JP5505919B2 - Manufacturing method of heat storage material microcapsule and heat storage material microcapsule - Google Patents

Description

  The present invention relates to a method for producing a heat storage material microcapsule and a heat storage material microcapsule, and more specifically, includes particles containing a heat storage material and a binder, and is superior to a long-term heat history, shear stress due to a pump, and the like. The present invention relates to a manufacturing method of a heat storage material microcapsule having durability and a heat storage material microcapsule.

In heat transfer systems used for air conditioning and the like, sensible heat storage materials represented by water, ethylene glycol and the like are mainly used as a heat transport medium. These sensible heat storage materials utilize a temperature difference generated in the medium.
On the other hand, a latent heat storage material that uses latent heat associated with phase transition has an advantage of having a large heat capacity and greatly improving the thermal efficiency of the heat transfer system. Any latent heat storage material can be used as long as it has a melting point and a freezing point. However, a material that is physicochemically stable and has a large latent heat is desirable. Typical latent heat storage materials include calcium chloride, sodium sulfate, and phosphorus. Examples include hydrates of inorganic compounds such as sodium oxyhydrogen, and organic compounds such as paraffin wax, higher fatty acids, and higher alcohols.

  These heat storage materials are usually used in the form of heat storage material microcapsules in which a heat storage material is used as a core substance and a film is formed around the heat storage material.

Many of the microcapsule production methods are widely known in which a liquid heat storage material is emulsified and dispersed in water to which an emulsifier is added, and a film made of melamine resin or the like is formed around the dispersed particles (for example, patent documents). 1).
This melamine resin film is obtained by polycondensation of melamine and formaldehyde, and has the characteristics of excellent mechanical strength and heat resistance. On the other hand, this method is more than twice as high as melamine in order to increase the reaction rate of melamine. Therefore, there is a problem that formaldehyde harmful to human body may remain.
Japanese Patent Laid-Open No. 5-117642

Further, when manufacturing microcapsules of a heat storage material made of an organic compound having a high melting point, in the conventional manufacturing method of emulsifying and dispersing the heat storage material in water, it is necessary to keep the heat storage material in a liquid state when the heat storage material is dispersed. . When manufacturing microcapsules containing a high-melting-point heat storage material whose melting point is near or above the boiling point of water, it becomes difficult to keep the entire liquid at a temperature higher than the melting point of the heat-storage material. When a portion that reaches a temperature lower than the melting point of the material is generated, the heat storage material in that portion is solidified, and an emulsified dispersion having a uniform droplet diameter cannot be obtained.
On the other hand, a method of dispersing the heat storage material in water at a high temperature equal to or higher than the melting point of the heat storage material using a pressurized sealed container has been reported (for example, see Patent Document 2), but the apparatus is expensive. There was a problem of becoming.
Japanese Patent Laid-Open No. 2002-80835

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to use an expensive apparatus such as a pressure sealed container, even if a high-melting-point heat storage material is used. It is another object of the present invention to provide a method for producing a heat storage material microcapsule and a heat storage material microcapsule that are stable against long-term thermal history and shearing stress due to a pump or the like.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have easily formed particles by using the binder (A) and the aliphatic hydrocarbon heat storage material (C) under a certain condition, The present inventors have found that the above problems can be solved and have completed the present invention.

That is, the first method for producing the heat storage material microcapsule of the present invention has a vinyl copolymer having an average of two or more carboxyl groups in one molecule and a solubility parameter value of 6.5 to 9.0. a binder (a) comprising a polymer, a melting point of 40 to 150 ° C. der is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax, microcrystalline wax, 10 or more higher fatty acid carbon number, the number of carbon atoms At least one aliphatic hydrocarbon heat storage material (C) selected from the group consisting of esters of 10 or more higher fatty acids, higher alcohols having 10 or more carbon atoms and ethers of higher alcohols having 10 or more carbon atoms , Solubility in the binder (A) and the heat storage material (C) in the temperature range from 50 ° C. below the melting point of the heat storage material (C) to less than the melting point (gut of solute dissolved in 100 g of solvent) Number beam) each Ri der least 100 g, and, comprising an aromatic organic solvent and / or aliphatic organic solvent is, and carbon atoms in the alkyl group is 4 or more n- butanol, isobutanol , Sec-butanol, tert-butanol, n-pentanol, and at least one alkyl alcohol selected from the group consisting of isopentanol , methyl isobutyl ketone having 4 or more carbon atoms in the alkyl group, and n-amyl ketone Selected from the group consisting of at least one ketone selected from the group, n-butyl acetate having an alkyl group having 4 or more carbon atoms , isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate and butyl propionate at least one ester, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl Agent Le, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, at least one glycol ether selected from the group consisting of propylene glycol dimethyl ether and propylene glycol diethyl ether, benzene, toluene At least one aromatic hydrocarbon selected from the group consisting of xylene and ethylbenzene , exon aromatic naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) And reacting the curing agent (B) having an average of two or more epoxy groups that react with the carboxyl group of the binder (A) in the molecule and the carboxyl group in the binder (A). Features.
Further, the second method for producing the heat storage material microcapsule of the present invention has a vinyl copolymer having an average of two or more epoxy groups in one molecule and a solubility parameter value of 6.5 to 9.0. a binder (a) comprising a polymer, a melting point of 40 to 150 ° C. der is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax, microcrystalline wax, 10 or more higher fatty acid carbon number, the number of carbon atoms At least one aliphatic hydrocarbon heat storage material (C) selected from the group consisting of esters of 10 or more higher fatty acids, higher alcohols having 10 or more carbon atoms and ethers of higher alcohols having 10 or more carbon atoms , Solubility in the binder (A) and the heat storage material (C) in a temperature range from 50 ° C. below the melting point of the heat storage material (C) to less than the melting point (gram of solute dissolved in 100 g of solvent) ) Is Ri der least 100g respectively, and, comprising an aromatic organic solvent and / or aliphatic organic solvent is, and carbon atoms in the alkyl group is 4 or more n- butanol, isobutanol, sec -At least one alkyl alcohol selected from the group consisting of butanol, tert-butanol, n-pentanol and isopentanol, from the group consisting of methyl isobutyl ketone and n-amyl ketone having 4 or more carbon atoms in the alkyl group At least one selected from the group consisting of at least one selected ketone, n-butyl acetate having an alkyl group having 4 or more carbon atoms , isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate and butyl propionate. species esters, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether Ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, at least one glycol ether selected from the group consisting of propylene glycol dimethyl ether and propylene glycol diethyl ether, benzene, toluene, xylene And at least one aromatic hydrocarbon selected from the group consisting of ethylbenzene and exon aromatic naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) And reacting the epoxy group in the binder (A) with the curing agent (B) having an average of two or more carboxyl groups that react with the epoxy group of the binder (A) in one molecule. Features.

  Moreover, the microcapsule of the present invention is characterized by being produced by the above method for producing a heat storage material microcapsule.

  According to the present invention, since the particles are easily formed by using the binder (A) and the aliphatic hydrocarbon heat storage material (C) under certain conditions, even if a heat storage material having a high melting point is used. Providing a heat storage material microcapsule manufacturing method and a heat storage material microcapsule that do not require the use of expensive equipment such as pressurized airtight containers and that are stable against long-term thermal history and shear stress due to pumps, etc. it can.

  Hereinafter, the manufacturing method of the heat storage material microcapsule of this invention is demonstrated in detail. In the present specification and claims, “%” for concentration, content, filling amount and the like represents a mass percentage unless otherwise specified.

As described above, the present invention relates to a binder (A) comprising a vinyl copolymer having an average of two or more carboxyl groups in one molecule and a solubility parameter value of 6.5 to 9.0. , a melting point of 40 to 150 ° C. der is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, esters of paraffin wax, microcrystalline wax, having 10 or more higher fatty acids carbon, 10 or more higher fatty acid carbons, carbon At least one aliphatic hydrocarbon heat storage material (C) selected from the group consisting of higher alcohols of several tens or more and ethers of higher alcohols of ten or more carbons is 50 from the melting point of the heat storage material (C). der in a temperature range of ℃ from a low temperature to below the melting point, (the number of grams solute dissolved in a solvent 100g) solubility the binder (a) and the heat storage material (C) is more than 100g each And, comprising the aromatic organic solvent and / or aliphatic organic solvent is, and the carbon number of 4 or more n- butanol alkyl group, isobutanol, sec- butanol, tert- butanol, n -At least one alkyl alcohol selected from the group consisting of pentanol and isopentanol, at least one ketone selected from the group consisting of methyl isobutyl ketone and n-amyl ketone having 4 or more carbon atoms in the alkyl group At least one ester selected from the group consisting of n-butyl acetate having an alkyl group with 4 or more carbon atoms , isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate and butyl propionate , methyl cellosolve, Ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, at least one glycol ether selected from the group consisting of propylene glycol dimethyl ether and propylene glycol diethyl ether, benzene, toluene, xylene and ethylbenzene At least one aromatic hydrocarbon selected from the group consisting of exon aromatic naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) And by reacting a curing agent (B) having an average of two or more epoxy groups that react with the carboxyl group of the binder (A) in one molecule and the carboxyl group in the binder (A), Alternatively, the binder (A) comprising a vinyl copolymer having an average of two or more epoxy groups in one molecule and a solubility parameter value of 6.5 to 9.0, and a melting point of 40 to 150 ° C. der is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax, microcrystalline wax, having 10 or more higher fatty acid carbons, esters having 10 or more higher fatty acid carbon number of 10 or more higher alcohol carbon At least one aliphatic hydrocarbon-based heat accumulating material selected from the group consisting of ethers of the fine carbon number 10 or more higher alcohols and (C), but below the melting point from 50 ° C. lower than the melting point of the heat storage material (C) in a temperature range of up state, and are solubility (gram solute dissolved in a solvent 100g) or more 100g respectively for the binder (a) and the heat storage material (C), and an aromatic organic solvent and / or Ri comprising the aliphatic organic solvent, and, having 4 or more carbon atoms of n- butanol alkyl group, isobutanol, sec- butanol, tert- butanol, from the group consisting of n- pentanol and isopentanol at least one alkyl alcohol selected, small number of carbon atoms in the alkyl group is selected from the group consisting of 4 or more methyl isobutyl ketone and n- amyl ketone With one ketones, acetate n- butyl 4 or more carbon atoms in the alkyl group, isobutyl acetate, n- amyl, isoamyl acetate, at least one ester selected from the group consisting of hexyl acetate and butyl propionate At least selected from the group consisting of methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether and propylene glycol diethyl ether one glycol ether, benzene, toluene, at least one aromatic hydrocarbons selected from the group consisting of xylenes and ethylbenzene, et Xon Aromatic Naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) By reacting the curing agent (B) having an average of two or more carboxyl groups in one molecule that react with the epoxy group of the binder (A) with the epoxy group in the binder (A), Manufacturing heat storage material microcapsules.

  Accordingly, even if a heat storage material having a high melting point is used, it is not necessary to use an expensive device such as a pressurized sealed container, and the manufacture of microcapsules is facilitated. In particular, it is suitable as a method for producing a heat storage material microcapsule containing a high-melting-point heat storage material, and the obtained heat storage material microcapsule exhibits excellent durability against a long-term heat history, shear stress due to a pump or the like.

Details of the present invention will be specifically described below.
First, the binder (A) having an average of two or more functional groups in one molecule will be described.
As the binder (A), various resins such as a vinyl copolymer, a polyester resin, and an epoxy resin can be used. In particular, it is preferable to use a vinyl-based copolymer because the obtained heat storage material microcapsules have good heat resistance, water resistance and mechanical strength, and are excellent in durability.

Moreover, there is no restriction | limiting in particular as a functional group which the said binder (A) has, A hydroxyl group, a carboxyl group, an epoxy group, a hydrolysable silyl group, an amide group, an acid anhydride group, (block) isocyanate group etc. are mentioned. Since the obtained heat storage material microcapsule is excellent in heat resistance, water resistance and mechanical strength, a functional group according to a hydroxyl group, a carboxyl group, an epoxy group or a hydrolyzable silyl group, and any combination thereof. Is preferred.
In addition, the said binder (A) may have 2 or more types of functional groups. The binder (A) may be composed of only one kind of resin or a blend of two or more kinds of resins.

  Furthermore, it is essential that the binder (A) has an average of two or more functional groups in one molecule. Among them, heat resistance, water resistance, mechanical properties of the obtained heat storage material microcapsules are particularly important. In order to make the strength good and to make it excellent in durability, those having an average of 3 to 50 functional groups in one molecule are preferable. Moreover, what has 10-30 functional groups on average in 1 molecule is more preferable.

  As a method for preparing the binder (A), when the binder (A) is a vinyl copolymer, the preparation method is not particularly limited, and various methods can be used. Among them, the most convenient method is the so-called solution polymerization method in which each of these monomers is polymerized in an organic solvent using a vinyl monomer containing a functional group and other vinyl monomers. Recommended because there is.

  When preparing a vinyl copolymer by the above solution polymerization method, the whole amount of vinyl monomers to be used, a polymerization initiator and an organic solvent are collectively charged into a reactor and polymerized, or vinyl monomers The remaining vinyl monomers and the polymerization initiator were added to the reactor charged with a part of the organic solvent and the organic solvent, respectively, continuously or in a divided manner for polymerization, or only the organic solvent was charged. It is possible to apply a method in which the total amount of vinyl monomers to be used and the polymerization initiator are respectively added to the reactor and polymerized by adding them in portions.

  Examples of the functional group of the vinyl copolymer include a hydroxyl group, a carboxyl group, an epoxy group, a hydrolyzable silyl group, an amide group, an acid anhydride group, and a (block) isocyanate group. In particular, since the heat storage, water resistance, mechanical strength of the heat storage material microcapsule obtained is easy and excellent in durability, the hydroxyl group, carboxyl group, epoxy group or hydrolyzable silyl group, and It is desirable that these functional groups are arbitrarily combined.

  As vinyl monomers having a functional group, when the functional group is a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Hydroxyl-containing (meth) acrylates such as 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. An addition reaction product of (meth) acrylates as described above and ε-caprolactone;

2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl Hydroxyl group-containing vinyl ethers such as vinyl ether; addition reaction products of vinyl ethers as listed above with ε-caprolactone;

2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, Hydroxyl-containing allyl ethers such as 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl ether, 6-hydroxyhexyl (meth) allyl ether; various allyl ethers as listed above And an addition reaction product of ε-caprolactone.

  When the functional group is a carboxyl group, for example, carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; monomethyl fumarate, monoethyl fumarate, monobutyl fumarate , Monoisobutyl fumarate, mono tert-butyl fumarate, monohexyl fumarate, monooctyl fumarate, mono-2-ethylhexyl fumarate, monomethyl maleate, monoethyl maleate, monobutyl maleate, monoisobutyl maleate, mono tert maleate Monoesters of α, β-unsaturated dicarboxylic acids such as butyl, monohexyl maleate, monooctyl maleate, mono-2-ethylhexyl maleate and the like and monohydric alcohols having 1 to 18 carbon atoms; monomethyl itaconate; Monoethyl itaconate, ita Examples include itaconic acid monoalkyl esters such as monobutyl konate, monoisobutyl itaconate, monohexyl itaconate, monooctyl itaconate, mono-2-ethylhexyl itaconate, and the like.

  When the functional group is an epoxy group, for example, epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, glycidyl vinyl ether, and allyl glycidyl ether; (2-oxo-1 , 3-oxolane) methyl (meth) acrylate and other (2-oxo-1,3-oxolane) group-containing vinyl monomers; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( And alicyclic epoxy group-containing vinyl monomers such as (meth) acrylate and 3,4-epoxycyclohexylethyl (meth) acrylate.

  When the functional group is a hydrolyzable silyl group, for example, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane And hydrolyzable silyl group-containing vinyl monomers.

  Furthermore, other copolymerizable vinyl monomers can be used as required. Examples of such other copolymerizable monomers include methyl (meth) acrylate and (meth) acrylic. Ethyl acetate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate or (meth) acrylate n -Hexyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic such as dodecyl, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Acid alkyl esters;

Alkyl carbitol (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate; isobornyl (Meth) acrylates such as (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate;

Α-olefins such as ethylene, propylene, butene-1; various halogenated olefins (halo-olefins) such as vinyl chloride and vinylidene chloride, excluding fluoroolefins; styrene, α-methylstyrene, vinyltoluene, etc. Aromatic vinyl monomers;

Dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, etc. Diesters of saturated dicarboxylic acids and monohydric alcohols having 1 to 18 carbon atoms;

Acid anhydride group-containing vinyl monomers such as maleic anhydride, itaconic anhydride, citraconic anhydride, (meth) acrylic anhydride, and tetrahydrophthalic anhydride;

Diethyl-2- (meth) acryloyloxyethyl phosphate, dibutyl-2- (meth) acryloyloxybutyl phosphate, dioctyl-2- (methacryloyloxyethyl phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate Phosphoric ester group-containing vinyl monomers such as

Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched (branched) aliphatic vinyl carboxylates with 9 carbon atoms, carbon atoms Aliphatic vinyl carboxylates such as branched aliphatic vinyl carboxylate having several tens, branched aliphatic vinyl carboxylate having 11 carbon atoms, and vinyl stearate;

Examples thereof include vinyl esters of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, and vinyl p-tert-butylbenzoate.

  As the total amount used of various functional group-containing vinyl monomers as exemplified above, the heat storage material microcapsule obtained has excellent heat resistance, water resistance, mechanical strength, and excellent durability. Therefore, the range of 2 to 50% of the total amount of vinyl monomers to be used is preferable, and the range of 5 to 20% is more preferable.

  Various organic solvents can be used as the organic solvent used in the preparation of the vinyl copolymer. Examples of the organic solvent include alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and isopentanol;

Glycol ethers such as methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Exon Aromatic Naphtha No. Mixed hydrocarbons containing aromatic hydrocarbons such as 2 (made by Exxon USA); aliphatic hydrocarbons such as n-pentane, n-hexane and n-octane; Isopar C, Isopar E, Exol DSP 100/140 , Exol D30 (all manufactured by US Exxon Corporation), IP hydrocarbon 1016 (manufactured by Idemitsu Petrochemical Co., Ltd.), and other mixed hydrocarbons containing aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and other alicyclic rings Group hydrocarbons;

Ethers such as tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, n-amyl ketone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Examples thereof include esters such as butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate, and butyl propionate.

  As the polymerization initiator used in the preparation of the vinyl copolymer, various compounds can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-methyl Butyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis- 4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2,2'-azobis (2-methyl-propionamide) 2 water Azo compounds such as Japanese, 2,2′-azobis [2- (2-imidazolin-2-yl) propene] or 2,2′-azobis (2,2,4-trimethylpentane);

Benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, potassium persulfate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert- Butyl peroxyisobutyrate, 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl peroxylaurate, tert-butyl peroxyisophthalate, tert-butyl peroxyacetate , Tert-butyl peroxybenzoate, dicumyl peroxide or ketone peroxides such as di-tert-butyl peroxide; peroxyketals; hydroperoxides; dialkyl Okishido like; diacyl peroxides like; peroxy esters; peroxydicarbonates like; hydrogen peroxide and the like.

  The number average molecular weight of the vinyl copolymer is suitably in the range of 1,000 to 200,000. Among these, it is preferable that it exists in the range of 5,000-100,000. When the number average molecular weight of the vinyl copolymer is within the above-described range, a heat storage material microcapsule having excellent durability can be obtained.

  When the binder (A) is a polyester resin, the preparation method for obtaining the polyester resin is not particularly limited, and various methods can be used that are produced by a method of condensing a polyhydric alcohol and a polybasic acid.

  As the functional group, one or both of a carboxyl group and a hydroxyl group are preferably employed from the viewpoint of ease of preparation.

  Various compounds can be used as polyhydric alcohols and polybasic acids that can be used as raw materials. By adjusting the amount of these polyhydric alcohol and polybasic acid used, a polyester resin having one or both of a carboxyl group and a hydroxyl group can be obtained.

  First, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , Neopentyl glycol, triethylene glycol, bis-hydroxyethyl terephthalate, cyclohexanedimethanol, octanediol, diethylpropanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentane Diol, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, grease Phosphorus, pentaerythritol, tris-hydroxyethyl isocyanurate, etc. hydroxypivalic valyl hydroxy pivalate and the like.

  On the other hand, examples of the polybasic acid include terephthalic acid, isophthalic acid, phthalic acid, methyl terephthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof; succinic acid, adipic acid, azelaic acid, and sebacic acid. Or an anhydride thereof; maleic acid, itaconic acid, or an anhydride thereof; fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, or an anhydride thereof; cyclohexanedicarboxylic acid Examples thereof include acid and 2,6-naphthalenedicarboxylic acid.

  Furthermore, as a raw material, a compound having both a carboxyl group and a hydroxyl group in one molecule such as dimethanolpropionic acid and hydroxypivalate; “Cardura E10” (a glycidyl ester of a branched aliphatic carboxylic acid manufactured by Shell of the Netherlands), etc. Mono-epoxy compounds; monohydric alcohols such as methanol, propanol, butanol and benzyl alcohol; monovalent basic acids such as benzoic acid and p-tert-butylbenzoic acid; fatty acids such as castor oil fatty acid, coconut oil fatty acid and soybean oil fatty acid Etc. can also be used.

  As the polyester resin obtained by using various polyhydric alcohols, polybasic acids, and other raw materials as mentioned above, the total of acid value and hydroxyl value is 10 to 250 mgKOH / mg. g; the same shall apply hereinafter), and the number average molecular weight is preferably in the range of 500 to 10,000.

  When the sum of the acid value and the hydroxyl value is within the above range, a heat storage material microcapsule having excellent mechanical properties can be obtained. Moreover, if the number average molecular weight is within the above-described range, a heat storage material microcapsule having excellent durability can be obtained.

  The structure of the polyester resin is not particularly limited as long as it is within the range of various characteristic values of the resin as described above, and may have a branched structure or a linear structure.

In the present invention, the measurement of the number average molecular weight of the vinyl copolymer or polyester resin is obtained by polystyrene conversion using a gel permeation chromatograph under the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. Guard column H _XL- H
+ Tosoh Corporation TSKgel G5000H _XL
+ Tosoh Corporation TSKgel G4000H _XL
+ Tosoh Corporation TSKgel G3000H _XL
+ Tosoh Corporation TSKgel G2000H _XL
Detector: RI (differential refractometer)
Data processing; Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 1.0 ml / min Standard: Polystyrene sample; 0.4% tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 μl)

  The epoxy resin that can be used as the binder (A) is not particularly limited, and examples thereof include an epoxy resin such as polyglycidyl ether of bisphenol-A.

  In the present invention, the binder (A) preferably has an affinity for the aliphatic hydrocarbon heat storage material (C).

The affinity of the binder (A) with the aliphatic hydrocarbon heat storage material (C) is greatly influenced by the solubility parameter of the binder (A).
Here, the solubility parameter of the binder (A) can be determined by the following method.

0.5 g of the binder (A) as a sample resin is weighed into a 100 ml Meyer flask, and 10 ml of tetrahydrofuran (THF) is added to dissolve the resin. While the dissolved solution is kept at a liquid temperature of 25 ° C. and stirred with a magnetic stirrer, hexane is added dropwise using a 50 ml burette, and the dropping amount (v _h ) of the point at which the solution becomes turbid (turbid point) is determined. Ask.

Next, the dropping amount (v _d ) at the cloud point when deionized water is used instead of hexane is determined.

From v _h and v _d , the solubility parameter value δ of the resin is SUH, CLARKE [J. Polym. Sci. A-1, Vol. 5, 1671-1681 (1967)] can be obtained as follows.
δ = [(V _mh ) ^(1/2) · δ _mh + (V _md ) ^(1/2) · δ _md ] / [(V _mh ) ^(1/2) + (V _md ) ^(1/2) ]
here,
V _mh = (V _h · V _t ) / (φ _h · V _t + φ _ht · V _h ),
V _md = (V _d · V _t ) / (φ _d · V _t + φ _dt · V _d )
δ _mh = φ _h · δ _h + φ _ht · δ _t ,
δ _md = φ _d · δ _d + φ _dt · δ _t
φ _h , φ _ht ; volume fraction of hexane and THF at the cloud point when hexane is used as the titration solvent φ _d , φ _dt ; deionized water at the cloud point when deionized water is used as the titration solvent , THF volume fraction [φ _h = v _h / (v _h +10), φ _ht = 10 / (v _h +10), φ _d = v _d / (v _d +10), φ _dt = 10 / (v _d +10)] [where 10 is the use volume of THF (10 ml). ]
δ _h , δ _d , δ _t ; Solubility parameter values of hexane, deionized water, and THF V _h , V _d , V _t ; Molecular volume of hexane, deionized water, and THF (ml / mol)

  The solubility parameter value of the binder (A) is preferably in the range of 6.5 to 9.0, and more preferably in the range of 7.0 to 9.0. If the value of the solubility parameter of the binder (A) is in the range of 6.5 to 9.0, there is sufficient affinity between the binder (A) and the aliphatic hydrocarbon heat storage material (C). In addition, since the separation of the binder (A) and the aliphatic hydrocarbon heat storage material (C) can be prevented during the precipitation of these mixtures, a heat storage material microcapsule having excellent mechanical strength can be produced. It is preferable to be within a range of ˜9.0, and it is more preferable to be within a range of 7.0 to 9.0.

  Next, the curing agent (B) preferably has an average of two or more functional groups that react with the functional group of the binder (A) in one molecule, and is appropriately selected and used.

  As the curing agent (B), when the functional group of the binder (A) is a hydroxyl group, a typical example is a block polyisocyanate compound or an acid anhydride-containing group vinyl copolymer. it can.

  Examples of the block polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclic aliphatic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate. Organic diisocyanates such as aromatic diisocyanates; adducts of the above organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins (polyester polyols) or water; polymers of the above organic diisocyanates (isocyanurate type) Including polyisocyanate compounds) and various polyisocyanate compounds such as isocyanate and biuret bodies And of the form obtained allowed blocking Te than the dosage, uretdione bond as a structural unit, such as a so-called self-blocked polyisocyanate compound.

  When the functional group of the binder (A) is a carboxyl group, examples of the curing agent (B) include epoxy resins such as polyglycidyl ether of bisphenol A; epoxy group-containing acrylic resins such as glycidyl group-containing acrylic resins; Polyglycidyl ethers of polyhydric alcohols such as 1,6-hexanediol, trimethylolpropane and trimethylolethane; phthalic acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyro Polyglycidyl esters of polycarboxylic acids such as merit acid; alicyclic epoxy group-containing compounds such as bis (3,4-epoxycyclohexyl) methyl adipate; hydroxyamides such as triglycidyl isocyanurate and β-hydroxyalkylamide Etc. That.

  Furthermore, when the functional group of the binder (A) is an epoxy group, examples of the curing agent (B) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. , Aicosane diacid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexene-1,2-dicarboxylic acid, trimellitic acid, Examples include pyromellitic acid, acid anhydrides and urethane-modified products thereof, carboxyl group-containing vinyl copolymers, and carboxyl group-containing polyester resins.

  Furthermore, when the functional group of the binder (A) is a hydrolyzable silyl group, examples of the curing agent (B) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and glycerin. Polyhydric alcohols; Hydrolyzable silyl group-containing compounds such as trimethoxysilane and triethoxysilane; hydroxyl group-containing vinyl copolymers, hydroxyl group-containing polyester resins, and the like.

  The curing agent (B) may have two or more functional groups. Moreover, a hardening | curing agent (B) may be individual, or may use 2 or more types together.

  The blending ratio of the binder (A) and the curing agent (B) is preferably in the range of (A) / (B) = 2/1 to 1/2 in terms of the equivalent ratio of functional groups. More preferably, it is in the range of ½. If the blending ratio is within the above range, a microcapsule film having excellent mechanical strength can be formed.

  The heat storage material microcapsules obtained by reacting the binder (A) with the curing agent (B) have good dispersibility in a heat transport medium composed of water, ethylene glycol, a mixed solvent thereof or the like. Therefore, it is preferable to use a combination in which the reaction product of the binder (A) and the curing agent (B) has self-emulsifying properties.

  A combination of the reaction product of the binder (A) and the curing agent (B) having a self-emulsifying property is not particularly limited, but among them, the reaction of the binder (A) and the curing agent (B). A combination in which the product has an acid group neutralized with a basic compound is preferred. Specifically, as one or both of the binder (A) and the curing agent (B), a combination using an acid group such as a carboxyl group may be used. In order to do this, neutralization with a basic compound may be performed during or after these reactions.

  The combination in which the reaction product of the binder (A) and the curing agent (B) has self-emulsifying properties is the reaction of the binder (A) and the curing agent (B) with the reaction of an acid group and an epoxy group. Since the reaction between the acid group and the epoxy group is promoted, the acid for imparting self-emulsifying property to the reaction product in the reaction of the binder (A) and the curing agent (B). It is preferred to simultaneously carry out neutralization of the group with a basic compound.

  In addition, when the said binder (A) has a carboxyl group as a functional group for making it react with the said hardening | curing agent (B), it is self in the reaction material of the said binder (A) and the said hardening | curing agent (B). In order to obtain a combination that imparts emulsifying properties, it is necessary to make the carboxyl group in the binder (A) excessive with respect to the group that reacts with the carboxyl group in the curing agent (B). For example, the blending ratio of the binder (A1) having a carboxyl group and the curing agent (B) is preferably in the range of (A1) / (B) = 20/1 to 1.3 / 1 in terms of equivalent ratio.

  Conversely, when the curing agent (B) has a carboxyl group as a functional group for reacting with the binder (A), the reaction between the binder (A) and the curing agent (B). In order to give a product a combination that imparts self-emulsifying properties, it is necessary to make the carboxyl group in the curing agent (B) excessive with respect to the group that reacts with the carboxyl group in the binder (A). For example, the blending ratio of the binder (A) and the curing agent (B1) having a carboxyl group is preferably set to an equivalent ratio of (A) / (B1) = 1/20 to 1 / 1.3.

Next, as the aliphatic hydrocarbon heat storage material (C) used in the present invention, for example, an aliphatic hydrocarbon having 10 to 20 carbon atoms, paraffin wax (oil or natural gas is used as a raw material under reduced pressure distillation distillate) Produced by separating and refining from a solid wax at normal temperature; about 20 to 40 carbon atoms), microcrystalline wax (petroleum is used as a raw material and separated from vacuum distillation residue oil or heavy distillate oil and solid at normal temperature. Typical examples include aliphatic hydrocarbons such as waxes of about 30 to 60 carbon atoms, higher fatty acids having 10 or more carbon atoms and esters thereof, higher alcohols having 10 or more carbon atoms and ethers thereof.
Among these aliphatic hydrocarbon heat storage materials (C), those having a melting point of 40 to 150 ° C. control the precipitation temperature of particles containing the binder (A) and the aliphatic hydrocarbon heat storage material (C). It is preferable because it can be easily performed. Furthermore, paraffin wax and microcrystalline wax are both particularly preferable because they both have a high heat storage capacity, are excellent in performance as a heat storage material, have high safety, and have a melting point corresponding to the purpose of use.

  As such paraffin wax, for example, “HNP-9”, “FNP-0090”, “FT115” (all manufactured by Nippon Seiki Co., Ltd.); as microcrystalline wax, “Hi-Mic-1090”, “Hi-Mic-1070” (all manufactured by Nippon Seiki Co., Ltd.) and the like are exemplified.

  Moreover, these aliphatic hydrocarbon heat storage materials (C) can be used in combination of two or more. If necessary, it is also possible to adjust the thermal conductivity, specific gravity and the like by adding metal powder, various pigments and the like.

  The amount of the aliphatic hydrocarbon heat storage material (C) used is the weight ratio of the aliphatic hydrocarbon heat storage material (C) to the total of the binder (A) and the curing agent (B) [(C) / (A + B )] Is preferably in the range of 95/5 to 50/50. A range of 90/10 to 75/25 is more preferable. If the weight ratio is within the above range, a microcapsule having excellent heat storage performance, excellent heat resistance, water resistance, mechanical strength, and excellent durability can be obtained.

  Next, as the organic solvent (D) used in the present invention, the binder (A) and the aliphatic hydrocarbon heat storage material (C) are heated at a temperature below the melting point of the aliphatic hydrocarbon heat storage material (C). When the organic solvent solution (I) is cooled under mixing conditions, the binder (A) and the aliphatic hydrocarbon heat storage material (C As long as it is an organic solvent that precipitates a mixture of)), it may be composed of only one organic solvent or a mixed organic solvent composed of two or more organic solvents. Precipitation of mixture of aliphatic hydrocarbon heat storage material (C) is easy, and during this precipitation, separation of binder (A) and aliphatic hydrocarbon heat storage material (C) can be prevented, and heat storage material micro excellent in mechanical strength Because capsules can be manufactured efficiently Any temperature within the temperature range lower than the melting point of the aliphatic hydrocarbon heat storage material (C) [usually a temperature range lower than the melting point and close to the melting point, such as an aliphatic hydrocarbon heat storage material (C ) Below the melting point to a temperature lower than the melting point by 50 ° C.], the solubility (grams of solute dissolved in 100 g of solvent) in the binder (A) and the aliphatic hydrocarbon heat storage material (C) is 100 g. Within the temperature range below the melting point of the organic solvent (D1) and the aliphatic hydrocarbon heat storage material (C), the solubility in the binder (A) and the aliphatic hydrocarbon heat storage material (C) is 10 g or less, respectively. A mixed organic solvent of the organic solvent (D2) is preferable.

  In selecting the organic solvent (D1), the organic solvent (D1) preferably has an affinity for both the binder (A) and the aliphatic hydrocarbon heat storage material (C).

  Alcohols, ketones, esters, glycol ethers, aromatic organic solvents, aliphatic organic solvents (including cycloaliphatic organic solvents, the same applies hereinafter) having an alkyl group with 4 or more carbon atoms are described above. The affinity between the binder (A) and the aliphatic hydrocarbon heat storage material (C) is high, and the aliphatic hydrocarbon heat storage material (C) can be dissolved within a temperature range below its melting point, Since microcapsules can be produced under low temperature conditions, they can be preferably used as the organic solvent (D1).

  Among the organic solvents (D1), the aromatic organic solvent and the aliphatic organic solvent have higher affinity with the aliphatic hydrocarbon heat storage material (C), and in the presence of the organic solvent, Since the mixing of the binder (A) and the aliphatic hydrocarbon heat storage material (C) is easy and the mechanical strength of the resulting microcapsules is increased, the organic solvent (D1) is an aromatic organic solvent or an aliphatic organic solvent. Particularly preferred is an organic solvent containing one or both of the solvents.

  Examples of the organic solvent (D1) include alkyl alcohols having 4 or more alkyl groups such as n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and isopentanol; Ketones having 4 or more alkyl groups such as methyl isobutyl ketone and n-amyl ketone; n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, butyl propionate, etc. Esters having 4 or more carbon atoms;

Glycol ethers such as methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Exon Aromatic Naphtha No. 2 (manufactured by Exxon, USA), etc., mixed hydrocarbons containing aromatic hydrocarbons; aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane; Isopar C, Isopar E, Exol DSP100 / 140, Exol D30 (all manufactured by Exxon, USA), IP Solvent 1016 (manufactured by Idemitsu Petrochemical Co., Ltd.), etc., mixed hydrocarbons containing aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. And cycloaliphatic hydrocarbons.

  The organic solvent (D2) has a solubility in the binder (A) and the aliphatic hydrocarbon heat storage material (C) of 10 g within a temperature range below the melting point of the aliphatic hydrocarbon heat storage material (C). In the following organic solvents, that is, below the melting point of the aliphatic hydrocarbon heat storage material (C), most of the binder (A) and the aliphatic hydrocarbon heat storage material (C) are organic solvents that do not dissolve. Yes, by using this organic solvent (D2) in combination with the organic solvent (D1), the binder (A) during precipitation of the mixture of the binder (A) and the aliphatic hydrocarbon heat storage material (C). And the separation of the aliphatic hydrocarbon heat storage material (C), and the gelation of the entire system when the binder (A) and the curing agent (B) in the precipitated particles are reacted can be prevented. Thermal storage microphone Capsule is obtained.

  Examples of the organic solvent (D2) include alcohols having 3 or less carbon atoms such as methanol, ethanol, n-propanol and isopropanol; polyhydric alcohols such as ethylene glycol and propylene glycol.

  Furthermore, in the present invention, an organic solvent (D3) other than those described above may be used in combination, if necessary, but the amount used is usually preferably 20% or less with respect to the total of the organic solvents (D1) to (D3). Examples of the organic solvent (D3) include ethers such as tetrahydrofuran, dioxane, diisopropyl ether and di-n-butyl ether; ketones having an alkyl group with 3 or less alkyl groups such as acetone and methyl ethyl ketone; methyl acetate and acetic acid. Examples thereof include esters having an alkyl group with 3 or less carbon atoms, such as ethyl, n-propyl acetate, isopropyl acetate, and ethyl propionate.

  The organic solvent used in the preparation of the binder (A) or the curing agent (B) by solution polymerization or the like is not separated and is a part of the organic solvent (D1), (D2) or (D3). Or they can be used as a whole. In addition, the organic solvents (D1), (D2), and (D3) may be used by mixing two or more organic solvents.

  When the mixed organic solvent of the organic solvents (D1) and (D2) is used as the organic solvent (D), these use ratios are any in a temperature range below the melting point of the aliphatic hydrocarbon heat storage material (C). The ratio of the solubility to the binder (A) and the aliphatic hydrocarbon heat storage material (C) (grams of solute dissolved in 100 g of solvent) may be 100 g or more, but the weight ratio (D1 / D2) is preferably in the range of 10/90 to 80/20. Moreover, it is more preferable that it exists in the range used as 30 / 70-60 / 40.

  Further, the content of the organic solvent (D) in the organic solvent solution (I) is such that the binder (A) and the aliphatic hydrocarbon heat storage material (C) are melted by the aliphatic hydrocarbon heat storage material (C). It is sufficient if it is more than the amount necessary to dissolve within a temperature range of less than, and is not particularly limited, but solid content [total of binder (A), curing agent (B) and aliphatic hydrocarbon heat storage material (C) It is preferable that the concentration is within a range of 5 to 70%. Moreover, it is more preferable that it is within the range of 10 to 40%.

  If the solvent composition of the organic solvent solution (I) and the solid content concentration are within the above-mentioned range, the aliphatic hydrocarbon heat storage material (C) does not aggregate at the time of production, or the entire system does not gel. A target heat storage material microcapsule can be efficiently produced.

  In order to manufacture a heat storage material microcapsule by the manufacturing method of the present invention, a binder (A) having two or more functional groups in one molecule and an aliphatic hydrocarbon heat storage material (C) are used as an organic solvent (D). Mixing conditions at a temperature lower than the melting point of the aliphatic hydrocarbon heat storage material (C) after preparing the organic solvent solution (I) which is dissolved and further contains various additives as required Below, it cools below to the precipitation temperature of the mixture of the said binder (A) and an aliphatic hydrocarbon thermal storage material (C), and the particle | grains containing the said binder (A) and an aliphatic hydrocarbon thermal storage material (C) ( What is necessary is just to make it react with the hardening | curing agent (B) which reacts with the functional group in the said binder (A), after depositing E).

  In the step of precipitating the particles (E), the mixing conditions are very important. If the conditions are not appropriate, the particles (E) are aggregated and solidified during cooling, and heat storage material microcapsules cannot be obtained. Sometimes.

As the mixing conditions, the stirring speed and cooling speed of the system are important. For example, when a stirrer having a rotary stirring blade such as a turbine blade or a paddle blade is used, the organic solvent solution (I) is 150 rpm or more. More preferably, while mixing at a stirring speed of 250 rpm or more, cooling is preferably performed at a cooling rate of 1 to 50 ° C./hr, and more preferably gradually cooled at a cooling rate of 1 to 20 ° C./hr.
The precipitated particles (E) are particles comprising a mixture of the binder (A) and the aliphatic hydrocarbon heat storage material (C), but the mixed state is not necessarily uniform. For example, in the case of particles having an inclined structure having a high content of the binder (A) on the surface side, it is preferable because a heat storage material microcapsule with more excellent mechanical strength can be obtained.

  A dispersion liquid of the heat storage material microcapsules can be obtained by reacting the binder (A) and the curing agent (B) at an arbitrary temperature lower than the precipitation temperature under the mixing conditions as described above.

As a method of adding the curing agent (B) to the organic solvent solution (I),
1) A curing agent (B) is added in advance to the organic solvent solution (I) in which the binder (A) and the aliphatic hydrocarbon heat storage material (C) are dissolved, and the organic solvent solution (I) is mixed. And cooling the binder to precipitate particles containing the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C), and then reacting the binder (A) and the curing agent (B),
2) After cooling the organic solvent solution (I) to precipitate particles containing the binder (A) and the aliphatic hydrocarbon heat storage material (C), the curing agent (B) is added to react with the binder (A). How to
Any method can be used.
In addition, a part of the curing agent (B) is added and mixed in advance with the organic solvent solution (I) in which the binder (A) and the aliphatic hydrocarbon heat storage material (C) are dissolved. After cooling I) and precipitating particles containing the binder (A), a part of the curing agent (B) and the aliphatic hydrocarbon heat storage material (C), the remaining curing agent (B) is added, You may make a binder (A) and a hardening | curing agent (B) react.
In this case, the reaction condition of the binder (A) and the curing agent (B) is not particularly limited as long as the binder (A) and the curing agent (B) are sufficiently reacted. The temperature is in the range of 15 ° C. lower than the precipitation temperature of the particles to less than the precipitation temperature, and the reaction time is usually 1 to 40 hours, preferably 5 to 20 hours.

  In the case of the method 1), since the binder (A) and the curing agent (B) are mixed in advance, the reaction between the binder (A) and the curing agent (B) is promptly performed. Can do. Moreover, since the reaction of the binder (A) and the curing agent (B) occurs not only on the particle surface but also inside the particle, internally crosslinked particles can be formed, and the mechanical strength of the particles can be improved.

  In the case of the above method 2), the reaction of the binder (A) and the curing agent (B) can selectively proceed on the particle surface to form a firm film.

  However, in the case of the above method 1), since the reaction between the binder (A) and the curing agent (B) gradually proceeds even before the precipitation of particles, the curing agent (I) in the organic solvent solution (I) The time from the addition of B) to the precipitation of particles, the concentration of the functional groups in the binder (A) and the curing agent (B), the total of the binder (A) and the curing agent (B) in the organic solvent solution (I). The concentration may be adjusted as appropriate so that the reaction between the binder (A) and the curing agent (B) does not proceed greatly until the particles are precipitated, and the process may be shifted to a step of depositing the particles immediately after dissolving the curing agent (B). preferable. If the reaction between the binder (A) and the curing agent (B) proceeds greatly before the particles are precipitated, the entire system may gel and the desired heat storage material microcapsules may not be obtained.

  During the reaction of the binder (A) and the curing agent (B), the temperature may or may not be kept constant, but the heat storage material microcapsule having a more uniform film is obtained by reacting at a constant temperature. Since it is obtained, it is preferable. In this reaction, a curing catalyst may be used.

  The heat storage material microcapsule dispersion thus obtained is obtained by removing part or all of the organic solvent (D) as necessary, and then the obtained heat storage material microcapsule or the dispersion liquid is mixed with water, ethylene glycol, a mixed solvent thereof or the like. And added to the heat transport medium.

  In addition, when the organic solvent containing the organic solvent (D1) is used as the organic solvent (D), it is necessary to remove the organic solvent (D1). If the organic solvent (D1) is not removed, aliphatic carbonization is required. The melting point and freezing point of the hydrogen-based heat storage material (C) may change, and the phase transition of the heat storage material may not occur in the target temperature range, and the heat efficiency of the heat transfer system cannot be improved.

  The means for removing a part of the organic solvent (D) from the heat storage material microcapsule dispersion is not particularly limited, and various methods such as distillation can be used. Moreover, there is no restriction | limiting in particular as a means to remove and solidify all the organic solvents (D) from a thermal storage material microcapsule dispersion, Room temperature drying, heating forced drying, vacuum drying, freeze drying, spray drying, pressurization Various methods such as filtration and suction filtration can be used, and two or more methods may be used in combination. Among them, the spray drying method is recommended because it has a high processing capacity per unit time, and can remove organic solvents and collect solid particles in one step.

  The apparatus used for spray drying may be any device that can remove the organic solvent from the sprayed heat storage material microcapsule dispersion. For example, the sprayed heat storage material microcapsule dispersion is brought into contact with the heat source gas to form the organic solvent. A spray-drying device that volatilizes can be used. Since the organic solvent is volatilized, it is desirable that the apparatus has explosion-proof specifications. Further, from the viewpoint of keeping the vapor content of the solvent in the heat source gas used for drying the sprayed heat storage material microcapsule dispersion, it is desirable to provide a solvent recovery device.

  In the case of using a spray drying apparatus in which the sprayed heat storage material microcapsule dispersion is brought into contact with the heat source gas to volatilize the organic solvent, the contact method of the heat storage material microcapsule dispersion and the heat source gas is not particularly limited and is usually used. Any method such as a cocurrent type, a countercurrent type, and a cocurrent / countercurrent type may be used. The pressure in the apparatus may be normal pressure, reduced pressure or increased pressure, and is not particularly limited.

  As the spraying method of the heat storage material microcapsule dispersion, any of the commonly used ones such as a rotating disk type, a two-fluid nozzle type, and a pressure nozzle type can be used.

  Moreover, what is necessary is just to determine suitably the non-volatile content density | concentration of the thermal storage material microcapsule dispersion at the time of spray-drying according to the specification of a spray-drying apparatus, and the conditions for spray-drying.

  Usually, the heat source gas containing the heat storage material microcapsules obtained by spray drying is continuously led to a classifier represented by a cyclone to collect and classify particles. In order to adjust the particle size distribution of the heat storage material microcapsules obtained by the production method of the present invention, a commercially available general classifier can be used when classification for removing coarse particles and fine particles is necessary.

  As the heat source gas, an inert gas is desirable. In particular, it is desirable to use nitrogen gas from the viewpoint of cost. Further, in order to more efficiently evaporate the organic solvent (D), the heat storage material microcapsule dispersion may be preheated before spray drying.

  The heat storage material microcapsules thus obtained can be used as they are, but may be further subjected to secondary drying by other drying methods such as vacuum drying, aeration drying and fluidized bed drying, if necessary.

  Further, the obtained heat storage material microcapsules may be used after adjusting the particle diameter by a granulation step or the like, if necessary.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in full detail, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are all based on mass.

1. Preparation of binder (A-1) 560 parts of n-butanol was put into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, and the temperature was raised to 80 ° C. 150 parts of styrene, 100 parts of methyl methacrylate, 650 parts of stearyl methacrylate, 70 parts of acrylic acid, 30 parts of γ-methacryloyloxypropyltriethoxysilane, 10 parts of tert-butylperoxy 2-ethylhexanoate and n-butanol A mixture of 100 parts was added dropwise over 4 hours. After completion of the dropwise addition, the polymerization reaction was continued for 10 hours at the same temperature to complete the reaction, whereby a solution (A′-1) of binder (A-1) was obtained.
The binder (A-1) obtained had a number average molecular weight of 35,000, a solubility parameter of 7.9, and the solid content concentration of the solution (A′-1) was 60.2%.

2. Preparation of binder (A-2) 560 parts of toluene was put into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, and the temperature was raised to 80 ° C. A mixture of 150 parts of styrene, 300 parts of n-butyl methacrylate, 400 parts of 2-ethylhexyl acrylate, 150 parts of glycidyl methacrylate, 20 parts of tert-butylperoxy 2-ethylhexanoate and 100 parts of toluene was added for 4 hours. It was dripped over. After completion of dropping, the polymerization reaction was continued for 10 hours at the same temperature to complete the reaction, whereby a solution (A′-2) of binder (A-2) was obtained.
The obtained binder (A-2) had a number average molecular weight of 25,000, a solubility parameter of 8.6, and the solid content concentration of the solution (A′-2) was 60.3%.

3. Preparation of curing agent (B) 1100 parts of isopropyl alcohol was placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen inlet, and the temperature was raised to 80 ° C. A mixture consisting of 300 parts of styrene, 350 parts of n-butyl methacrylate, 350 parts of methacrylic acid, 70 parts of tert-butyl peroxy 2-ethylhexanoate and 100 parts of isopropyl alcohol was added dropwise over 6 hours. After completion of dropping, the polymerization reaction is continued for 10 hours at the same temperature to complete the reaction, thereby obtaining a solution (B′-1) of a curing agent (B-1) containing a carboxyl group. It was.
The obtained curing agent (B-1) had a number average molecular weight of 3,800, and the solid content concentration of the solution (B′-1) was 47.0%.

Example 1
In a reaction vessel equipped with a stirrer equipped with a turbine blade, a thermometer, a condenser and a nitrogen gas inlet, 2000 parts of “FNP-0090” (paraffin wax manufactured by Nippon Seiki Co., Ltd., melting point 90 ° C.) as a heat storage material, 800 parts of the binder (A-1) solution (A′-1), 2200 parts of n-butanol, 1700 parts of toluene, 1300 parts of ethylene glycol and 10 parts of γ-glycidoxypropyltriethoxysilane as the curing agent (B). The temperature was increased while charging and stirring. At 85 ° C., it was confirmed that the heat storage material was completely dissolved. When heating was stopped at the same temperature and the mixture was gradually cooled at a cooling rate of 5 ° C./hr while stirring at 300 rpm, precipitation of particles was observed at 80 ° C. Dispersion of the heat storage material microcapsule (P-1) was carried out by adding 0.8 parts of “dibutyltin dilaurate” as a curing catalyst to the particle dispersion thus obtained and reacting at 75 ° C. for 10 hours while stirring at 300 rpm. A liquid (S-1) was obtained.
The solid content concentration of the dispersion (S-1) was 18.5%, and the volume average particle diameter of the heat storage material microcapsules (P-1) was 25 μm. The volume average particle diameter is a value measured using a particle size distribution measuring device “Microtrac HRA (X-100)” manufactured by Nikkiso Co., Ltd. (the same applies hereinafter).

(Evaluation Test 1)
30 parts of dimethylethanolamine was added to 11000 parts of the dispersion (S-1) of the obtained heat storage material microcapsule (P-1) and stirred to neutralize the acid groups of the binder (A-1). Further, after removing n-butanol and toluene by distillation under reduced pressure at 75 ° C. and 0.1 kPa, ion-exchanged water and ethylene glycol were added and stirred, whereby the dispersion medium composition was ion-exchanged water / ethylene glycol = 5/5. A heat storage material microcapsule dispersion having a solid content concentration of 30.0% (by weight) was prepared. The obtained heat storage material microcapsule dispersion liquid is used in an electric pump in a cooling water circulation circuit including a heat dissipation system such as a radiator, the maximum flow rate is 12 L / min, the piping finest (core part) flow rate is 0.3 m / s, the refrigerant As a result of circulating at a maximum temperature of 95 ° C., no damage to the heat storage material microcapsules was observed.

(Example 2)
“Hi-Mic-1090” as a heat storage material (microcrystalline wax produced by Nippon Seisaku Co., Ltd., melting point 88 ° C.) in a reaction vessel equipped with a stirrer equipped with a turbine blade, a thermometer, a condenser and a nitrogen gas inlet 2000 parts, 640 parts of a binder (A-2) solution (A′-2), 1200 parts of toluene and 4000 parts of isopropyl alcohol were charged, and the temperature was increased while stirring. At 83 ° C., it was confirmed that the heat storage material was completely dissolved. When the heating was stopped at the same temperature and the mixture was gradually cooled at a cooling rate of 5 ° C./hr while stirring at 400 rpm, precipitation of particles was observed at 80 ° C. While maintaining the liquid temperature at 79 ° C., 352 parts of the solution (B′-1) of the curing agent (B-1) was added and maintained at the liquid temperature of 79 ° C. for 12 hours, and the binder (A-2) and the curing agent. By allowing (B-1) to react, a dispersion liquid (S-2) of the heat storage material microcapsule (P-2) was obtained.
The solid content concentration of the obtained dispersion (S-2) was 31.0%.

To the dispersion (S-2) thus obtained, 8000 parts of isopropyl alcohol was added and spray-dried with an explosion-proof vertical descending co-current spray dryer equipped with a solvent recovery device. A two-fluid nozzle system was used as the spray system, and the spray gas pressure was 0.3 MPa. Nitrogen gas was used as the heat source gas, and the temperature of the heat source gas was set to 45 ° C. By spraying the heat storage material microcapsule dispersion (S-2) preheated to 50 ° C. into the spray drying device at a supply rate of 5 kg / hr, and collecting the heat storage material microcapsules dried in the device with a cyclone. The heat storage material microcapsule (P-2) was obtained.
The obtained heat storage material microcapsule (P-2) had a volume average particle size of 35 μm and a non-volatile content of 99.2%.

(Evaluation test 2)
2000 parts of the obtained heat storage material microcapsules (P-2) and 11 parts of potassium hydroxide were added to 4000 parts of a dispersion medium of ion-exchanged water / ethylene glycol = 5/5 (weight ratio), and the heat storage material was stirred. A microcapsule dispersion was prepared. The obtained heat storage material microcapsule dispersion liquid is used in an electric pump in a cooling water circulation circuit including a heat dissipation system such as a radiator, the maximum flow rate is 12 L / min, the piping finest (core part) flow rate is 0.3 m / s, the refrigerant As a result of circulating at a maximum temperature of 95 ° C., no damage to the heat storage material microcapsules was observed.

Claims (9)

A binder (A) comprising a vinyl copolymer having an average of two or more carboxyl groups in one molecule and a solubility parameter value of 6.5 to 9.0; and a melting point of 40 to 150 ° C. Ah is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax, microcrystalline wax, having 10 or more higher fatty acid carbons, esters having 10 or more higher fatty acid carbon, higher alcohols and carbon having 10 or more carbon atoms At least one aliphatic hydrocarbon heat storage material (C) selected from the group consisting of ethers of higher alcohols of several tens or more, from a temperature lower by 50 ° C. than the melting point of the heat storage material (C) to less than the melting point in a temperature range, (grams solute dissolved in a solvent 100g) solubility the binder (a) and the heat storage material (C) is Ri der least 100g respectively, and, aromatic organic Formed SQLDESC_BASE_TABLE_NAME This contain agent and / or aliphatic organic solvents, and, having 4 or more carbon atoms of n- butanol alkyl group, isobutanol, sec- butanol, tert- butanol, n- pentanol and isopentanol At least one alkyl alcohol selected from the group consisting of, at least one ketone selected from the group consisting of methyl isobutyl ketone and n-amyl ketone having 4 or more carbon atoms in the alkyl group, and carbon number of the alkyl group At least one ester selected from the group consisting of n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate and butyl propionate , methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, at least one glycol ether selected from the group consisting of propylene glycol dimethyl ether and propylene glycol diethyl ether, benzene, toluene, the group consisting of xylenes and ethylbenzene At least one aromatic hydrocarbon selected from Exxon Aromatic Naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) And reacting the curing agent (B) having an average of two or more epoxy groups that react with the carboxyl group of the binder (A) in the molecule and the carboxyl group in the binder (A). A method for producing a heat storage material microcapsule. A binder (A) made of a vinyl copolymer having an average of two or more epoxy groups in one molecule and a solubility parameter value of 6.5 to 9.0, and a melting point of 40 to 150 ° C. Ah is, and aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax, microcrystalline wax, having 10 or more higher fatty acid carbons, esters having 10 or more higher fatty acid carbon, higher alcohols and carbon having 10 or more carbon atoms At least one aliphatic hydrocarbon heat storage material (C) selected from the group consisting of ethers of higher alcohols of several tens or more, from a temperature lower by 50 ° C. than the melting point of the heat storage material (C) to less than the melting point in a temperature range, (grams solute dissolved in a solvent 100g) solubility the binder (a) and the heat storage material (C) is Ri der least 100g respectively, and, aromatic organic solvents Beauty / or contain aliphatic organic solvents Ri formed, and, four or more n- butanol carbon atoms in the alkyl group, isobutanol, sec- butanol, tert- butanol, from n- pentanol and isopentanol At least one alkyl alcohol selected from the group consisting of at least one ketone selected from the group consisting of methyl isobutyl ketone and n-amyl ketone having 4 or more carbon atoms in the alkyl group, and the carbon number of the alkyl group. At least one ester selected from the group consisting of n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate and butyl propionate , methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene Glycol diethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, at least one glycol ether selected from the group consisting of propylene glycol dimethyl ether and propylene glycol diethyl ether, benzene, selected from the group consisting of toluene, xylene and ethylbenzene At least one aromatic hydrocarbon, exon aromatic naphtha NO. Mixed hydrocarbons containing 2, at least one aliphatic hydrocarbon selected from the group consisting of n-pentane, n-hexane and n-octane , Isopar C, Isopar E, Exol DSP 100/140, Exol D30 And at least one cyclic hydrocarbon selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, and mixed hydrocarbons containing at least one aliphatic hydrocarbon selected from the group consisting of IP solvent 1016 An organic solvent (D1) containing at least one selected from the group consisting of aliphatic hydrocarbons, and the binder (A) and the heat storage material (C) in a temperature range below the melting point of the heat storage material (C) der solubility less 10g respectively for is, and the number 3 or less methanol carbon, ethanol, n An organic solvent (D2) containing at least one alcohol selected from the group consisting of propanol and isopropanol and / or at least one polyhydric alcohol selected from the group consisting of ethylene glycol and propylene glycol , From the melting point of the heat storage material (C) to the mixed organic solvent (D) in which the mixing ratio (D1 / D2) of the organic solvent (D1) and the organic solvent (D2) is 10/90 to 80/20 in terms of weight. An organic solvent solution in which the total concentration of the binder (A), the curing agent (B) and the aliphatic hydrocarbon heat storage material (C) dissolved at a low temperature is 5 to 70% by mass ,
The mixture is cooled at a cooling rate of 1 to 50 ° C./hr below the precipitation temperature of the mixture of the binder (A) and the heat storage material (C) under a mixing condition of 150 rpm or more, and the binder (A) and the heat storage material. Precipitating particles containing (C),
Added so that the mixing ratio [(C) / (A + B)] 95 / 5-50 / 50 by weight in terms of the heat storage material (C) to the total amount of the binder (A) and the curing agent (B) And reacting the epoxy group in the binder (A) with the curing agent (B) having an average of two or more carboxyl groups that react with the epoxy group of the binder (A) in one molecule. A method for producing a heat storage material microcapsule. The heat storage according to claim 1 or 2 , wherein a ratio of the vinyl monomer having the functional group is 2 to 50% by mass based on the total amount of the vinyl monomer constituting the vinyl copolymer. A manufacturing method of a material microcapsule. The number average molecular weight of the said vinyl type copolymer is 1000-200000, The manufacturing method of the thermal storage material microcapsule as described in any one of Claims 1-3 characterized by the above-mentioned. The total concentration of the binder (A), the curing agent (B), and the heat storage material (C) is 5 to 70% by mass based on the total amount of the organic solvent solution . The manufacturing method of the thermal storage material microcapsule as described in one term . According to any one of claims 1 to 5, wherein the addition of the curing agent after the precipitation operations previously added the curing agent (B) or the particles prior to the deposition operations the particles Manufacturing method of heat storage material microcapsules. The production of the heat storage material microcapsule according to any one of claims 1 to 6, wherein the reaction is performed for 1 to 40 hours in a range of a temperature 15 ° C lower than the precipitation temperature of the particles to a temperature lower than the precipitation temperature. Method. The said mixed organic solvent (D) is removed by the spray-drying method, The manufacturing method of the thermal storage material microcapsule as described in any one of Claims 1-7 characterized by the above-mentioned. A microcapsule produced by the method for producing a heat storage material microcapsule according to any one of claims 1 to 8 .