.

  The heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder. To 100 parts by mass of the obtained heat storage material microcapsule powder, 25 parts by mass of polysiloxane acrylic graft polymer dispersion (manufactured by Nippon Shokubai Co., Ltd., GF255, solid content concentration 40% by mass) and an appropriate amount are added. After adding water and mixing, extrusion molding is performed by an extrusion granulator, and drying is performed at 100 ° C., and a heat storage material microcapsule having a minor axis direction average diameter of 1.1 mm and a major axis direction average diameter of 2.3 mm is manufactured. Grains were obtained.

When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area of the heat storage material microcapsule granulation was 5.1 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 95%.

  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, polycyclohexyl isocyanate, dicyclohexylmethane 4,4-diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., aliphatic isocyanate, trade name) Desmodur W) 14g dissolved in 5% polyvinyl alcohol (Kuraray Co., Ltd., trade name POVAL PVA-117) in 100g aqueous solution, stirred and emulsified at room temperature until the average particle size becomes 1.6μm Went. Next, 55 g of a 3% aqueous polyether solution (manufactured by Asahi Denka Kogyo Co., Ltd., polyether, trade name Adeka Polyether EDP-450) was added to the emulsion, and the mixture was heated and stirred at 60 ° C. A heat storage material microcapsule dispersion having low viscosity and good dispersion stability was obtained. The volume average particle diameter of the obtained microcapsules was 1.7 μm.

  The heat storage material microcapsule dispersion was spray-dried by spray drying to obtain a heat storage material microcapsule powder. To 100 parts by mass of the obtained heat storage material microcapsule powder, 8 parts by mass of SBR latex (manufactured by JSR Co., Ltd., 0640, solid content concentration 40% by mass) and an appropriate amount of added water were added and mixed. Then, extrusion molding was performed with an extrusion granulator and dried at 100 ° C. to obtain a heat storage material microcapsule granulated product having a minor axis direction average diameter of 2.0 mm and a major axis direction average diameter of 4.5 mm.

When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 1.5 N / mm ² . Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 93%.

(Comparative Example 1)
The heat storage material microcapsule powder was obtained in the same manner as in Example 1 until the heat storage material microcapsule powder was obtained. In the same manner as in Example 1, except that 2 parts by mass of an aqueous carboxymethyl cellulose solution (solid content concentration: 10% by mass) was used as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder, Grains were obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.08 N / mm ² , and the strength was inferior. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 87%.

(Comparative Example 2)
The heat storage material microcapsule powder was obtained in the same manner as in Example 1 until the heat storage material microcapsule powder was obtained. Example 1 except that 100 parts by mass of the obtained heat storage material microcapsule powder was used as a binder, 100 parts by mass of a polyvinyl alcohol aqueous solution (manufactured by Kuraray Co., Ltd., PVA-235, solid content concentration: 30% by mass). In the same manner, a heat storage material microcapsule granulated product was obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 65 N / mm ² , and the strength was excessive. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 76%, resulting in poor heat history durability.

(Comparative Example 3)
The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. In the same manner as in Example 3, except that 2 parts by mass of an aqueous carboxymethyl cellulose solution (solid content concentration: 10% by mass) was used as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder. Grains were obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.1 N / mm ² , and the strength was inferior. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 88%.

(Comparative Example 4)
The heat storage material microcapsule powder was obtained in the same manner as in Example 3 until the heat storage material microcapsule powder was obtained. Example 3 except that 100 parts by mass of the obtained heat storage material microcapsule powder was used as a binder, 100 parts by mass of an aqueous polyvinyl alcohol solution (manufactured by Kuraray Co., Ltd., PVA-235, solid content concentration: 30% by mass). In the same manner, a heat storage material microcapsule granulated product was obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 76 N / mm ² , and the strength was excessive. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 73%, resulting in poor heat history durability.

(Comparative Example 5)
The heat storage material microcapsule powder was obtained in the same manner as in Example 10 until the heat storage material microcapsule powder was obtained. In the same manner as in Example 10, except that 2 parts by mass of an aqueous carboxymethyl cellulose solution (solid content concentration: 10% by mass) was used as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder, Grains were obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.13 N / mm ² , and the strength was inferior. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 89%.

(Comparative Example 6)
The heat storage material microcapsule powder was obtained in the same manner as in Example 10 until the heat storage material microcapsule powder was obtained. Example 10 except that 100 parts by mass of the obtained heat storage material microcapsule powder was used as a binder, 100 parts by mass of an aqueous polyvinyl alcohol solution (manufactured by Kuraray Co., Ltd., PVA-235, solid content concentration: 30% by mass). In the same manner, a heat storage material microcapsule granulated product was obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 82 N / mm ² , and the strength was excessive. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 72%, resulting in poor heat history durability.

(Comparative Example 7)
The heat storage material microcapsule powder was obtained by the same operation as in Example 11 until the heat storage material microcapsule powder was obtained. In the same manner as in Example 11, except that 2 parts by mass of a carboxymethyl cellulose aqueous solution (solid content concentration: 10% by mass) was used as a binder for 100 parts by mass of the obtained heat storage material microcapsule powder, Grains were obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 0.17 N / mm ² , and the strength was inferior. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 86%.

(Comparative Example 8)
The heat storage material microcapsule powder was obtained by the same operation as in Example 11 until the heat storage material microcapsule powder was obtained. Example 11 except that 100 parts by mass of the obtained heat storage material microcapsule powder was used as a binder, 100 parts by mass of an aqueous polyvinyl alcohol solution (manufactured by Kuraray Co., Ltd., PVA-235, solid content concentration: 30% by mass). In the same manner, a heat storage material microcapsule granulated product was obtained. When the crushing strength of the obtained heat storage material microcapsule granule was measured, the value obtained by dividing the crushing strength by the projected sectional area in the compression direction of the heat storage material microcapsule granulation was 91 N / mm ² , and the strength was excessive. As a result. Moreover, the heat history durability of the obtained heat storage material microcapsule granulated product was 67%, resulting in poor heat history durability.

<Evaluation A> Evaluation in bedding Using the heat storage material microcapsule granules obtained in Examples 1 and 2 and Comparative Examples 1 and 2, respectively, 100 parts by mass of the heat storage material microcapsule granules and 100 parts by weight of buckwheat husk Then, the cotton fabric was filled into a bag having a length of 40 cm and a width of 60 cm, and pillows having heat storage properties were obtained. These pillows were evaluated for the experience during use after being left in a room at room temperature of 25 ° C. for 6 hours.

  When the heat storage material microcapsule granulated product of Example 1 according to the present invention is used, a comfortable cooling feeling lasts for 1 hour, and even if this pillow is struck 1000 times with a rubber spherical body weighing 10 kg, The phenomenon that the heat storage material microcapsule granulated material collapses and was pulverized was not observed, and the pillow had excellent heat storage properties.

  In addition, when the heat storage material microcapsule granulated product of Example 2 which is the present invention is used, a comfortable cooling feeling lasts for 1 hour, and this pillow is struck 1000 times with a rubber spherical body weighing 10 kg. However, the phenomenon that the heat storage material microcapsule granulated material collapses and was pulverized was not observed, and the pillow had excellent heat storage properties.

  On the other hand, when the heat storage material microcapsule granulated product of Comparative Example 1 which is outside the present invention was used, although a comfortable cooling sensation lasted for 1 hour, this pillow was struck 1000 times with a rubber spherical body weighing 10 kg. As a result, a part of the heat storage material microcapsule granulated material collapsed and pulverized, and the pulverized product was seen to fall to the outside of the pillow. It was gradually damaged.

  Moreover, when the heat storage material microcapsule granulated product of Comparative Example 2 which is outside the present invention was used, the comfortable cooling feeling lasted only 30 minutes, and the heat storage performance was inferior.

<Evaluation B> Evaluation in microwave irradiation type heat insulating material Using each of the heat storage material microcapsule granules obtained in Examples 3 to 9 and Comparative Examples 3 and 4, 30 parts by mass of the heat storage material microcapsule granules and The mixture was mixed with 70 parts by mass of silica gel particles having a particle diameter of 2 mm, and 500 g was filled in a cotton bag to obtain microwave irradiation type heat insulating materials. These thermal insulation materials were heated for 2 minutes using a household microwave oven (high-frequency output = 500 W), and the temperature sensation when they were taken out from the microwave oven and used was observed.

  When the heat storage material microcapsule granulated product of Example 3 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 70 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  When the heat storage material microcapsule granulated product of Example 4 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 73 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  When the heat storage material microcapsule granulated product of Example 5 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 72 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  When the heat storage material microcapsule granulated product of Example 6 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 66 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  When the heat storage material microcapsule granulated product of Example 7 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 60 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  When the heat storage material microcapsule granulated product of Example 8 according to the present invention was used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasted for 75 minutes, and a heat insulating material that maintained warmth for a long time was obtained. . Moreover, when this operation was repeated 100 times, a phenomenon that the heat storage material microcapsule granulated material collapsed and was pulverized was slightly seen, but there was no change in the time for maintaining the temperature of 43 ° C. or higher. .

  When the heat storage material microcapsule granulated product of Example 9 according to the present invention is used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasts for 50 minutes, and a heat insulating material that maintains warmth for a relatively long time is obtained. It was. Further, even when this operation was repeated 100 times, the phenomenon of the heat storage material microcapsule granulated material collapsing and pulverizing was not observed, and no change occurred in the time for maintaining the temperature of 43 ° C. or higher.

  On the other hand, when the heat storage material microcapsule granulated product of Comparative Example 3 that is outside the present invention is used, a temperature of 43 ° C. or more, which is a comfortable temperature range, lasts for 76 minutes, and the heat retaining material that maintains warmth for a long time is Obtained. However, when this operation was repeated 100 times, a part of the heat storage material microcapsule granulated material collapsed and pulverized, and a phenomenon in which the pulverized material pulverized to the outside of the bag was observed. As the powder fluttered, the time for maintaining the temperature of 43 ° C. or higher was gradually shortened, and the heat storage property gradually deteriorated.

  Moreover, when the heat storage material microcapsule granulated product of Comparative Example 4 which is outside the present invention was used, a comfortable temperature range of 43 ° C. or higher lasted only for 30 minutes, resulting in poor heat storage performance. .

<Evaluation C> Evaluation on wooden board Using the heat storage material microcapsule granulated product obtained in Example 10 and Comparative Examples 5 and 6, respectively, 25 parts by mass of the heat storage material microcapsule granulated product and a major axis of 3 mm as a filling material After thoroughly mixing 75 parts by mass of the following wood powder and 30 parts by mass of an initial condensate aqueous solution of urea formalin having a concentration of 30% by mass, pressure and heat molding are performed under conditions of a pressure of 3 MPa and a temperature of 160 ° C. Wood boards having a heat storage property of 5 mm in thickness on each side were obtained.

  When the heat storage material microcapsule granulated product of Example 10 according to the present invention was used, the obtained wooden board had sufficient strength as a building material. A cubic box was made by combining six wooden boards. After putting the cubic box in a large constant temperature chamber and leaving it in the chamber chamber temperature of 15 ° C. for 6 hours, switching the chamber chamber temperature to 30 ° C., the air temperature inside the cubic box inside is 25 ° C. or less. It could be maintained for 3 hours. Further, 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 within a relatively narrow range of 17 to 28 ° C. The thermal storage performance was excellent, and excellent heat storage performance was confirmed. Furthermore, even when this operation was repeated 100 times, the heat storage component did not ooze out from the heat storage material microcapsule granulated product, and no change occurred in the air temperature fluctuation range in the central portion of the box.

  On the other hand, when the heat storage material microcapsule granulated product of Comparative Example 5 which is outside the present invention is used, when the obtained wooden board is observed, the heat storage material microcapsule granulated product partially collapses and the collapsed material However, it was localized on one side of the wooden board, and the wooden board did not have sufficient strength as a building material. A cube-shaped box was prepared by combining six wooden boards, and the cubic box was placed in a large constant temperature chamber and allowed to stand at a chamber temperature of 15 ° C. for 6 hours, and then the chamber temperature was switched to 30 ° C. However, the air temperature inside the cubic box was maintained at 25 ° C. or lower for 3 hours. However, when the operation of switching the internal temperature of the large temperature chamber alternately between 10 ° C. and 35 ° C. every 2 hours is repeated 100 times, the heat storage component oozes out from the granule of the heat storage material into the wooden board. As a result, heat storage performance gradually decreased.

  When the heat storage material microcapsule granulated product of Comparative Example 6 which is outside the present invention was used, the obtained wood board did not have sufficient strength as a building material. However, six wooden boards are combined to produce a cubic box, the cubic box is placed in a large constant temperature chamber and left at a chamber temperature of 15 ° C. for 6 hours, and then the chamber temperature is set to 30 ° C. As a result, the air temperature in the central part inside the cubic box could only be maintained at 25 ° C. or lower for 1 hour and a half, resulting in poor heat storage performance. In addition, when the operation of alternately switching the internal temperature of the large constant temperature chamber between 10 ° C. and 35 ° C. every 2 hours was repeated 10 times, the air temperature in the central portion of the box was in a relatively wide range of 13-30 ° C. As a result, the heat storage performance was inferior.

<Evaluation D> Evaluation in space-filling type air conditioning A heat insulating plate sandwiched between 20 mm thick glass wool and 10 mm thick wood is processed to produce a cubic space of 1 m on each side, and further 15 cm above the inner floor surface. A heat insulating plate of 80 cm square was made of the same material so that a 10 cm gap was left from each wall surface, and a three-dimensional space having a double floor structure was produced. While using the heat storage material microcapsule granules obtained in Example 11 and Comparative Examples 7 and 8, respectively, 3 kg of the heat storage material microcapsule granules are spread on the lower floor surface of the three-dimensional space of the double floor structure. A small air supply fan was installed in the center of the underfloor space. Next, while operating the installed small air supply fan, the central portion of the space in the box when the ambient temperature around these three-dimensional space boxes is raised or lowered at a rate of 1 ° C./min between 0 to 40 ° C. Each air temperature was measured.

  When the heat storage material microcapsule granulated product of Example 11 according to the present invention was used, the air temperature in the box space changed only in the range of 15 to 28 ° C., and was maintained within the so-called comfortable temperature range. Also, no powder was seen.

  On the other hand, when the heat storage material microcapsule granulated product of Comparative Example 7 that is outside the present invention was used, the air temperature in the space in the box changed in the range of 13 to 29 ° C, but the heat storage material microcapsule granulated product Partly disintegrated pulverized material was blown away by the air supply fan, causing a phenomenon that the upper floor surface was contaminated with the pulverized material, resulting in an undesirable result.

  When the heat storage material microcapsule granulated product of Comparative Example 8 that is outside the present invention is used, the air temperature in the box space fluctuates so as to be greatly influenced by the range of 7 to 34 ° C. and the external environmental temperature, The heat storage performance was inferior.

As is clear from the above, in the heat storage material microcapsule granulated product in which a plurality of heat storage material microcapsules encapsulating the heat storage material are fixed together with the binder, the heat storage material microcapsule granulated product according to JIS Z 8841 the divided by the projected cross-sectional area of the measured compressive strength accumulating Netsuzai microcapsule granules, by a range of 0.2~50N / mm ^2, accumulating Netsuzai microcapsules granulation is moderate strength Even if the heat storage material microcapsule granulated filler or processed material is used in an environment where external force is applied, the heat storage effect will not be reduced and the performance that can be used over a long period of time will be maintained. Became possible.

  The heat storage material microcapsule granulated product according to the present invention includes pillows, bed pads, sheets, futons, blankets, etc., heat insulation materials that heat and store heat by microwave irradiation, building materials such as ceilings, walls, floors, etc. In addition to frame heat storage and space-filling air conditioning, fabric processed materials such as clothing materials, overheating and / or supercooling suppression materials such as electronic parts and gas adsorbents, floor heating, air conditioning applications, civil engineering such as roads and bridges It can be applied to various fields of use, such as materials for use, waste heat utilization equipment such as fuel cells and incinerators, hot water heat storage applications, industrial heat insulation materials, agricultural heat insulation materials, household goods, health supplies, and medical materials.

Claims (4)

In a heat storage material microcapsule granulated product in which a plurality of heat storage material microcapsules encapsulating the heat storage material are fixed together with a binder, the crushing strength measured by JIS Z 8841 of the heat storage material microcapsule granulation product is measured. A heat storage material microcapsule granulated product, wherein the value obtained by dividing the capsule granulated product by the projected cross-sectional area is in the range of 0.2 to 50 N / mm ² .   The heat storage material microcapsule granulated product according to claim 1, wherein the addition ratio of the binder in the heat storage material microcapsule granulated product is in the range of 0.1 to 20% by mass.   The heat storage material microcapsule granulated product according to claim 1 or 2, wherein the heat storage material microcapsule granulated product has a minor axis direction average diameter of 0.1 to 100 mm.   The heat storage material microcapsule granulated product according to any one of claims 1 to 3, wherein the binder is a polyamide epihalohydrin resin.