JP2006176761A - Microcapsule solid material including thermal storage material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microcapsule solid material including a thermal storage material which can be used without reducing a thermal storage effect even when used under a certain condition of water and humidity or used under the exposure to organic solvents, in a microcapsule solid material including a thermal storage material. <P>SOLUTION: By obtaining the solid material having the microcapsule including a latent heat storage material and a self-crosslinking resin having a cationic group, the microcapsule solid material including the thermal storage material whose thermal storage effect does not decrease even under a certain condition of the water and the humidity or under the exposure to organic solvents can be provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a microcapsule solid containing a heat storage material.

  A method of storing heat by using latent heat accompanying the phase change of a material 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.

  There has been proposed a method of microcapsulating a latent heat storage material that stores heat using latent heat associated with a phase change of a substance. By microencapsulation, leakage of the heat storage material caused by phase change can be prevented. 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-mentioned microencapsulation method is obtained in a state where microcapsules are dispersed in a medium. 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, the heat storage material microcapsule solid can be used in a wider range of applications.

However, if the microcapsules are solidified as they are, the water resistance is low, the microcapsules flow out, and the heat storage performance is lowered, so that it is difficult to use under conditions with water and humidity. Binders are used for the purpose of improving the strength of solids, but generally used binders are polyvinyl alcohol, acrylic latex, styrene-butadiene latex, etc. The capsules flowed out and the heat storage performance was lowered, so that it was difficult to use under conditions with water and humidity. Furthermore, the solvent resistance against various organic solvents such as a cleaning solvent is not sufficient (see, for example, Patent Document 5).
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 2001-81447 A

  In the present invention, in a solid body of a microcapsule containing a latent heat storage material, heat storage that can be used without reducing the heat storage effect even when used under conditions where water or humidity is present or exposed to an organic solvent. A material microcapsule solid is provided.

  As a result of investigations to solve the above-mentioned problems, it is possible to obtain a solid substance containing a microcapsule enclosing a latent heat storage material and a self-crosslinking resin having a cationic group, under conditions of water or humidity, or organic It has been found that a heat storage material microcapsule solid that does not reduce the heat storage effect even when used under conditions exposed to a solvent can be provided. The heat storage material microcapsule solid may further contain a binder in order to enhance the binding ability.

  According to the present invention, the water resistance and solvent resistance of the solid matter of the microcapsule encapsulating the heat storage material can be improved, and further, the filling of the heat storage material microcapsule solid and the heat storage material microcapsule solid can be used as a resin. In addition, it has become possible to provide products that do not reduce heat storage performance even when products such as fibers and members processed and applied to building materials are used under conditions with water, humidity, and organic solvents (including solvent vapor).

  The latent heat storage material included in the microcapsule used in the present invention is used for the purpose of storing heat using latent heat accompanying the 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 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 heat storage materials having different melting points.

  As a method for producing a microcapsule according to 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. 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 of producing a polyamide-coated microcapsule by interfacial polycondensation reaction (Japanese Patent Laid-Open No. 2-258052), and the like. The method is used.

  As a membrane material of the microcapsule, polystyrene, acrylic resin, polyacrylonitrile, polyamide, polyacrylamide, ethyl cellulose, polyurethanes, polyurea, amino resin, or the like obtained by a method such as an interfacial polymerization method, an in-situ method, or the like A synthetic or natural resin using a coacervation method of gelatin and carboxymethyl cellulose or gum arabic is used. Melamine formalin resin film by physically and chemically stable in situ method, microcapsule using urea formalin resin film, or polyurethane resin film, polyurethane urea resin film, microcapsule using polyurea resin film by interfacial polymerization method It is particularly preferred to use it.

  The solid material of the heat storage material microcapsule of the present invention is characterized by containing at least a microcapsule containing the latent heat storage material and a cationic and self-crosslinking resin. Since the resin has a cationic property, it is considered that the resin can be efficiently arranged on the surface of an anionic microcapsule and can exhibit an effect. In addition, since it has self-crosslinkability, not only water resistance is imparted, but also resin components and heat storage material components for organic solvents such as petroleum solvents and alcohols used for dry cleaning, for example. A solid having solvent resistance that is not eluted or extracted can be obtained, and a solid having sufficient mechanical strength can be obtained with a small addition amount.

  The cationic and self-crosslinking resin according to the present invention refers to a resin that has a cationic site in the resin and becomes a water-insoluble resin when heated alone. Specific examples include methylolated melamine resins and polyamide epihalohydrin resins.

  Methylolated melamine resin can provide excellent water resistance and solvent resistance, but formaldehyde which is harmful to human body may be diffused, so polyamide epihalohydrin resin is particularly suitable as a more suitable one Of these, polyamide epichlorohydrin resin is used. The molecular weight of these resins is not particularly limited, and any resin that exhibits water solubility before crosslinking can be used.

  The cationic and self-crosslinking resin is preferably added in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the microcapsules. If the amount is less than 0.1 parts by mass, sufficient water resistance and solvent resistance may not be obtained. If the amount exceeds 20 parts by mass, the amount of heat per unit mass may decrease.

  As a method of obtaining the heat storage material microcapsule solid matter of the present invention, the microcapsule dispersion liquid usually produced in the state of an aqueous dispersion is used as a drying apparatus and a dehydrating apparatus such as a spray dryer, a drum dryer, a freeze dryer, and a filter press. Can be used to evaporate, dehydrate and dry the medium water to form a powder or solid. As a preferable drying method, there is a spray dryer because there is little destruction of the microcapsules. Various granulations such as extrusion granulation, tumbling granulation, stirring granulation, etc. after making powder or solid state with the above apparatus or adding a thickener or dehydrating agent to the microcapsule dispersion It is also possible to increase the particle size by granulating using the method, and to make the granulated body easy to handle. In the present invention, these powders, solid bodies, and granulated bodies are collectively referred to as solid bodies.

  When obtaining a powder or solid, a cationic and self-crosslinking resin is added to the microcapsule dispersion and dried and dehydrated. When obtaining a granulated product, add a cationic and self-crosslinking resin to a powder or solid obtained with or without the addition of a cationic and self-crosslinking resin. Granulate. Alternatively, a powder or solid obtained by adding a cationic and self-crosslinking resin is granulated (a cationic and self-crosslinking resin may or may not be added at the time of granulation. ). Furthermore, various binders, antioxidants, VOC adsorbents, activated carbon, photocatalysts, organic or inorganic pigments, incombustible materials, and flame retardant powders can be added during drying or granulation. 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, a cylinder, and the size is not limited.

  Various binders may be added to the heat storage material microcapsule solid of the present invention. These various binders are components that have the effect of further increasing the cohesive force, binding force, and strength between the microcapsules. As the binder used in the present invention, any binder can be used as long as it does not inhibit the reaction of the cationic and self-crosslinking resin. Any of these binders can be used alone or in combination of two or more. As specific examples, conventionally known natural polymers, natural polymer modified products (semi-synthetic products), synthetic polymers and inorganic compounds having binding ability and film forming ability 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 Ene copolymers, methyl butadiene acrylate copolymer, latexes such as ethylene-vinyl acetate copolymer, polyurethane elastomer dispersions, polysiloxane acrylic graft polymer dispersions, silicone-based polymers, thermoplastic elastomers, and the like.

  These binders alone cannot exhibit sufficient water resistance and solvent resistance, but they can ensure sufficient water resistance and solvent resistance when used together with a cationic and self-crosslinking resin. it can. The amount of these binders added is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the microcapsules. If the amount is less than 0.1 parts by mass, sufficient binding ability may not be obtained, and if it exceeds 20 parts by mass, the amount of heat per unit mass may decrease. The compounding ratio of the binder to the cationic and self-crosslinking resin is preferably in the range of 0.5 / 99.5 to 99.5 / 0.5 in parts by mass.

  As a method of blending these binders, when obtaining powders and solids, 1) powders and solids are obtained by adding a binder to the microcapsule dispersion together with a cationic and self-crosslinking resin. Method 2) A method in which only a cationic and self-crosslinking resin is added to the microcapsule dispersion to form a powder or solid, and then a binder is applied by surface coating or the like. 3) The microcapsule dispersion Examples thereof include a method in which only a binder is added to form a powder or a solid and then a cationic and self-crosslinking resin is later applied by surface coating or the like. In addition, when obtaining a granulated body, 4) a method of obtaining a granulated body by adding a binder to the powder or solid body together with a cationic and self-crosslinking resin, and 5) to the powder or solid body. A method in which only a cationic and self-crosslinking resin is added to form a granulated product, and then a binder is applied by surface coating, etc. 6) Granulation by adding only the binder to a powder or solid A method of post-applying a cationic and self-crosslinking resin by surface coating after forming into a body, 7) adding a binder to a powder or solid containing a cationic and self-crosslinking resin 8) A method in which a powder or solid containing a cationic and self-crosslinking resin is used to form a granulated material, and then a binder is applied by surface coating or the like. Can be mentioned. Of the above methods, the cationic and self-crosslinking resin is not buried in the heat storage material microcapsule solid material, and is easily present on the surface or in the vicinity thereof 1), 3), 4 ) And 6) are particularly preferred.

  The volume average particle size of the microcapsules according to the present invention is preferably 10 μm or less, more preferably in the range of 0.5 to 5 μm. If the particle diameter is smaller than 0.5 μm, emulsification by physical strong stirring requires an extremely long time or a high temperature, which is not industrially advantageous. On the other hand, if the particle diameter is larger than 10 μm, it is difficult to maintain the strength against physical pressure. 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.

  The particle size of the microcapsule is the type and concentration of the emulsifier used at the time of capsule preparation, the temperature of the emulsion during emulsification, the emulsification ratio (volume ratio of water phase to oil phase), atomization called emulsifier, disperser, etc. The operation conditions (stirring speed, time, etc.) of the apparatus are adjusted as appropriate to set the desired particle size.

  The heat storage material microcapsule solid material of the present invention can be used alone, but is dispersed and mixed in fibers, resins, inorganic materials, etc., combined with an adsorbent and a heating material, It is also possible to use it by filling it. Due to the improved water resistance, the microcapsules do not flow out due to sweat or moisture and can be washed. In addition, since the solvent resistance is improved, the elution / extraction of the resin component and the heat storage material component due to the liquid or vapor of the organic solvent is suppressed. It becomes possible to disperse and mix in a resin or an inorganic material, and also develops durability in applications exposed to an organic solvent such as dry cleaning and organic solvent gas adsorption.

  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 that is in direct or indirect contact, thereby enabling heat storage. Heat storage material microcapsule solids containing a cationic and self-crosslinking resin give water resistance, water vapor released from a compound having a polar structure during heat storage or heat dissipation, or touch during use Even if sweat from the human body comes into contact with the heat storage material microcapsule solids, the heat storage material microcapsule solids are prevented from flowing out or falling off, maintaining high heat storage performance over a long period of time. It becomes possible.

  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 natural fibers or synthetic fibers alone, or cotton inside. , Filled with synthetic or natural materials such as wool, feathers, urethane foam, sponge, gel cushion material, buckwheat husk, 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 solids containing a cationic and self-crosslinking resin give water resistance and solvent resistance, sweat from the human body touched during use, water during washing, dry cleaning Even if the solvent at the time comes into contact with the heat storage material microcapsule solids, the outflow and dropout of the heat storage material microcapsules from the heat storage material microcapsule solids and the elution / extraction of the resin component and the heat storage material component are suppressed. It is possible to maintain a high heat storage performance over a wide range.

  Utilization of the heat storage material microcapsule solid of the present invention as a building material is an example of use that can effectively exhibit the effects of the present invention. Heat storage material microcapsule building material that uses solid material here refers to concrete, cement board, gypsum board, resin board, fiber board using wood fiber, mineral fiber, synthetic resin fiber, etc. Solids are mixed and coated. By using these for the frame, ceiling, wall, floor, etc., it becomes possible to create an environment in which the indoor temperature is hardly raised or lowered. Moreover, it can also be used as a heating and / or cooling system in combination with a heater or a cooler. By making the heat-storing material microcapsule solid containing a resin that is cationic and self-crosslinkable, water resistance is imparted, and moisture added when building materials are produced and absorbed into building materials when building materials are used Even if moisture from the moisture in the air contacts the heat storage material microcapsule solids, the heat storage material microcapsules from the solids of the heat storage material microcapsules are prevented from flowing out or falling off, and high heat storage at the initial stage It is possible to ensure performance and maintain a long-term heat storage performance with a high calorific value.

  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 solids containing a cationic and self-crosslinking resin give water resistance and solvent resistance, moisture in air and gas, petroleum gas, acid gas, basic Even if a gas such as gas or organic solvent gas comes into contact with the heat storage material microcapsule solid, the heat storage material microcapsule flows out or drops from the heat storage material microcapsule solid, and the resin component or heat storage material component is eluted or extracted. Is suppressed, and it is possible to maintain a high heat storage performance over a long period of time.

(Example)
Hereafter, the implementation procedure of this invention is demonstrated concretely as an Example. In addition, as long as there is no notice in particular, the number of parts and percentage in an Example are mass references | standards. The amount of heat stored was determined by the amount of heat of fusion measured with a differential scanning calorimeter (Perkin Elmer, DSC7, USA).
<water resistant>
1 part by mass of heat storage material microcapsule solids was added to 100 parts by mass of warm water at 40 ° C., and after 30 minutes of stirring, filtration was performed, and the remaining unfiltered while maintaining the form was added to warm water having a dry mass. The rate of decrease from the mass of the solid was evaluated as the loss on washing. The smaller the value, the better the water resistance. A heat storage material microcapsule solid that has a loss on washing of 10% or less is preferred.
<Solvent extraction rate>
After 1 g of heat storage material microcapsule solids are extracted by shaking with 50 mL of n-hexane for 5 minutes, the hexane phase is measured by gas chromatography, and the amount of the detected heat storage agent component is charged into the heat storage material microcapsule solids. The value divided by the amount was evaluated as the solvent extraction rate (percentage). The smaller the solvent extraction rate, the better the solvent resistance.

  Production of microcapsule dispersion: 100 parts by mass of a sodium salt aqueous solution of 5% by mass of styrene-maleic anhydride copolymer adjusted to pH 4.5, 80 parts of paraffin wax having a melting point of 25 ° C. as a latent heat storage material The portion was added with vigorous stirring to effect emulsification. Next, 6 parts by mass of melamine, 9 parts by mass of 37% formaldehyde aqueous solution and 15 parts by mass of water were mixed, adjusted to pH 8, and a melamine-formalin initial condensate aqueous solution was prepared at about 80 ° C. The entire amount was added to the emulsion and encapsulated by heating and stirring at 70 ° C. for 2 hours. Next, the pH of this dispersion was adjusted to 9 to complete the encapsulation, and a microcapsule dispersion was obtained. The volume average particle diameter of the obtained microcapsules was 2 μm.

  Preparation of heat storage material microcapsule solid: 25% by mass aqueous solution of polyamide epichlorohydrin (Sumirez resin 675, manufactured by Sumitomo Chemical Co., Ltd.) as a cationic and self-crosslinking resin to the microcapsule dispersion obtained above. 2 parts by mass were added to 100 parts by mass of the microcapsule dispersion (the amount of polyamide epichlorohydrin solid added relative to 100 parts of microcapsule solids was 1.2 parts). Spray drying was performed by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 134 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 5%, and the solvent extraction rate was 0.3%.

  Preparation of heat storage material microcapsule solid: The microcapsule dispersion prepared in the same manner as in Example 1 was spray-dried by spray drying to obtain a powdered heat storage material microcapsule solid. As a cationic and self-crosslinking resin, a 25% by mass aqueous solution of polyamide epichlorohydrin (Sumirays Resin 675, manufactured by Sumitomo Chemical Co., Ltd.) is used, and 4 parts by mass is added to 100 parts by mass of the heat storage material microcapsule solid. (The amount of polyamide epichlorohydrin solid added relative to 100 parts of microcapsule solid is 1 part). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The obtained heat storage material microcapsule solid had a heat of fusion of 135 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.2%.

  Production of microcapsule dispersion: 80 parts by mass of paraffin wax having a melting point of 25 ° C. as a latent heat storage material and 5 parts by mass of isophorone diisocyanate as polyisocyanate were mixed at room temperature to prepare an oil phase mixture. This oil phase mixture was put into 100 parts by mass of a 5% by mass aqueous solution of polyvinyl alcohol, and emulsified with an emulsifier for 30 minutes. To the obtained emulsion, 40 parts by mass of a 5% by mass aqueous solution of diethylenetriamine was added as an active hydrogen compound, and the mixture was stirred at 80 ° C. for 3 hours for encapsulation to obtain a microcapsule dispersion. The volume average particle size of the obtained microcapsules was 3 μm.

  Preparation of heat storage material microcapsule solid: 25% by mass aqueous solution of polyamide epichlorohydrin (Sumirez resin 675, manufactured by Sumitomo Chemical Co., Ltd.) as a cationic and self-crosslinking resin to the microcapsule dispersion obtained above. 4 parts by mass was added to 100 parts by mass of the microcapsule dispersion (the amount of polyamide epichlorohydrin added relative to 100 parts of microcapsule solids was 2.3 parts). Spray drying was performed by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 5%, and the solvent extraction rate was 0.3%.

  Preparation of heat storage material microcapsule solid: The microcapsule dispersion prepared in the same manner as in Example 3 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. As a cationic and self-crosslinking resin, a 25% by mass aqueous solution of polyamide epichlorohydrin (Sumirays Resin 675, manufactured by Sumitomo Chemical Co., Ltd.) is used, and 4 parts by mass is added to 100 parts by mass of the heat storage material microcapsule solid. (The amount of polyamide epichlorohydrin solid added relative to 100 parts of microcapsule solid is 1 part). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 138 J / g. The heat loss of the obtained heat storage material microcapsule solids was 2%, and the solvent extraction rate was 0.2%.

  Production of heat storage material microcapsule solid: A microcapsule dispersion produced in the same manner as in Example 1, using a 25% by weight aqueous solution of polyamide epichlorohydrin (Smirez resin 675) as a resin having cationic and self-crosslinking properties, 2 parts by mass are added to 100 parts by mass of the capsule dispersion (the amount of polyamide epichlorohydrin solid added to 100 parts of microcapsule solids is 1.2 parts), and polyvinyl alcohol as a binder (Corporation) 5 parts by mass of a 20% by mass aqueous solution of Kuraray, PVA217) was added to 100 parts by mass of the microcapsule dispersion (the amount of binder solid added to 100 parts of microcapsule solids was 2.4 parts) . Spray drying was performed by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 131 J / g. The heat loss of the obtained heat storage material microcapsule solids was 5%, and the solvent extraction rate was 0.2%.

  Preparation of heat storage material microcapsule solid: The microcapsule dispersion prepared in the same manner as in Example 1 was spray-dried by spray drying to obtain a powdered heat storage material microcapsule solid. As a cationic and self-crosslinking resin, a 25% by mass aqueous solution of polyamide epichlorohydrin (Smileze Resin 675) is used, and 4 parts by mass is added to 100 parts by mass of the heat storage material microcapsule solid (microcapsule solid content 100 The addition amount of polyamide epichlorohydrin solid to 1 part is 1 part), and further, ethylene-vinyl acetate copolymer latex (solid content concentration 40% by mass) as a binder is added to 100 parts by mass of heat storage material microcapsule solids. 20 parts by mass was added (addition amount of binder solid content to 100 parts of microcapsule solid content was 8 parts). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 125 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.2%.

  Production of heat storage material microcapsule solid: A microcapsule dispersion produced in the same manner as in Example 3, using a 25% by mass aqueous solution of polyamide epichlorohydrin (Smirez resin 675) as a cationic and self-crosslinking resin 2 parts by mass are added to 100 parts by mass of the capsule dispersion (the amount of polyamide epichlorohydrin solid added to 100 parts of microcapsule solids is 1.2 parts), and polyvinyl alcohol as a binder (Corporation) 2 parts by mass of a 20% by mass aqueous solution of Kuraray, PVA217) was added to 100 parts by mass of the microcapsule dispersion (the amount of binder solid added to 100 parts of microcapsule solids was 0.9 parts) . Spray drying was performed by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 5%, and the solvent extraction rate was 0.3%.

  Preparation of heat storage material microcapsule solid: The microcapsule dispersion prepared in the same manner as in Example 3 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. As a cationic and self-crosslinking resin, a 25% by mass aqueous solution of polyamide epichlorohydrin (Smileze Resin 675) is used, and 4 parts by mass is added to 100 parts by mass of the heat storage material microcapsule solid (microcapsule solid content 100 The addition amount of polyamide epichlorohydrin solid to 1 part is 1 part), and further, ethylene-vinyl acetate copolymer latex (solid content concentration 40% by mass) as a binder is added to 100 parts by mass of heat storage material microcapsule solids. 25 parts by mass were added (the amount of binder solid added to 100 parts of microcapsule solid was 10 parts). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 125 J / g. The heat loss of the obtained heat storage material microcapsule solids was 2%, and the solvent extraction rate was 0.3%.

  Preparation of microcapsule dispersion: A microcapsule dispersion was obtained in the same manner as in Example 1 except that the latent heat storage material in Example 1 was changed to dodecyl laurate having a melting point of 27 ° C.

  Preparation of heat storage material microcapsule solid: A 25 mass% aqueous solution of polyamide epichlorohydrin (Smirez resin 675) was used as a cationic and self-crosslinking resin in the obtained microcapsule dispersion, and 100 mass of microcapsule dispersion 3 parts by weight per part (the amount of polyamide epichlorohydrin solid added to 100 parts of microcapsule solids is 1.8 parts), and further polyvinyl alcohol as a binder (Kuraray Co., Ltd., PVA217) Was added in an amount of 4 parts by mass with respect to 100 parts by mass of the microcapsule dispersion (the amount of the binder solid content added to 100 parts of the microcapsule solid content was 1.9 parts). Spray drying was performed by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 164 J / g. The heat loss of the obtained heat storage material microcapsule solids was 5%, and the solvent extraction rate was 0.2%.

  Preparation of microcapsule dispersion: A microcapsule dispersion was obtained in the same manner as in Example 1 except that the latent heat storage material in Example 1 was changed to dodecyl laurate having a melting point of 27 ° C.

  Preparation of heat storage material microcapsule solid: The obtained microcapsule dispersion was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. As a cationic and self-crosslinking resin, a 25% by mass aqueous solution of polyamide epichlorohydrin (Smileze Resin 675) is used, and 5 parts by mass is added to 100 parts by mass of the heat storage material microcapsule solid (microcapsule solid content 100 The amount of solid content of polyamide epichlorohydrin to 1.3 parts is 1.3 parts), and further, ethylene-vinyl acetate copolymer latex (solid content concentration 40% by mass) as a binder is 100 parts by mass of heat storage material microcapsule solids. 15 parts by mass relative to 100 parts of microcapsule solids (addition amount of binder solids to 6 parts is 6 parts). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The amount of heat of fusion of the obtained heat storage material microcapsule solid was 159 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.3%.

  Exactly the same operation as in Example 1 except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 0.1 part (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 0.06 part). To obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid substance was 13%, the solvent extraction rate became 0.9%, and the result was that water resistance was a little inferior.

  Exactly the same operation as in Example 1 except that the addition amount of the polyamide epichlorohydrin aqueous solution in Example 1 was 0.2 part (the addition amount of the polyamide epichlorohydrin solid content was 0.12 parts with respect to 100 parts of the microcapsule solid content). To obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 8%, and the solvent extraction rate was 0.6%.

  The same operation as in Example 1 was performed except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 1 part (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 0.6 part). A powdery heat storage material microcapsule solid was obtained. The obtained heat storage material microcapsule solid had a heat of fusion of 135 J / g. Further, the washing loss of the obtained heat storage material microcapsule solid was 6%, and the solvent extraction rate was 0.4%.

  The same operation as in Example 1 was carried out except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 4 parts (the amount of polyamide epichlorohydrin solids added was 2.4 parts with respect to 100 parts of the microcapsule solids). A powdery heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 133 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 5%, and the solvent extraction rate was 0.3%.

  The same operation as in Example 1 was performed except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 8 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 4.7 parts). A powdery heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 130 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 4%, and the solvent extraction rate was 0.2%.

  The same operation as in Example 1 was performed except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 15 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 8.8 parts). A powdery heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 125 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 4%, and the solvent extraction rate was 0.2%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 30 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 18 parts), the same operation as in Example 1 was performed, A solid heat storage material microcapsule solid was obtained. The obtained heat storage material microcapsule solid had a heat of fusion of 116 J / g, and the heat amount was slightly low. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 4%, and the solvent extraction rate was 0.1%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 1 was 50 parts (the amount of polyamide epichlorohydrin solids added relative to 100 parts of the microcapsule solids was 29 parts), the same operation as in Example 1 was performed, A solid heat storage material microcapsule solid was obtained. The obtained heat storage material microcapsule solid had a heat of fusion of 105 J / g, and the heat amount was low. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 4%, and the solvent extraction rate was 0.1%.

  Exactly the same operation as in Example 2 except that the addition amount of the polyamide epichlorohydrin aqueous solution in Example 2 was 0.2 part (the addition amount of the polyamide epichlorohydrin solid part was 0.05 parts with respect to 100 parts of the microcapsule solids). To obtain a granulated body heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. In addition, the washing loss of the obtained heat storage material microcapsule solid was 11%, the solvent extraction rate was 0.8%, and the water resistance was slightly inferior.

  Exactly the same operation as in Example 2 except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 0.4 parts (the amount of polyamide epichlorohydrin solids added relative to 100 parts of the microcapsule solids was 0.1 parts). To obtain a granulated body heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 7%, and the solvent extraction rate was 0.5%.

  The same operation as in Example 2 was performed except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 2 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 0.5 part). A solid heat storage material microcapsule solid was obtained. The obtained heat storage material microcapsule solid had a heat of fusion of 135 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 4%, and the solvent extraction rate was 0.3%.

  The same operation as in Example 2 was performed except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 10 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 2.5 parts). A solid heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 133 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.2%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 20 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 5 parts), the same operation as in Example 2 was carried out. A granular heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 130 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.2%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 40 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 10 parts), the same operation as in Example 2 was carried out. A granular heat storage material microcapsule solid was obtained. The heat storage material microcapsule solid thus obtained had a heat of fusion of 124 J / g. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.1%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 60 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 15 parts), the same operation as in Example 2 was carried out, A granular heat storage material microcapsule solid was obtained. The amount of heat of fusion of the obtained heat storage material microcapsule solid was 118 J / g, and the amount of heat was slightly low. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.1%.

  Except that the amount of the polyamide epichlorohydrin aqueous solution added in Example 2 was 90 parts (the amount of polyamide epichlorohydrin solid added relative to 100 parts of the microcapsule solids was 23 parts), the same operation as in Example 2 was carried out, A granular heat storage material microcapsule solid was obtained. The amount of heat of fusion of the obtained heat storage material microcapsule solid was 111 J / g, and the amount of heat was somewhat low. Moreover, the washing | cleaning weight loss of the obtained heat storage material microcapsule solid was 3%, and the solvent extraction rate was 0.1%.

(Comparative Example 1)
The microcapsule dispersion prepared in the same manner as in Example 1 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 136 J / g. In addition, the washing loss of the obtained heat storage material microcapsule solids was 43%, the solvent extraction rate was 3%, and the result was that the water resistance was very poor and the solvent resistance was also poor.

(Comparative Example 2)
The microcapsule dispersion prepared in the same manner as in Example 1 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. 5 mass parts of 20 mass% polyvinyl alcohol aqueous solution was added with respect to 100 mass parts of microcapsules (addition amount of binder solid content with respect to 100 parts of microcapsule solid content is 1 part). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The obtained heat storage material microcapsule solid had a heat of fusion of 135 J / g. In addition, the washing loss of the obtained heat storage material microcapsule solids was 32%, the solvent extraction rate was 2%, and the results were poor water resistance and solvent resistance.

(Comparative Example 3)
The microcapsule dispersion produced in the same manner as in Example 3 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 139 J / g. Further, the weight loss of the obtained heat storage material microcapsule solids was 46%, the solvent extraction rate was 3%, and the water resistance was very poor and the solvent resistance was poor.

(Comparative Example 4)
The microcapsule dispersion produced in the same manner as in Example 3 was spray-dried by spray drying to obtain a powdery heat storage material microcapsule solid. 5 mass parts of 20 mass% polyvinyl alcohol aqueous solution was added with respect to 100 mass parts of microcapsules (addition amount of binder solid content with respect to 100 parts of microcapsule solid content is 1 part). After stirring and mixing, it was molded to a diameter of 2 mm with an extrusion granulator and dried at 100 ° C. for 1 hour to obtain a granulated heat storage material microcapsule solid. The heat storage material microcapsule solid thus obtained had a heat of fusion of 138 J / g. In addition, the washing loss of the obtained heat storage material microcapsule solid was 30%, and the solvent extraction rate was 2%, resulting in poor water resistance and solvent resistance.

  As described above, according to the present invention, it is possible to provide a heat storage material microcapsule solid that maintains heat storage performance even when used under conditions where water or humidity exists or is exposed to an organic solvent.

  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 (4)

  A heat storage material microcapsule solid containing a microcapsule enclosing a latent heat storage material and a cationic and self-crosslinking resin.   The heat storage material microcapsule solid according to claim 1, wherein the cationic and self-crosslinking resin is a polyamide epihalohydrin resin.   The heat storage material microcapsule solid according to claim 1 or 2, wherein the heat storage material microcapsule solid contains 0.1 to 20 parts by mass of a cationic and self-crosslinking resin with respect to 100 parts by mass of the microcapsules.   The heat storage material microcapsule solid according to any one of claims 1 to 3, further comprising a binder in the heat storage material microcapsule solid.