JP4808476B2 - Thermal storage material microcapsule, thermal storage material microcapsule dispersion and thermal storage material microcapsule solid - Google Patents

Description

  The present invention relates to a microcapsule encapsulating a heat storage material, and specifically relates to a microcapsule having excellent temperature buffering properties near the melting temperature and / or solidification temperature of the heat storage material.

  A heat storage material is a material that can literally store heat, and is used in various fields from a low temperature range to a high temperature range. The most common heat storage materials are water and ice. Water has a very large specific heat for its low molecular weight, is a safe and inexpensive heat storage material, and can be used as a heat storage material for either cold insulation or heat insulation. In addition, ice obtained by cooling water to 0 ° C. or less has a heat of fusion of about 320 kJ / kg, and has a large amount of heat of fusion that is prominent compared to other compounds. Therefore, it is used as the most familiar cold insulation material.

  By the way, heat storage material microcapsules are made of textile materials such as clothing materials and bedding, heat insulation materials that heat and store heat by microwave irradiation, waste heat utilization equipment such as fuel cells and incinerators, overheating of electronic components and gas adsorbents, etc. In addition to suppression materials and / or overcooling suppression materials, building materials, building heat storage and space filling air conditioning, floor heating, air conditioning applications, civil engineering materials such as roads and bridges, industrial and agricultural thermal insulation materials, It is used in various fields such as household goods, health goods, and medical materials. The phase change temperature of the heat storage material, that is, the melting point and the freezing point, are roughly classified into a low temperature range (10 ° C. or lower), a middle temperature range (10 to 40 ° C.), and a high temperature range (40 ° C. or higher). As the heat storage material, inorganic compounds, saccharides, aliphatic hydrocarbon compounds that are organic compounds, and the like are used. Of these, aliphatic hydrocarbon compounds are often used for thermal storage microcapsules (Patent Documents 1 to 5).

Since aliphatic hydrocarbon compounds having a melting point in the middle temperature range are produced in large quantities industrially, they are relatively inexpensive and easy to encapsulate. However, be isolated from natural product of an aliphatic hydrocarbon compound having a melting point in the Atsushi Ko region, it is difficult to quantitatively in cost also. Usually, aliphatic hydrocarbons having 20 or more carbon atoms are commercially available in a mixture called paraffin wax. Paraffin wax is used as a release agent, brightener, water repellent, and the like, but can also be used as a heat storage material. However, as compared with a single compound product of an aliphatic hydrocarbon compound, there is a drawback that the heat of fusion of a paraffin wax having a large number of constituent compounds is low. Moreover, the phase change responsiveness at the time of phase change is poor, and when heating is performed on the paraffin wax in a solid state, the temperature range from the start of melting to the end of melting can be seen. For this reason, when heat is stored or taken out in a narrow temperature fluctuation range, only a part of the heat of fusion / solidification inherent in the compound can be used, and the effective heat usage per mass of the heat storage material is reduced. There was a thing.

  In addition, a mixture of an aliphatic hydrocarbon compound having about 10 to 20 carbon atoms, which is used as a heat storage material having a melting point in the middle to low temperature range near 0 to 30 ° C., is more easily available. However, in this case as well as the aliphatic hydrocarbon compound having a melting point of 40 ° C. or higher, the heat of fusion is low, and the phase change responsiveness is poor. For this reason, only a part of the heat of fusion / solidification inherent in the compound can be used, or the effective heat of use per mass of the heat storage material may be reduced.

  It has been proposed to use higher alcohols, higher fatty acids, and ester compounds as heat storage materials as compounds having a melting point of 40 ° C. or higher, a high heat of fusion of 80 kJ / kg or higher, and excellent phase change responsiveness (Patent Literature). 6). These are commercialized as high-purity compounds, and the temperature range from the beginning of melting to the end of melting is relatively narrow. Even when heat is accumulated or taken out in a narrow temperature fluctuation range, these compounds have inherent properties. Most of the heat of fusion / solidification can be utilized, and the effective heat utilization per mass of the heat storage material is large. Also, the price is relatively low. However, when these compounds are used in a bulk state, they can be used without hindrance, but there are various problems when emulsifying and dispersing into microcapsules.

That is, when a higher alcohol or higher fatty acid is microencapsulated, the crystallization rate of the compound is high, so that the emulsification dispersibility is poor, a good microcapsule film is hardly formed, and the encapsulation rate is low. was there. In addition, there is a problem of a specific odor depending on the number of carbon atoms. In particular, in the emulsification and dispersion process, since a strange odor is generated, it is not suitable as a heat storage material for a heat storage material microcapsule.

  On the other hand, in the ester compounds, most of the readily available ester compounds are mainly methyl esters, ethyl esters, and butyl esters, and ester compounds in which these alcohol residues have 4 or less carbon atoms are fatty acid residues. Even if it is a high-grade product having 10 or more carbon atoms, it has high hydrophilicity, and therefore has the following problems in the microencapsulation process. For example, when a heat storage material microcapsule is prepared by emulsifying and dispersing a heat storage material in a dispersion medium such as water, an ester compound obtained by a reaction between a higher fatty acid and a lower alcohol having 4 or less carbon atoms is used as the heat storage material. However, since a part of the ester compound is dissolved in the dispersion medium, it is lost without being encapsulated, and there is a problem that the ratio (encapsulation ratio) that can be effectively encapsulated is lowered. Furthermore, the ester compound dissolved in the dispersion medium often causes phenomena such as deterioration of the emulsification dispersibility, inhibition of the encapsulation reaction, and deterioration of the dispersion stability of the heat storage material microcapsule dispersion. .

  Further, the ester compound obtained by the reaction of a higher fatty acid and a lower alcohol having 4 or less carbon atoms has a melting point of room temperature when the total number of carbons of the fatty acid residue and the alcohol residue is about 20 Be near. Looking at the melting point, it is in the range that can be used as a heat storage material, but this ester compound is easily hydrolyzed, and when used for repeated heating and cooling for a long period of time, it gradually decomposes, lowering the heat of fusion and the purpose of the melting point There was a problem that a deviation from the temperature occurred.

  Also, in the case of ketone compounds other than ester compounds, ether compounds, amide compounds, amine compounds, etc., when the carbon number of at least one hydrocarbon group as viewed from the linking group is 4 or less, the above ester There were the same problems as the compound.

By the way, the target melting temperature (or solidification temperature) of the heat storage material is determined by the melting point (or freezing point) of the compound. However, a compound suitable for the target melting temperature (or solidification temperature) does not exist, or it is a special product and an industrially necessary amount may not be obtained. In this case, two or more kinds of compounds may be mixed to obtain a desired melting temperature (or solidification temperature). However, when two or more kinds of aliphatic hydrocarbon compounds are mixed, the mixture is mixed as described above. In many cases, the heat of fusion (or the amount of heat of solidification) of the material is much lower than the heat of fusion (or the amount of heat of solidification) of each single compound before mixing. Moreover, when two or more types of aliphatic hydrocarbon compounds having greatly different melting points are mixed, two or more melting temperatures derived from the mixed compounds appear as they are, and the melting temperature is often not shown at an intermediate temperature. Therefore, it is difficult for an aliphatic hydrocarbon compound to store heat at a temperature other than the melting point of the compound.
JP-A-5-25471 JP 2000-178545 A JP 2000-38577 A JP 2001-081447 A JP 2001-288458 A Japanese Patent No. 2847267

  The problem of the present invention is that it is not easily hydrolyzed, has excellent stability over time and phase change repetition durability, melts or solidifies in a target temperature range, and is excellent in high heat quantity and phase change thermal response. It is to provide a heat storage material.

As a result of intensive studies, the present inventors have found the following invention.
(1) compound represented by the following general formula the total number of carbon atoms is 20 to 28 (I), the heat storage material mixture the difference of the total number of carbon atoms is mixed for at least two or more compounds is within 4 is included Thermal storage material microcapsule, characterized by

[Wherein, R 1 and R 2 each independently represent a hydrocarbon group having 6 or more carbon atoms. X represents a divalent linking group containing a hetero atom represented by the following general formula . ]

[Wherein R3 represents an n-valent hydrocarbon group. R4 represents an independent hydrocarbon group having 6 or more carbon atoms. Y represents a divalent linking group containing a hetero atom. ]

[Wherein, A represents an m-valent atom, atomic group or linking group. R5 represents an independent hydrocarbon group having 6 or more carbon atoms. Z represents a divalent linking group containing a hetero atom or a direct bond. ]
(2) The heat storage material microcapsule according to (1), wherein the content of the most abundant compound in the heat storage material mixture is 20 to 95% by mass,
(3) The heat storage material microcapsule according to (1), wherein the heat storage material has a purity of 75% or more ,
(4) The heat storage material microcapsule according to (1) , wherein the acid value of the heat storage material is 8 or less and the hydroxyl value is 20 or less ,
(5) A heat storage material microcapsule dispersion in which the heat storage material microcapsules according to any one of (1) to (4) are dispersed in a dispersion medium,
(6) A heat storage material microcapsule solid obtained by fixing one or more heat storage material microcapsules according to any one of (1) to (4) above.

The heat storage material microcapsule of the present invention uses at least two kinds of compounds represented by the general formula (I ) as the heat storage material, but the hydrocarbon group of each compound has 6 or more carbon atoms. It is difficult to dissolve in a dispersion medium and is difficult to hydrolyze even in an environment where the amount of water and pH are likely to change. Therefore, a stable thermophysical property can be obtained and a high heat of fusion can be maintained even if it is used for a long period of time in applications where heating and cooling are repeated. Further, in the microencapsulation step, most of the heat storage material compound becomes oil droplets, which are effectively encapsulated and the encapsulation rate can be increased. Furthermore, the obtained heat storage material microcapsule dispersion has good dispersion stability.

The heat storage material microcapsule of the present invention is a heat storage material in which a mixture obtained by mixing at least two kinds of compounds having a total carbon number difference of 4 or less among the compounds represented by the general formula (I 1 ) is included in the microcapsule. As a result, it was possible to obtain temperature characteristics that could not be obtained with aliphatic hydrocarbon compounds. That is, when it becomes necessary to set an arbitrary target melting temperature (or solidification temperature), the melting heat range (or solidification temperature range) is 2 without causing a decrease in the heat of fusion (or heat of solidification). A temperature characteristic of showing one melting temperature (or solidification temperature) could be obtained without dividing into two or more.

The heat storage material according to the present invention is selected from compounds represented by the general formula (I ) .

  In the general formula (I), R1 and R2 are hydrocarbon groups having 6 or more carbon atoms, which may be the same or different from each other. Specific examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, hetacosyl, , Nonacosyl, triacontyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, tetracontyl, hentetracontyl , Dotetracontyl, tritetracontyl, tetratetracontyl, pentatetracontyl, hexatetracontyl, heptatetra Linear hydrocarbon groups such as n-til, octatetracontyl, nonatetracontyl, pentacontyl, etc., or branched hydrocarbon groups such as 2-ethylhexyl, 2-ethyloctyl, isododecyl, isooctadecyl, or hexenyl, heptenyl , Octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, dococenyl, tricocenyl, tetracocenyl, pentacocenyl, pentacocenyl, pentacocenyl, pentacocenyl, pentacocenyl, pentacocenyl, hexacocenyl, pentacocenyl, pentacocenyl Triacontenyl, dotriacontenyl, tritriacontenyl, tetratriacontenyl, pentatriaco Tenenyl, hexatriacontenyl, heptatriacontenyl, octatriacontenyl, nonatriacontenyl, tetracontenyl, hentetracontenyl, detetracontenyl, tritetracontenyl, tetratetracontenyl, pentatetracontenyl, And hydrocarbon groups having an unsaturated bond such as hexatetracontenyl, heptatetracontenyl, octatetracontenyl, nonatetracontenyl, and pentacontenyl. In R1 and R2, the carbon number is more preferably 8 to 60, and still more preferably 10 to 40. If the number of carbon atoms is less than 8, the stability to hydrolysis may be reduced, or the necessary amount of heat may be insufficient. On the other hand, when the number of carbon atoms exceeds 60, the amount of the raw material existing in nature may be extremely small and expensive.

  In general formula (I), X is a divalent linking group containing a hetero atom.

X in the present invention is a divalent linking group containing a hetero atom represented by the following general formula .

  In the general formula (II), R3 is an n-valent hydrocarbon group, and examples thereof include a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a cycloparaffin ring-containing hydrocarbon group. . N represents an integer of 2 to 60. Here, the n valence means that there are n parts bonded to Y.

  In the general formula (II), R4 is a hydrocarbon group having 6 or more carbon atoms, which may be the same or different from each other. Specific examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triaconyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriaconyl Chill, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, tetracontyl, hentetracontyl, dotetracontyl Linear hydrocarbon group such as tritetracontyl, tetratetracontyl, pentatetracontyl, hexatetracontyl, heptatetracontyl, octatetracontyl, nonatetracontyl, pentacontyl, or 2-ethylhexyl , 2-ethyloctyl, isododecyl, isooctadecyl, etc., branched hydrocarbon groups, or hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, nonadecenyl, nonadecenyl, Henecocenyl, dococenyl, tricocenyl, tetracocenyl, pentacocenyl, hexacocenyl, heptacocenyl, octacocenyl, nonacosenyl, triaconenyl, hen Triacontenyl, detriacontenyl, tritriacontenyl, tetratriacontenyl, pentatriacontenyl, hexatriacontenyl, heptatriacontenyl, octatriacontenyl, nonatriacontenyl, tetracontenyl, hentetracontenyl , Carbon atoms with unsaturated bonds such as detetracontenyl, tritetracontenyl, tetratetracontenyl, pentatetracontenyl, hexatetracontenyl, heptatetracontenyl, octatetracontenyl, nonatetracontenyl, pentacontenyl And a hydrogen group. In R4, the number of carbon atoms is more preferably 8 to 60, and still more preferably 10 to 40. If the number of carbon atoms is less than 8, the stability to hydrolysis may be reduced, or the necessary amount of heat may be insufficient. On the other hand, when the number of carbon atoms exceeds 60, the amount of the raw material existing in nature may be extremely small and expensive.

  In the general formula (II), Y is a divalent linking group containing a hetero atom.

And so on.

  In general formula (III), R5 is a hydrocarbon group having 6 or more carbon atoms, which may be the same or different from each other. Specific examples include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triaconyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriaconyl Chill, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl, tetracontyl, hentetracontyl, dotetracontyl Linear hydrocarbon group such as tritetracontyl, tetratetracontyl, pentatetracontyl, hexatetracontyl, heptatetracontyl, octatetracontyl, nonatetracontyl, pentacontyl, or 2-ethylhexyl , 2-ethyloctyl, isododecyl, isooctadecyl, etc., branched hydrocarbon groups, or hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, nonadecenyl, nonadecenyl, Henecocenyl, dococenyl, tricocenyl, tetracocenyl, pentacocenyl, hexacocenyl, heptacocenyl, octacocenyl, nonacosenyl, triaconenyl, Triacontenyl, detriacontenyl, tritriacontenyl, tetratriacontenyl, pentatriacontenyl, hexatriacontenyl, heptatriacontenyl, octatriacontenyl, nonatriacontenyl, tetracontenyl, hentetracontenyl , Carbon atoms with unsaturated bonds such as detetracontenyl, tritetracontenyl, tetratetracontenyl, pentatetracontenyl, hexatetracontenyl, heptatetracontenyl, octatetracontenyl, nonatetracontenyl, pentacontenyl And a hydrogen group. In R5, the carbon number is more preferably 8 to 60, and still more preferably 10 to 40. If the number of carbon atoms is less than 8, the stability to hydrolysis may be reduced, or the necessary amount of heat may be insufficient. On the other hand, when the number of carbon atoms exceeds 60, the amount of the raw material existing in nature may be extremely small and expensive.

  In general formula (III), Z is a divalent linking group containing a hetero atom or a direct bond. Specific examples of the divalent linking group containing a hetero atom include the groups exemplified above for Y.

  In the general formula (III), A is an m-valent atom, an atomic group or a linking group. Specific examples include a nitrogen atom, a sulfur atom, an oxygen atom, a silicon atom, a phosphorus atom, a heterocyclic ring, and a heteroatom-containing hydrocarbon. Examples include groups. Moreover, m represents the integer of 2-60. Here, the m value represents that there are m parts bonded to Z.

  The melting point of the heat storage material according to the present invention is not particularly limited. Even in the case of a compound having a melting point of 100 ° C. or higher, microencapsulation using an aqueous medium can be performed by emulsification and reaction in a high-pressure kettle. Is possible. In view of using general microencapsulation equipment, the melting point of the heat storage material is preferably set in the range of about −50 to 100 ° C., preferably in the range of −20 to 90 ° C. Furthermore, each independently a hydrocarbon group having 6 or more carbon atoms represented by R1, R2, R4 and R5 is preferably a linear saturated hydrocarbon group from the viewpoint of heat of fusion and harmfulness.

  As the heat storage material according to the present invention, in particular, fatty acid ester compound of fatty acid and monohydric alcohol, diester compound of dibasic acid and monohydric alcohol, ester compound of polyhydric alcohol and fatty acid, N-substituted fatty acid amide compound A ketone compound is preferred. In particular, fatty acid ester compounds can be suitably used from the viewpoint of easy availability of raw materials and ease of synthesis. That is, in the general formula (I), an ester compound in which X is a —COO— bond, R 1 is a hydrocarbon group having 6 or more carbon atoms, and R 2 is a hydrocarbon group having 6 or more carbon atoms. R1 and R2 may have the same or different carbon numbers. The number of carbon atoms in the hydrocarbon group of R1 and R2 is more preferably in the range of 8 to 60, and further preferably in the range of 10 to 40. R1 and R2 are most preferably a linear saturated hydrocarbon group.

  The heat storage material microcapsule of the present invention encapsulates a mixture obtained by mixing at least two kinds of heat storage materials in which the difference in total carbon number of the heat storage material is 4 or less. The difference in total carbon number within 4 means that, for example, in general formula (I), when X is a —COO— bond, R 1 is a tridecyl group having 13 carbon atoms, and R 2 is a dodecyl group having 12 carbon atoms. This refers to the case of using an ester compound (total carbon number = 26) and an ester compound (total carbon number = 24) in which R1 is an undecyl group having 11 carbon atoms and R2 is a dodecyl group having 12 carbon atoms (total carbon number). Number difference = 2). When it is necessary to set the target melting temperature (or solidification temperature) by encapsulating a mixture of at least two types of heat storage materials with a total carbon number difference of 4 or less in the heat storage materials in a microcapsule However, a temperature that shows one melting temperature (or solidification temperature) without causing a decrease in the heat of fusion (or solidification heat) and without dividing the melting temperature range (or solidification temperature range) into two or more. It becomes possible to obtain characteristics.

  On the other hand, when a mixture obtained by mixing at least two kinds of heat storage materials having a total carbon number difference of 5 or more, which is outside the present invention, is used, it is the same as when two or more types of aliphatic hydrocarbon compounds are mixed. A phenomenon may occur. That is, the heat of fusion (or the heat of solidification) of the mixture after mixing is much lower than the heat of fusion (or the heat of solidification) of each single product before mixing, or the temperature range (or the solidification temperature) showing the melting temperature or endotherm. That is, the temperature range showing heat dissipation may be divided into two or more.

The content of the most abundant compound in the heat storage material mixture in the present invention is preferably 20 to 95% by mass, more preferably 25 to 90% by mass, and still more preferably 30 to 85% by mass. When the content of the most contained compound is smaller than 20% by mass, at least five kinds of heat storage materials are mixed, and the number of constituent compounds is increased, so that the heat of fusion (or the heat of solidification) is reduced, Phase change responsiveness at the time of phase change is poor, that is, the temperature range from the start of melting to the end of melting (or the temperature range from the start of setting to the end of setting) may be widened. In addition, when the content of the most abundant compound exceeds 95% by mass, the difference between the melting temperature and the solidification temperature of the heat storage material mixture in the stage before encapsulating in the microcapsule increases, that is, the supercooling phenomenon may increase. is there. When the heat storage material mixture having a large supercooling phenomenon is encapsulated in a microcapsule, even if an additive acting as a supercooling inhibitor is added, the difference between the melting temperature and the solidification temperature of the heat storage material microcapsule It does not become smaller than the difference between the melting temperature and the solidification temperature in the state of the heat storage material mixture before being encapsulated. In other words, the supercooling phenomenon occurs even in the heat storage material microcapsule, which may hinder the use in which the difference between the melting temperature and the solidification temperature is required to be small (for example, the temperature difference is within about 5 ° C.). .

  The purity of the heat storage material according to the present invention is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more. If the purity of the heat storage material is less than 75%, the heat storage material contained in the microcapsule is melted or melted outside the desired temperature range due to the solidification promoting action by impurities and the solidification / precipitation / nucleation action of the impurities themselves. Solidification may occur, and the heat of fusion and heat of solidification in a desired temperature range may be low. The purity of the heat storage material here refers to the content of the main component contained in the entire heat storage material in the state of each heat storage material before mixing. The purity of the heat storage material according to the present invention can be measured by a gas chromatography method, a liquid chromatography method, or the like. The gas chromatography method is measured according to JIS K0114, and the area percentage method or the corrected area percentage method can be suitably applied. The liquid chromatography method is measured according to JIS K0124.

  The acid value of the heat storage material according to the present invention is preferably 8 or less, more preferably 5 or less, and still more preferably 3 or less. The hydroxyl value of the heat storage material according to the present invention is preferably 20 or less, more preferably 10 or less, and still more preferably 5 or less. When the acid value of the heat storage material exceeds 8 or the hydroxyl value exceeds 20, the progress of the capsule film formation reaction due to carboxylic acid compounds or alcohol compounds mixed as impurities or unreacted materials in the heat storage material May be partially inhibited, and it may not be possible to secure a film strength that can withstand long-term use with repeated phase changes. Of the acid value and hydroxyl value, the acid value has a greater influence on the film strength. The acid value and the hydroxyl value according to the present invention are measured in accordance with JIS K0070, and both the acid value and the hydroxyl value are expressed in mgKOH / g.

  The heat storage material according to the present invention may contain a supercooling inhibitor, a specific gravity adjusting agent, a deterioration preventing agent and the like as required.

  The heat storage material according to the present invention is used as a heat insulating material by filling a container and packaging material that is strong and has good heat stability so as not to leak at the time of melting, or is mixed with an oleophilic gelling agent and solidified, or It can be suspended in water and used as a dispersion. However, it can be processed into a form that is easy to use for various purposes by being microencapsulated as in the present invention.

  In the present invention, a physical method and a chemical method are known as a method for producing a microcapsule. 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). 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 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, polystyrene, polyacrylonitrile, poly (meth) acrylate, polyamide, polyacrylamide, ethyl cellulose, polyurethane, which are obtained by a method such as an interfacial polymerization method, an in-situ method, a radical polymerization method, An aminoplast resin, or a synthetic or natural resin using a coacervation method of gelatin and carboxymethyl cellulose or gum arabic is used. In the present invention, melamine formalin resin, urea formalin resin, polyamide, polyurea, and polyurethane urea are preferable, and further, physically and chemically stable in situ melamine formalin resin film, urea formalin resin film, or interfacial polymerization method. It is particularly preferable to use a microcapsule using a polyurea film or a polyurethaneurea film.

  The volume average particle diameter of the heat storage material microcapsules of 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 may be suppressed, but the film thickness may be reduced and the heat resistance may be poor. The volume average particle diameter described in the present invention represents the average particle diameter of the microcapsule particles in terms of volume, and in principle, particles having a fixed volume are sieved in order from the smallest, and the particles corresponding to 50% of the volume. Means the particle size at the time of separation. The volume average particle size can be measured by microscopic observation, but can be automatically measured by using a commercially available electrical or optical particle size measuring device. Measurement was performed using a particle size measuring device Multisizer type II manufactured by Coulter.

  The heat storage material microcapsules of the present invention are usually produced in the state of an aqueous dispersion, but can be used in the state of this dispersion (slurry), as well as spray dryers, drum dryers, freeze dryers, filter presses, etc. The water of the medium can be evaporated, dehydrated and dried by using various drying and dehydrating apparatuses to be used in the form of powder or solid. Furthermore, by adding a binder or the like to the powder or solid as necessary, the particle size is increased by granulation using various granulation methods such as extrusion granulation, rolling granulation, stirring granulation, etc. It can also be used in the form of a simplified granulated body. In the present invention, these powders, solid bodies, and granulated bodies are collectively referred to as solid bodies. The shape of the solid material may be any shape such as a sphere, an ellipse, a cube, a rectangular parallelepiped, a cylinder, a cone, a disk, a bowl, a bowl, a regular polyhedron, a star, a cylinder.

(Example)
Hereinafter, the present invention will be described in more detail by way of examples. The parts and percentages in the examples are based on mass unless otherwise specified. In addition, the melting temperature and solidification temperature of the heat storage material microcapsules in the examples, and the heat of fusion are samples obtained by using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer, USA) for the obtained heat storage material microcapsules. Heat capacity resulting from the melting behavior of the heat storage material encapsulated in microcapsules at the time of temperature rise when measured at an amount of 2 ± 0.2 mg, a temperature rise rate of 10 ° C./min and a temperature drop rate of 10 ° C./min The onset (intersection of the base line and the tangent of the endothermic curve) at the rise of the endothermic peak of the curve is the melting temperature, and the heat capacity curve of the heat capacity curve due to the solidification behavior of the heat storage material encapsulated in the microcapsule during the temperature drop The onset (intersection of the base line and the tangent to the heat release curve) temperature at the rise of the heat release peak is the solidification temperature, and the heat absorption peak and base of the heat capacity curve at the time of temperature rise The integral value of the difference between the ins and the heat of fusion. Moreover, also about the heat storage material before encapsulating in a microcapsule, the melting temperature and the solidification temperature were measured on the same conditions as the above, and the difference between the melting temperature and the solidification temperature was determined.

  The heat history durability in the examples refers to the dried product obtained by evaporating the water of the medium by collecting 5 g of the obtained dispersion liquid of the heat storage material microcapsule and heating it at 100 ° C. for 2 hours. Put it in a thermostatic chamber where temperature control is possible, change the temperature from -10 ° C to 60 ° C as the temperature range sandwiching the phase change temperature, measure the amount of heat storage after giving 300 temperature changes, and change the temperature The ratio with the heat storage amount before giving was defined as the heat history durability. The temperature change is 1 cycle for temperature increase, 30 minutes at 60 ° C., 1 hour for temperature decrease, and 30 minutes at −10 ° C. for one cycle. It shows that it is excellent in the retention of the heat storage amount 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.

  As a heat storage material, 70 parts of dodecyl myristate [total carbon number = 26] having a purity of 88%, an acid value of 2.6 and a hydroxyl value of 4.8 and a purity of 87%, an acid value of 2.7 and a hydroxyl value of 4.3 A certain amount of dodecyl laurate [total carbon number = 24] 30 parts was uniformly mixed to prepare a mixture A of heat storage materials. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 0.7 ° C.

  100 parts of the above mixture A is added to 125 parts of an aqueous sodium salt solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5 with vigorous stirring, and the average particle size becomes 12.0 μm. Emulsification was carried out. Next, 10 parts of melamine, 14 parts of a 37% aqueous formaldehyde solution and 25 parts of water were mixed, adjusted to pH 8, and an aqueous melamine-formalin condensate solution was prepared at about 80 ° C. The entire amount was added to the emulsion, and the mixture was heated and stirred at 70 ° C. for 2 hours to carry out an encapsulation reaction. Next, the pH of this dispersion was adjusted to 9 to complete the encapsulation. A dispersion of heat storage material microcapsules with a melamine-formalin resin film having a low viscosity and good dispersion stability was obtained. The obtained heat storage material microcapsule had a volume average particle diameter of 12.3 μm. The heat storage material microcapsules thus obtained had a melting temperature of 28.4 ° C., a solidification temperature of 24.8 ° C., a difference between the melting temperature and the solidification temperature of 3.6 ° C., and the heat of fusion per solid content of the heat storage material microcapsules. Was 167 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 93%.

  As a heat storage material, the purity is 92%, the acid value is 1.4, and the hydroxyl value is 3.2. Dodecyl laurate [total carbon number = 24] is 80 parts, the purity is 91%, the acid value is 1.6, and the hydroxyl value is 3.5. A certain amount of decyl laurate [total carbon number = 22] 20 parts was uniformly mixed to prepare a mixture B of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.1 ° C.

  1 part of N-stearyl palmitic acid amide as a supercooling inhibitor was added to 125 parts of an aqueous sodium salt solution of 5% styrene-maleic anhydride copolymer adjusted to pH 4.5. The product was added with vigorous stirring and emulsified until the average particle size was 2.0 μm. Next, 10 parts of melamine, 14 parts of a 37% aqueous formaldehyde solution and 25 parts of water were mixed, adjusted to pH 8, and an aqueous melamine-formalin condensate solution was prepared at about 80 ° C. The whole amount was added to the emulsion, and the mixture was heated and stirred at 70 ° C. for 2 hours to carry out an encapsulation reaction. Then, the pH of the dispersion was adjusted to 9 to complete the encapsulation. A dispersion of microcapsules of heat storage material with a low viscosity and good dispersion stability and a melamine formalin resin film was obtained. The obtained heat storage material microcapsule had a volume average particle diameter of 2.1 μm. The heat storage material microcapsules obtained had a melting temperature of 21.4 ° C., a solidification temperature of 19.1 ° C., a difference between the melting temperature and the solidification temperature of 2.3 ° C., and the heat of fusion per solid content of the heat storage material microcapsules. Was 159 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 97 parts of the same dodecyl laurate as used in Example 2 and 3 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture C of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 3.8 ° C.

  Except that the mixture C was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsule had a melting temperature of 27.4 ° C., a solidification temperature of 21.8 ° C., and the difference between the melting temperature and the solidification temperature was 5.6 ° C., indicating that the difference between the melting temperature and the solidification temperature was slightly larger. became. The heat of fusion per heat storage material microcapsule solid was 169 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 95 parts of the same dodecyl laurate as used in Example 2 and 5 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture D of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 3.6 ° C.

  Except that the mixture D was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules thus obtained had a melting temperature of 27.2 ° C., a solidification temperature of 22.3 ° C., a difference between the melting temperature and the solidification temperature of 4.9 ° C., and the heat of fusion per heat storage material microcapsule solid content was 167 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 90 parts of the same dodecyl laurate as used in Example 2 and 10 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture E of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 2.6 ° C.

  Encapsulation was performed in the same manner as in Example 2 except that the mixture E was used in place of the mixture B to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsule thus obtained had a melting temperature of 24.8 ° C., a solidification temperature of 21.0 ° C., a difference between the melting temperature and the solidification temperature of 3.8 ° C., and the heat of fusion per heat storage material microcapsule solid content was 167 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 85 parts of the same dodecyl laurate as used in Example 2 and 15 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture F of heat storage materials. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 1.4 ° C.

  Except that the mixture F was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsule thus obtained had a melting temperature of 23.1 ° C., a solidification temperature of 20.2 ° C., a difference between the melting temperature and the solidification temperature of 2.9 ° C., and the heat of fusion per heat storage material microcapsule solid content was 165 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As the heat storage material, 50 parts of the same dodecyl laurate as used in Example 2 and 50 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture G of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.5 ° C.

  Except that the mixture G was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 18.1 ° C., a solidification temperature of 15.6 ° C., a difference between the melting temperature and the solidification temperature of 2.5 ° C., and a heat of fusion per solid content of the heat storage material microcapsules of 152 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 15 parts of the same dodecyl laurate as used in Example 2 and 85 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a heat storage material mixture H. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 2.9 ° C.

  Except that the mixture H was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules thus obtained had a melting temperature of 17.8 ° C., a solidification temperature of 14.0 ° C., a difference between the melting temperature and the solidification temperature of 3.8 ° C., and the heat of fusion per heat storage material microcapsule solid content was 156 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 10 parts of the same dodecyl laurate as used in Example 2 and 90 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture I of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 3.1 ° C.

  Except that the mixture I was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 18.2 ° C., a solidification temperature of 13.9 ° C., a difference between the melting temperature and the solidification temperature of 4.3 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 157 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 5 parts of the same dodecyl laurate as used in Example 2 and 95 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture J of heat storage materials. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 3.0 ° C.

  Except that the mixture J was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsule thus obtained had a melting temperature of 18.7 ° C., a solidification temperature of 13.8 ° C., a difference between the melting temperature and the solidification temperature of 4.9 ° C., and the heat of fusion per solid heat storage material microcapsule was 159 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 3 parts of the same dodecyl laurate as used in Example 2 and 97 parts of the same decyl laurate as used in Example 2 were uniformly mixed to prepare a mixture K of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 3.7 ° C.

  Except that the mixture K was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 19.1 ° C., a solidification temperature of 13.3 ° C., and the difference between the melting temperature and the solidification temperature was 5.8 ° C., and the difference between the melting temperature and the solidification temperature was slightly large. became. The heat of fusion per heat storage material microcapsule solid was 160 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 50 parts of dodecyl myristate [total carbon number = 26] having a purity of 90%, an acid value of 1.8, and a hydroxyl value of 3.8 and the same decyl laurate [total carbon number] used in Example 2 = 22] 50 parts was uniformly mixed to prepare a mixture L of heat storage materials. The difference between the melting temperature and the solidification temperature before the encapsulation of the mixture in the microcapsule was 0.2 ° C.

  Except that the mixture L was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules thus obtained had a melting temperature of 16.5 ° C., a solidification temperature of 14.4 ° C., a difference between the melting temperature and the solidification temperature of 2.1 ° C., and the heat of fusion per solid heat storage material microcapsule was 144 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 70 parts of tetradecyl myristate [total carbon number = 28] having a purity of 93%, an acid value of 1.5, and a hydroxyl value of 3.1 and the same dodecyl myristate as used in Example 12 [total carbon number] = 26] 30 parts of the mixture were uniformly mixed to obtain a heat storage material mixture M. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 1.1 ° C.

  Supercooled to 100 parts of the above mixture M in 125 parts of a 5% ethylene-maleic anhydride copolymer sodium salt solution in which 7.5 parts of urea and 0.6 parts of resorcin were dissolved and the pH was adjusted to 3.0. A product added with 1 part of N-stearyl palmitic acid amide as an inhibitor was added with vigorous stirring, and emulsification was performed until the average particle size became 5 μm. Next, 19 parts of a 37% formaldehyde aqueous solution and 25 parts of water were added to this emulsion, followed by heating and stirring at 60 ° C. for 2 hours to carry out an encapsulation reaction. Next, the pH of this dispersion was adjusted to 9 to complete the encapsulation. A dispersion liquid of a heat storage material microcapsule with a urea formalin film having a low viscosity and good dispersion stability was obtained. The obtained heat storage material microcapsules had a volume average particle size of 5.2 μm. Moreover, the melting temperature of the obtained heat storage material microcapsule is 35.0 ° C., the solidification temperature is 33.4 ° C., the difference between the melting temperature and the solidification temperature is 1.6 ° C., and the heat of fusion per solid content of the heat storage material microcapsule. Was 172 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 95%.

  As a heat storage material, 85 parts of decyl laurate [total carbon number = 22] same as that used in Example 2, 92% purity, acid value 1.9, hydroxyl value 3.3 decyl decanoate [total carbon number = 20] 15 parts of the mixture were uniformly mixed to prepare a heat storage material mixture N. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 2.0 ° C.

  1 part of N-stearyl palmitic acid amide as a supercooling inhibitor is added to 100 parts of the above mixture, and 11 parts of polymeric diphenylmethane diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., aromatic isocyanate, trade name 44V20) as a polyvalent isocyanate. The dissolved product was added to 125 parts of an aqueous solution of 5% polyvinyl alcohol (product name: POVAL 117, manufactured by Kuraray Co., Ltd.), and stirred and emulsified at room temperature until the volume average particle size became 3 μm. Next, 69 parts of a 3% diethylenetriamine aqueous solution was added to the emulsion, followed by heating and stirring at 60 ° C. for 1 hour. A dispersion liquid of a heat storage material microcapsule having a polyurea film having low viscosity and good dispersion stability was obtained. The obtained heat storage material microcapsule had a volume average particle diameter of 3.2 μm. The heat storage material microcapsules obtained had a melting temperature of 15.6 ° C., a solidification temperature of 11.5 ° C., a difference between the melting temperature and the solidification temperature of 4.1 ° C., and the heat of fusion per solid content of the heat storage material microcapsules. Was 154 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 94%.

  As the heat storage material, 40 parts of the same dodecyl laurate [total carbon number = 24] as used in Example 2 and 60 parts of the same decyl laurate [total carbon number = 22] as used in Example 12 were uniformly used. Mixing was performed to prepare a mixture O of a heat storage material. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 1.9 ° C.

  1 part of N-stearyl palmitic acid amide is added to 100 parts of the mixture O as a supercooling inhibitor, and dicyclohexylmethane 4,4-diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., aliphatic isocyanate, trade name) as the polyvalent isocyanate. Desmodur W) 16 parts dissolved is added to 125 parts of 5% polyvinyl alcohol (Kuraray Co., Ltd., trade name POVAL 117) aqueous solution, and stirred and emulsified at room temperature until the average particle size becomes 4 μm. It was. Next, 69 parts 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 then heated and stirred at 60 ° C. A dispersion liquid of a heat storage material microcapsule having a polyurethane urea film having low viscosity and good dispersion stability was obtained. The obtained heat storage material microcapsule had a volume average particle diameter of 4.2 μm. The heat storage material microcapsules obtained had a melting temperature of 17.8 ° C., a solidification temperature of 14.2 ° C., a difference between the melting temperature and the solidification temperature of 3.6 ° C., and the heat of fusion per solid content of the heat storage material microcapsules. Was 150 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 95%.

  As a heat storage material, 50 parts of dodecyl myristate [total carbon number = 26] same as that used in Example 12 and 50 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 were uniformly used. Mixing was performed to prepare a heat storage material mixture P. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0 ° C.

  To 100 parts of the mixture P, 1 part of N-stearyl palmitic acid amide is added as a supercooling inhibitor, and further 11.9 parts of methyl methacrylate and 0.6 part of ethylene glycol dimethacrylate are dissolved as monomers. It put into 375 parts of 1% polyvinyl alcohol aqueous solution, and emulsified by strong stirring. Next, the inside of the polymerization vessel containing the emulsified liquid was kept in a nitrogen atmosphere while maintaining at 75 ° C., and then 2,2′-azobis {2- [1- (2-hydroxyethyl) dissolved in 19 parts of ion-exchanged water. 2-Imidazolin-2-yl] propane} dihydrochloride 0.5 part was added. After 7 hours, the polymerization was completed, the inside of the polymerization vessel was cooled to room temperature, and the encapsulation was completed. A dispersion liquid of a heat storage material microcapsule having a polymethyl methacrylate film by a radical polymerization method having low viscosity and good dispersion stability was obtained. The obtained heat storage material microcapsules had a volume average particle size of 5.3 μm. The heat storage material microcapsules obtained had a melting temperature of 26.9 ° C., a solidification temperature of 23.5 ° C., a difference between the melting temperature and the solidification temperature of 3.4 ° C., and the heat of fusion per solid content of the heat storage material microcapsules. Was 166 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 92%.

  20 parts of tetradecyl myristate [total carbon number = 28] same as that used in Example 13 and 70 parts of dodecyl myristate [total carbon number = 26] same as those used in Example 12 as heat storage materials 10 parts of the same dodecyl laurate [total carbon number = 24] used in 2 was mixed to prepare a heat storage material mixture Q. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 1.3 ° C.

  Except that the mixture Q was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules thus obtained had a melting temperature of 36.4 ° C., a solidification temperature of 34.4 ° C., a difference between the melting temperature and the solidification temperature of 2.0 ° C., and the heat of fusion per solid heat storage material microcapsule was 170 J. / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As a heat storage material, 50 parts of dodecyl myristate [total carbon number = 26] same as the one used in Example 12, purity 91%, acid value 1.7, hydroxyl value 3.4, tetradecyl laurate [total carbon number = 26] 50 parts was uniformly mixed to prepare a mixture R of heat storage materials. The difference between the melting temperature and the solidification temperature before the encapsulation of the mixture in microcapsules was 0.7 ° C.

  Except that the mixture R was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 35.1 ° C., a solidification temperature of 32.9 ° C., a difference between the melting temperature and the solidification temperature of 2.2 ° C., and a heat of fusion per solid content of the heat storage material microcapsules of 169 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  As heat storage material, 40 parts of dodecyl myristate [total carbon number = 26] same as that used in Example 12 and 30 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 and Example 13 parts of the same tetradecyl myristate [total carbon number = 28] as used in 13 was uniformly mixed to prepare a mixture S of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.6 ° C.

  Except that the mixture S was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The resulting heat storage material microcapsule had a melting temperature of 35.5 ° C., a solidification temperature of 33.2 ° C., a difference between the melting temperature and the solidification temperature of 2.3 ° C., and the heat of fusion per solid content of the heat storage material microcapsule was 165 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  30 parts of dodecyl myristate [total carbon number = 26] same as those used in Example 12 and 25 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 as heat storage materials 25 parts of tetradecyl myristate [total carbon number = 28] same as that used in No. 13 and 20 parts of tetradecyl laurate [total carbon number = 26] same as those used in Example 18 were uniformly mixed to obtain a heat storage material. A mixture T was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.5 ° C.

  Except that the mixture T was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 34.3 ° C., a solidification temperature of 32.3 ° C., a difference between the melting temperature and the solidification temperature of 2.0 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 162 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 97%.

  As the heat storage material, 25 parts of dodecyl myristate [total carbon number = 26] same as that used in Example 12 and 25 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 and Example 25 parts of tetradecyl myristate [total carbon number = 28] same as that used in No. 13 and 25 parts of tetradecyl laurate [total carbon number = 26] same as those used in Example 18 were uniformly mixed to obtain a heat storage material. A mixture U was prepared. The difference between the melting temperature and the solidification temperature before the encapsulation of the mixture in the microcapsule was 0.3 ° C.

  Except that the mixture U was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 34.1 ° C., a solidification temperature of 32.3 ° C., a difference between the melting temperature and the solidification temperature of 1.8 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 152 J. / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 97%.

  As heat storage material, 20 parts of dodecyl myristate [total carbon number = 26] same as that used in Example 12 and 20 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 and Example 20 parts of tetradecyl myristate [total carbon number = 28] same as those used in Example 13 and 20 parts of tetradecyl laurate [total carbon number = 26] same as those used in Example 18, purity 91%, acid value 1. 6 and 20 parts of dodecyl palmitate [total carbon number = 28] having a hydroxyl value of 3.9 were uniformly mixed to prepare a heat storage material mixture V. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.1 ° C.

  Except that the mixture V was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 35.2 ° C., a solidification temperature of 33.8 ° C., a difference between the melting temperature and the solidification temperature of 1.4 ° C., and a heat of fusion per solid content of the heat storage material microcapsules of 141 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 97%.

  17 parts of dodecyl myristate [total carbon number = 26] same as those used in Example 12 and 17 parts of dodecyl laurate [total carbon number = 24] same as those used in Example 2 as heat storage materials and examples 17 parts of tetradecyl myristate [total carbon number = 28] same as those used in 13 and 17 parts of tetradecyl laurate [total carbon number = 26] same as those used in Example 18 and those used in Example 22 16 parts of the same dodecyl palmitate [total carbon number = 28] and 16 parts of hexadecyl laurate [total carbon number = 28] having a purity of 90%, an acid value of 1.9 and a hydroxyl value of 3.5 are uniformly mixed, A mixture W of heat storage materials was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.1 ° C.

  Except that the mixture W was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules obtained had a melting temperature of 35.8 ° C., a solidification temperature of 34.5 ° C., and a difference between the melting temperature and the solidification temperature of 1.3 ° C. Moreover, the heat of fusion per solid content of the heat storage material microcapsule was 136 J / g, and the heat amount was slightly low. In addition, the heat history durability of the obtained heat storage material microcapsule was 97%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 2.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 86%, an acid value of 2.8, and a hydroxyl value of 4.7, and Were mixed uniformly to prepare a heat storage material mixture a. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.1 ° C.

  Except that the mixture a was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsule obtained had a melting temperature of 21.7 ° C., a solidification temperature of 19.7 ° C., a difference between the melting temperature and the solidification temperature of 2.0 ° C., and the heat of fusion per solid heat storage material microcapsule was 153 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 97%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 81%, an acid value of 2.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 82%, an acid value of 2.8, and a hydroxyl value of 4.7, and Were mixed uniformly to prepare a heat storage material mixture b. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture b was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 21.5 ° C., a solidification temperature of 19.7 ° C., a difference between the melting temperature and the solidification temperature of 1.8 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 150 J. / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 94%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 76%, an acid value of 2.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 77%, an acid value of 2.8, and a hydroxyl value of 4.7, and Were mixed uniformly to prepare a heat storage material mixture c. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.3 ° C.

  Except that the mixture c was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The heat storage material microcapsules thus obtained had a melting temperature of 21.3 ° C., a solidification temperature of 19.6 ° C., a difference between the melting temperature and the solidification temperature of 1.7 ° C., and the heat of fusion per solid heat storage material microcapsule was 147 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 90%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 71%, an acid value of 2.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 72%, an acid value of 2.8, and a hydroxyl value of 4.7, and Were mixed uniformly to prepare a mixture d of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.3 ° C.

  Except that the mixture d was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 21.2 ° C., a solidification temperature of 19.6 ° C., and a difference between the melting temperature and the solidification temperature of 1.6 ° C. Moreover, the heat of fusion per heat storage material microcapsule solid content was 139 J / g, and when the purity of the heat storage material was lower than the preferred range of the present invention, the result was that the amount of heat was slightly lower. In addition, the heat history durability of the obtained heat storage material microcapsule was 87%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 4.4 and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 86%, an acid value of 4.5 and a hydroxyl value of 4.7, and Were uniformly mixed to prepare a mixture e of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture e was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 21.6 ° C., a solidification temperature of 20.0 ° C., a difference between the melting temperature and the solidification temperature of 1.6 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 151 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 91%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 7.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 86%, an acid value of 7.3, and a hydroxyl value of 4.7, and Were uniformly mixed to prepare a heat storage material mixture f. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture f was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 21.4 ° C., a solidification temperature of 20.1 ° C., a difference between the melting temperature and the solidification temperature of 1.3 ° C., and a heat of fusion per solid content of the heat storage material microcapsules of 148 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule is 85%, and when the acid value of the heat storage material is close to the upper limit of the preferred range of the present invention, the phase change repeated durability of the heat storage material microcapsule is slightly inferior. It became the result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 9.5 and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 86%, an acid value of 9.4 and a hydroxyl value of 4.7, Were mixed uniformly to prepare a heat storage material mixture g. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture g was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The resulting heat storage material microcapsule has a melting temperature of 21.2 ° C., a solidification temperature of 20.0 ° C., a difference between the melting temperature and the solidification temperature of 1.2 ° C., and the heat of fusion per solid content of the heat storage material microcapsule is 143 J / G. The heat history durability of the obtained heat storage material microcapsule is 77%, and if the acid value of the heat storage material is higher than the preferred range of the present invention, the phase change repetition durability of the heat storage material microcapsule is slightly inferior. As a result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 2.6, and a hydroxyl value of 8 and 20 parts of decyl laurate having a purity of 86%, an acid value of 2.8, and a hydroxyl value of 9 are uniformly mixed. Then, a mixture h of heat storage materials was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture h was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a low viscosity and good dispersion stability. The obtained heat storage material microcapsules had a melting temperature of 21.5 ° C., a solidification temperature of 19.8 ° C., a difference between the melting temperature and the solidification temperature of 1.7 ° C., and the heat of fusion per solid content of the heat storage material microcapsules was 150 J. / G. In addition, the heat history durability of the obtained heat storage material microcapsule was 93%.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, acid value 2.6 and hydroxyl value 19 and 20 parts of decyl laurate having a purity of 86%, acid value 2.8 and hydroxyl value 18 are uniformly mixed. Then, a mixture i of heat storage materials was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture i was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The heat storage material microcapsule thus obtained had a melting temperature of 21.4 ° C., a solidification temperature of 20.0 ° C., a difference between the melting temperature and the solidification temperature of 1.4 ° C., and the heat of fusion per solid heat storage material microcapsule was 146 J / G. The thermal history durability of the obtained heat storage material microcapsule is 87%, and when the hydroxyl value of the heat storage material is close to the upper limit of the preferred range of the present invention, the phase change repeated durability of the heat storage material microcapsule is slightly inferior. It became the result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 2.6, and a hydroxyl value of 24 are mixed uniformly with 20 parts of decyl laurate having a purity of 86%, an acid value of 2.8, and a hydroxyl value of 25. Then, a mixture j of heat storage materials was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture j was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The heat storage material microcapsule obtained had a melting temperature of 21.3 ° C., a solidification temperature of 19.9 ° C., a difference between the melting temperature and the solidification temperature of 1.4 ° C., and a heat of fusion per solid content of the heat storage material microcapsule of 142 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule is 79%, and if the hydroxyl value of the heat storage material is higher than the preferred range of the present invention, the phase change repetition durability of the heat storage material microcapsule is slightly inferior. As a result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 76%, an acid value of 2.6 and a hydroxyl value of 19 and 20 parts of decyl laurate having a purity of 77%, an acid value of 2.8 and a hydroxyl value of 18 are uniformly mixed. Then, a mixture k of the heat storage material was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.3 ° C.

  Except that the mixture k was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 21.4 ° C., a solidification temperature of 20.1 ° C., a difference between the melting temperature and the solidification temperature of 1.3 ° C., and a heat of fusion per solid content of the heat storage material microcapsules of 148 J / G. In addition, the thermal history durability of the obtained heat storage material microcapsule is 84%, and when the hydroxyl value of the heat storage material is close to the upper limit of the preferred range of the present invention, the phase change repeated durability of the heat storage material microcapsule is slightly inferior. It became the result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 76%, an acid value of 4.4 and a hydroxyl value of 19 and 20 parts of decyl laurate having a purity of 77%, an acid value of 4.5 and a hydroxyl value of 18 are uniformly mixed. Then, a mixture m of heat storage materials was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.3 ° C.

  Except that the mixture m was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The melting temperature of the obtained heat storage material microcapsule was 21.3 ° C., the solidification temperature was 20.2 ° C., the difference between the melting temperature and the solidification temperature was 1.1 ° C., and the heat of fusion per solid content of the heat storage material microcapsule was 147 J / G. In addition, the heat history durability of the obtained heat storage material microcapsule is 80%, and when the hydroxyl value of the heat storage material is close to the upper limit of the preferred range of the present invention, the phase change repeated durability of the heat storage material microcapsule is slightly inferior. It became the result.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 76%, an acid value of 7.6, and a hydroxyl value of 4.5, and 20 parts of decyl laurate having a purity of 77%, an acid value of 7.3, and a hydroxyl value of 4.7, and Were mixed uniformly to prepare a mixture n of heat storage materials. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture n was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 21.5 ° C., a solidification temperature of 20.5 ° C., a difference between the melting temperature and the solidification temperature of 1.0 ° C., and the heat of fusion per solid heat storage material microcapsule was 146 J / G. The heat history durability of the obtained heat storage material microcapsule is 79%, the purity of the heat storage material is close to the lower limit of the preferred range of the present invention, and the acid value of the heat storage material is the upper limit of the preferred range of the present invention. As a result, the durability of the heat storage material microcapsule was slightly inferior in phase change.

  As a heat storage material, 80 parts of dodecyl laurate having a purity of 87%, an acid value of 7.6, and a hydroxyl value of 19 and 20 parts of decyl laurate having a purity of 86%, an acid value of 7.3, and a hydroxyl value of 18 are uniformly mixed. Then, a mixture p of the heat storage material was prepared. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 0.2 ° C.

  Except that the mixture p was used in place of the mixture B, encapsulation was carried out in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules having a slightly increased viscosity and slightly poor dispersion stability. The resulting heat storage material microcapsules had a melting temperature of 21.3 ° C., a solidification temperature of 20.3 ° C., a difference between the melting temperature and the solidification temperature of 1.0 ° C., and a heat of fusion per solid content of the heat storage material microcapsule of 147 J / G. The heat storage durability of the obtained heat storage material microcapsule is 78%, and when both the acid value and the hydroxyl value of the heat storage material are close to the upper limit of the preferred range of the present invention, the phase change of the heat storage material microcapsule is repeated. As a result, the durability was slightly inferior.

(Comparative Example 1)
Similar to Example 1 except that instead of Mixture A, only the same dodecyl myristate as used in Example 1 (the difference between the melting temperature and the solidification temperature before encapsulating in the microcapsules was 2.7 ° C.) was used. The capsule was encapsulated by the above operation to obtain a dispersion liquid of heat storage material microcapsules. The resulting heat storage material microcapsules had a melting temperature of 36.7 ° C., a solidification temperature of 28.5 ° C., a difference between the melting temperature and the solidification temperature of 8.2 ° C., and the difference between the melting temperature and the solidification temperature was slightly large. became. The heat of fusion per heat storage material microcapsule solid was 172 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 93%.

(Comparative Example 2)
Similar to Example 2 except that only the same dodecyl laurate (difference between the melting temperature and the solidification temperature before inclusion in the microcapsule 3.9 ° C.) as used in Example 2 was used instead of the mixture B. The capsule was encapsulated by the above operation to obtain a dispersion liquid of heat storage material microcapsules. The obtained heat storage material microcapsule had a melting temperature of 27.9 ° C., a solidification temperature of 21.1 ° C., and the difference between the melting temperature and the solidification temperature was 6.8 ° C., indicating that the difference between the melting temperature and the solidification temperature was slightly large. became. The heat of fusion per heat storage material microcapsule solid was 179 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

(Comparative Example 3)
Example 2 is the same as Example 2 except that the same decyl laurate as used in Example 2 (the difference between the melting temperature and the solidification temperature before encapsulating in the microcapsule is 2.9 ° C.) was used instead of the mixture B. Encapsulation was performed by the same operation to obtain a dispersion liquid of heat storage material microcapsules. The resulting heat storage material microcapsules had a melting temperature of 19.6 ° C., a solidification temperature of 12.1 ° C., a difference between the melting temperature and the solidification temperature of 7.5 ° C., and the difference between the melting temperature and the solidification temperature was slightly large. became. The heat of fusion per heat storage material microcapsule solid was 163 J / g. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

(Comparative Example 4)
As a heat storage material, 50 parts of the same dodecyl myristate [total carbon number = 26] as used in Example 12 and 50 parts of the same decyl decanoate [total carbon number = 20] as used in Example 14 were uniformly used. To prepare a heat storage material mixture q. The difference between the melting temperature and the solidification temperature before encapsulating the mixture in microcapsules was 0.4 ° C.

  Except that the mixture q was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules. The heat storage material microcapsules obtained had a melting temperature of 4.0 ° C., a solidification temperature of 1.6 ° C., and a difference between the melting temperature and the solidification temperature of 2.4 ° C. Moreover, the heat of fusion per heat storage material microcapsule solid content was 127 J / g, which was a low heat of fusion. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

(Comparative Example 5)
As a heat storage material, 50 parts of n-octadecane [total carbon number = 18] which is an aliphatic hydrocarbon compound and 50 parts of n-hexadecane [total carbon number = 16] are uniformly mixed to prepare a mixture r of heat storage materials. did. The difference between the melting temperature and the solidification temperature of the mixture before encapsulating in the microcapsules was 1.8 ° C.

  Except that the mixture r was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules. When the melting / solidification behavior of the obtained heat storage material microcapsules was evaluated, the melting temperature was 14.3 ° C., but the melting peak was very broad, and the solidification temperature was 11.2 ° C. Even got very broad. The difference between the melting temperature and the solidification temperature was 3.1 ° C. Moreover, the heat of fusion per heat storage material microcapsule solid content was also 119 J / g, resulting in a low heat of fusion. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

(Comparative Example 6)
As a heat storage material, 50 parts of n-octadecane [total carbon number = 18] which is an aliphatic hydrocarbon compound and 50 parts of n-tetradecane [total carbon number = 14] are uniformly mixed to prepare a mixture s of heat storage materials. did. The difference between the melting temperature and the solidification temperature appearing on the high temperature side before encapsulating the mixture in microcapsules was 2.5 ° C.

  Except that the mixture s was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules. When the melting / solidification behavior of the obtained heat storage material microcapsule was evaluated, the melting peak was divided into two peaks of 4 ° C. and 27 ° C., and the solidification peak was also divided into two broad peaks. The performance of causing melting (heat storage) and solidification (heat dissipation) only in the temperature range was not obtained. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

(Comparative Example 7)
As a heat storage material, 50 parts of n-octadecane [total carbon number = 18] which is a real aliphatic hydrocarbon compound and 50 parts of n-dodecane [total carbon number = 12] are uniformly mixed, and a mixture t of heat storage materials is obtained. Prepared. The difference between the melting temperature and the solidification temperature appearing on the high temperature side before being encapsulated in the microcapsules of this mixture was 1.3 ° C.

  Except that the mixture t was used in place of the mixture B, encapsulation was performed in the same manner as in Example 2 to obtain a dispersion liquid of heat storage material microcapsules. When the melting / solidification behavior of the obtained heat storage material microcapsule was evaluated, the melting peak was divided into two peaks of −10 ° C. and 28 ° C., and the solidification peak was also divided into two broad peaks. The performance of causing melting (heat storage) and solidification (heat dissipation) only in the temperature range of was not obtained. In addition, the heat history durability of the obtained heat storage material microcapsule was 98%.

  The heat storage material microcapsule dispersion obtained in Example 1 was spray-dried by spray drying to obtain a heat storage material microcapsule powder having an average particle size of 80 μm and a moisture content of 2%. The obtained heat storage material microcapsule powder had good fluidity and no odor was felt.

  The heat storage material microcapsule dispersion obtained in Example 2 was spray-dried by spray drying to obtain a heat storage material microcapsule powder having an average particle size of 100 μm and a moisture content of 3%. The obtained heat storage material microcapsule powder had good fluidity and no odor was felt.

  The heat storage material microcapsule dispersion obtained in Example 1 was spray-dried by spray drying to obtain a heat storage material microcapsule powder having an average particle size of 120 μm. The obtained powder had good fluidity and no odor was felt. Furthermore, after adding and mixing 30 parts of 30% polyvinyl alcohol aqueous solution as a binder and an appropriate amount of water to 100 parts of the obtained heat storage material microcapsule powder, extrusion molding is performed by an extrusion granulator, Drying was performed at 100 ° C. to obtain a granulated body of a cylindrical heat storage material microcapsule having a minor axis of 1 mm and a major axis of 3 mm. In the obtained heat storage material microcapsule granule, no seepage of the heat storage material was observed, and no odor was felt.

  The heat storage material microcapsule dispersion obtained in Example 2 was spray-dried by spray drying to obtain a heat storage material microcapsule powder having an average particle size of 120 μm. The obtained powder had good fluidity and no odor was felt. Furthermore, to 100 parts of the obtained heat storage material microcapsule powder, 30 parts of 30% polyvinyl alcohol aqueous solution as a binder and an appropriate amount of added water were added and mixed, and then extrusion molding was performed using an extrusion granulator. And dried at 100 ° C. to obtain a granulated body of a cylindrical heat storage material microcapsule having a minor axis of 2 mm and a major axis of 4 mm. In the obtained heat storage material microcapsule granule, no seepage of the heat storage material was observed, and no odor was felt.

  The heat storage material microcapsule according to the present invention is a textile processed material such as clothing material or bedding, a heat insulating material heated and stored by microwave irradiation, a waste heat utilization facility such as a fuel cell or an incinerator, an electronic component, a gas adsorbent, etc. In addition to overheat suppression materials and / or overcooling suppression materials, building materials, building heat storage and space filling air conditioning, floor heating, air conditioning applications, civil engineering materials such as roads and bridges, industrial and agricultural thermal insulation materials It can be applied to various fields such as household goods, health goods, and medical materials.

Claims (6)

It is a compound represented by the following general formula (I ) having a total carbon number of 20 to 28 and containing a heat storage material mixture in which at least two kinds of compounds having a total carbon number difference of 4 or less are mixed. A heat storage material microcapsule.

[Wherein, R 1 and R 2 each independently represent a hydrocarbon group having 6 or more carbon atoms. X represents a divalent linking group containing a hetero atom represented by the following general formula . ]

  The heat storage material microcapsule according to claim 1, wherein the content of the most abundant compound in the heat storage material mixture is 20 to 95 mass%. The heat storage material microcapsule according to claim 1, wherein the heat storage material has a purity of 75% or more . The heat storage material microcapsule according to claim 1, wherein the heat storage material has an acid value of 8 or less and a hydroxyl value of 20 or less .   The thermal storage material microcapsule dispersion liquid which disperse | distributed the thermal storage material microcapsule of any one of Claims 1-4 to the dispersion medium.   The heat storage material microcapsule solid substance which fixes the heat storage material microcapsule of any one of Claims 1-4 individually or in multiple numbers.