JP2009084363A - Manufacturing method of microcapsule of thermal storage medium, and microcapsule of thermal storage medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a microcapsule of a thermal storage medium stable to a long-term heat history and share stress by a pump, by which an expensive device such as a pressurized closed container is not needed even when the microcapsule uses a thermal storage medium having a high melting point and to provide the microcapsule of the thermal storage medium. <P>SOLUTION: In the manufacturing method of the microcapsule of the thermal storage medium, an organic solvent solution in which a resin (A1) having an acid group and a hydrolyzable silyl group and an aliphatic hydrocarbon based thermal storage medium (B) are dissolved in an organic solvent (C) and a basic compound (D) are mixed and the acid group in the resin (A1) is neutralized to form a resin (A2) having the neutralized acid group and the hydrolyzable silyl group, then the resultant material and water are mixed to be subjected to phase inversion emulsification, then the hydrolyzable silyl group in the resin (A2) is subjected to hydrolytic condensation and then the organic solvent (C) is removed. The microcapsule manufactured by the manufacturing method is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a microcapsule including a heat storage material and a heat storage material microcapsule. Specifically, the present invention relates to a method for manufacturing a heat storage material microcapsule that includes a heat storage material and has excellent durability against a long-term heat history, and a heat storage material microcapsule manufactured by this manufacturing method. The present invention is particularly useful as a method for producing a microcapsule that encloses a high-melting-point heat storage material.

  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. The latent heat storage material can be used as long as it has a melting point and a freezing point, but is preferably physicochemically stable and has a large latent heat. Typical latent heat storage materials include calcium chloride, sodium sulfate, Examples include hydrates of inorganic compounds such as sodium hydrogen phosphate, 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 possibility that formaldehyde harmful to the human body may remain.

  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 a microcapsule that contains a high-melting-point heat storage material whose melting point is close to or higher than that of water, it becomes difficult to keep the entire liquid at a temperature above 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 is a problem.

Japanese Patent Laid-Open No. 5-117642 Japanese Patent Laid-Open No. 2002-80835

  The problem to be solved by the present invention is that it is not necessary to use an expensive apparatus such as a pressurized sealed container, even if a high-melting-point heat storage material is used, and is stable against a long-term heat history, A heat storage material microcapsule manufacturing method and a heat storage material microcapsule are provided.

  In order to solve the above-mentioned problems, the present inventors have intensively and researched. As a result, the resin (A1) having an acid group and a hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) are organic solvents. The organic solvent solution dissolved in (C) and the basic compound (D) are mixed to neutralize the acid group in the resin (A1), and the neutralized acid group and hydrolyzable silyl group After having made resin (A2) having water, it is mixed with water for phase inversion emulsification, and then hydrolyzed and condensed the hydrolyzable silyl group in the resin (A2), and then the organic solvent (C) is removed. In the manufacturing method of the heat storage material microcapsule, it is not necessary to maintain a high temperature higher than the melting point of the heat storage material by using an expensive device such as a pressurized airtight container. Is easy to manufacture, and the heat storage material Microcapsules is found to be higher thermal storage material microcapsule practical exhibits excellent resistance to long-term thermal history, thereby completing the present invention.

  That is, in the present invention, as a result of diligent and research in order to solve the above-described problems, the resin (A1) having an acid group and a hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) are an organic solvent. The organic solvent solution dissolved in (C) and the basic compound (D) are mixed to neutralize the acid group in the resin (A1), and the neutralized acid group and hydrolyzable silyl group After having made resin (A2) having water, it is mixed with water for phase inversion emulsification, and then hydrolyzed and condensed the hydrolyzable silyl group in the resin (A2), and then the organic solvent (C) is removed. The present invention provides a method for producing a heat storage material microcapsule.

  Moreover, this invention provides the thermal storage material microcapsule produced by the said manufacturing method.

  Even if the heat storage material microcapsule manufacturing method of the present invention uses a high-melting-point heat storage material, it is not necessary to use an expensive apparatus such as a pressurized airtight container, and the microcapsule can be easily manufactured. Particularly suitable as a method for producing a heat storage material microcapsule containing a heat storage material having a melting point, the heat storage material microcapsule obtained by this production method exhibits excellent durability against a long-term heat history, and is an object of the present invention. The expression of various effects is recognized.

  First, as the resin (A1) having an acid group and a hydrolyzable silyl group, various resins such as a vinyl polymer, a polyurethane polymer, and a polyester resin having an acid group and a hydrolyzable silyl group are used. However, a vinyl polymer having an acid group and a hydrolyzable silyl group is preferred because the heat storage microcapsules obtained have good heat resistance, water resistance and mechanical strength, and particularly excellent durability.

  Representative examples of the acid group contained in the resin (A1) include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a sulfuric acid group, a sulfite group, a phosphoric acid group, an acidic phosphoric acid ester group, and a phosphorous acid group. Can be mentioned. These acid groups are converted to neutralized acid groups by neutralization with a basic compound. Of these acid groups, preferred is a carboxyl group.

  Examples of the hydrolyzable silyl group contained in the resin (A1) include an atomic group in which various hydrolyzable groups are bonded to a silicon atom represented by the following general formula (I). Can do.

（ただし、式中のＲ_１はアルキル基、アリール基またはアラルキル基を、Ｒ_２は水素原子、ハロゲン原子、アルコキシ基、置換アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基を表し、また、ｍは０、１または２なる整数を表す。）

(Wherein R ₁ is an alkyl group, aryl group or aralkyl group, R ₂ is a hydrogen atom, halogen atom, alkoxy group, substituted alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group) An amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and m represents an integer of 0, 1 or 2.)

Particularly preferred as R ₂ in the general formula (I) is an alkoxy group from the viewpoint that alcohol produced by hydrolysis can be easily removed.

  In order to prepare a vinyl polymer having an acid group and a hydrolyzable silyl group in the resin (A1), for example, (1) a vinyl monomer containing an acid group and a hydrolyzable silyl group (2) A polycarboxylic acid anhydride is added to a vinyl polymer having a hydroxyl group and a hydrolyzable silyl group prepared in advance. Methods such as a method of reacting, (3) a method of reacting a vinyl polymer having an acid anhydride group and a hydrolyzable silyl group prepared in advance with a compound having active hydrogen such as water, alcohol and amine can be applied. Among these, the method (1) is the simplest.

  The vinyl monomer having an acid group used in the method (1) is preferably a vinyl monomer containing a carboxyl group as an acid group, and a typical one is (meth) acrylic. Unsaturated carboxylic acids such as acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid, fumaric acid; monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n maleate -Monoesters of saturated dicarboxylic acids such as butyl, monomethyl fumarate, mono-n-butyl fumarate and saturated monohydric alcohols; monovinyl esters of saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate; anhydrous Free of saturated polycarboxylic acids such as succinic acid, glutaric anhydride, phthalic anhydride, trimellitic anhydride Addition reaction products of a group and a hydroxyl group-containing vinyl monomer as described later; monomers obtained by addition reaction of a carboxyl group-containing monomer and a lactone as described above, etc. Can be mentioned.

  Moreover, as a typical thing of the vinyl-type monomer which has a hydrolyzable silyl group used in order to introduce | transduce a hydrolyzable silyl group by the method of said (1), 3- (meth) acryloyloxy is used. Propyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyl-methyldimethoxysilane, 3- (meth) acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyl Oxypropyl-dimethylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (meth) acryloyloxypropyl-dimethylhydroxysilane, trimethoxysilylethyl vinyl ether, trimethoxysilylbuty Vinyl ether, and the like.

  Examples of other copolymerizable monomers used together with the vinyl monomer having a carboxyl group and the vinyl monomer having a hydrolyzable silyl group by the method (1) include methyl (meth) acrylate. , Ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate Esters of alkyl alcohols having 1 to 22 carbon atoms such as stearyl (meth) acrylate and (meth) acrylic acid; Aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate Cyclohexyl (meth) acrylate, isoboro Le (meth) cycloalkyl (meth) acrylates such as acrylate; 2-methoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate of ω- alkoxyalkyl (meth) acrylates;

Aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl benzoate Esters: alkyl esters of crotonic acid such as methyl crotonate and ethyl crotonate; dimethyl malate, di-n-butyl malate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate, di-n-butyl Dialkyl esters of unsaturated dibasic acids such as itaconate; cyano group-containing monomers such as (meth) acrylonitrile and crotononitrile; vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, Fluoroolefins such as hexafluoropropylene S; vinyl chloride, chlorinated olefins vinylidene chloride, ethylene, propylene, isobutylene, 1-butene, alpha-olefins of 1-hexene and the like;

Alkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and n-hexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and 4-methylcyclohexyl vinyl ether; (meth) acrylamide, N, N-dimethyl ( Examples thereof include tertiary amide group-containing monomers such as (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, and N-vinylpyrrolidone.

  Further, in order to improve the water dispersibility of the vinyl polymer, a vinyl monomer having a polyether chain can be copolymerized. Typical examples of such vinyl monomers include methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate, and (meth) acrylate of an ethylene oxide / propylene oxide copolymer having a methoxy group at one end. And the like.

  Furthermore, vinyl monomers having various reactive functional groups can be copolymerized. Examples of vinyl monomers having such a reactive functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, Hydroxyl group-containing vinyl monomers such as 4-hydroxybutyl vinyl ether; 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3-carbonate propyl (meth) acrylate, 3,4-carbonate butyl (meth) Cyclocarbonate group-containing vinyl monomers such as acrylate; epoxy group-containing vinyl such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and glycidyl vinyl ether Monomer;

Contains carbamate groups such as methyl N- (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate, ethyl N- [2- (meth) acryloyloxy] ethylcarbamate, 2-carbamoyloxyethyl (meth) acrylate Vinyl monomers: N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, vinyl monomers having an N-hydroxymethylamide group or N-alkoxymethylamide group such as N-butoxymethyl (meth) acrylamide Monomers; tertiary amino group-containing vinyl monomers such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, etc. Can be mentioned.

  Among the vinyl monomers described above, an acrylic polymer can be obtained by polymerizing a monomer mixture containing (meth) acrylic acid ester as an essential monomer. In addition, by polymerizing a monomer mixture having an aromatic vinyl monomer, a carboxylic acid vinyl ester monomer, and a fluoroolefin monomer as essential components, respectively, an aromatic vinyl polymer is obtained. Carboxylic acid vinyl ester polymers and fluoroolefin polymers can be obtained.

  In order to obtain a vinyl polymer having a carboxyl group and a hydrolyzable silyl group from the various vinyl monomers described above, various polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization are applied. However, the solution radical polymerization method in an organic solvent is the simplest.

  Examples of the organic solvent used in preparing a vinyl polymer having a carboxyl group and a hydrolyzable silyl group by a solution radical polymerization method in an organic solvent include methanol, ethanol, n-propanol, isopropanol, n- Alkyl alcohols such as butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol; methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, n-butyl cellosolve, isobutyl 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, glycol ethers such as 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 Formula 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, acetic acid Isopropyl, n-butyl acetate , Isobutyl acetate, n- amyl, isoamyl acetate, hexyl acetate, ethyl propionate, and the like esters such as butyl propionate.

  Examples of the polymerization initiator used in the preparation of the vinyl copolymer include 2,2′-azobisisobutyronitrile, 2,2′-azobis-methylbutyronitrile, and 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) dihydrate, 2,2'-azobis An azo compound such as [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-butylperoxybenzoate, dicumyl peroxide, or ketone peroxides such as di-tert-butyl peroxide; peroxyketals; hydroperoxides; Peroxides such; diacyl peroxides like; peroxy esters; peroxydicarbonates like; hydrogen peroxide and the like.

  The amount of acid groups such as carboxyl groups introduced into the vinyl polymer thus prepared is from 0.1 to 10.3 per 1000 g of vinyl polymer because a heat storage material microcapsule with good storage stability can be obtained. A range of 0 mol is preferable, a range of 0.2 to 7.0 mol is more preferable, and a range of 0.3 to 5.0 mol is particularly preferable.

  Further, the amount of the hydrolyzable silyl group introduced into the vinyl polymer makes it possible to obtain a heat storage material microcapsule that is less prone to thickening and gelation during the preparation process of the heat storage material microcapsule and is excellent in durability. Therefore, the range of 0.01 to 1.5 mol per 1000 g of the vinyl polymer is preferable, more preferably 0.02 to 1.3 mol, and particularly preferably 0.05 to 1.0 mol. It is a range.

  The number average molecular weight of the vinyl polymer is suitably in the range of 1,000 to 200,000, and more preferably in the range of 5,000 to 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.

  In order to prepare a polyurethane polymer having a carboxyl group and a hydrolyzable silyl group in the resin (A1), for example, in addition to various dihydroxy compounds and various diisocyanate compounds, dimethylol as a carboxyl group source is used. 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, which uses a dihydroxy compound having an acid group such as propionic acid, dimethylolbutanoic acid and the like, and as a hydrolyzable silyl group source As described in JP-A-51-90391, JP-A-55-73729, or JP-A-60-255817, using raw material components such as aminoalkoxysilane compounds such as , Ketone organic solvents such as methyl isobutyl ketone or N- Methylpyrrolidone, an aprotic polar organic solvent such as dimethylformamide, may be applied a method of heating and stirring to dissolve the above-mentioned ingredients.

  The amount of the carboxyl group introduced into the polyurethane polymer having a carboxyl group and a hydrolyzable silyl group prepared in this way is the heat storage material microcapsule having good storage stability. The range of 0.1 to 5.0 mol per 1000 g of the polymer is preferable, more preferably 0.2 to 4.0 mol, and particularly preferably 0.3 to 3.0 mol.

  Further, the amount of the hydrolyzable silyl group introduced into the polyurethane-based polymer is less likely to cause thickening or gelation in the process of preparing the heat storage material microcapsules, and furthermore, the heat storage material microcapsules having excellent durability can be obtained. Therefore, the range of 0.01 to 1.5 mol per 1000 g of the polyurethane polymer is preferable, more preferably 0.02 to 1.3 mol, and particularly preferably 0.05 to 1.0 mol. Range.

  The number average molecular weight of the polyurethane polymer is preferably in the range of 2,000 to 150,000, more preferably 3,000 to 100,000, since a heat storage material microcapsule having good storage stability can be obtained. It is a range, Especially preferably, it exists in the range of 4,000-50,000.

  In order to prepare a polyester-based resin having a carboxyl group and a hydrolyzable silyl group in the resin (A1), for example, first, various polyhydric alcohols and various polycarboxylic acids or acid anhydrides thereof are prepared. A compound having both a carboxyl group or a hydroxyl group of a polyester resin obtained by dehydration condensation and a functional group capable of reacting with the carboxyl group and a hydrolyzable silyl group, or a compound having both a functional group capable of reacting with a hydroxyl group and a hydrolyzable silyl group It can be obtained by mixing and reacting under heating.

  Examples of the polyhydric alcohol include aliphatic or alicyclic rings such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 3-methylpentadiol, 1,4-hexanediol, and 1,6-hexanediol. A dihydric alcohol of the formula is mainly used, and a trihydric or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol may be used in combination as necessary. Examples of the polyvalent carboxylic acid or acid anhydride thereof include terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, maleic anhydride, tetrahydromaleic anhydride, hexahydrophthalic anhydride, and the like. A tribasic or higher polyvalent carboxylic acid such as dibasic acid or acid anhydride thereof, trimellitic anhydride, methylhydroexcentricarboxylic acid, pyromellitic anhydride or acid anhydride thereof is used. These polyhydric alcohols and polyhydric carboxylic acids or acid anhydrides thereof may be used in combination.

  Further, examples of the compound having both a functional group capable of reacting with the carboxyl group and a hydrolyzable silyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidide. Xylpropyldimethoxysilane, 3-glycidoxypropyldiethoxysilane, and the like are also included. Examples of the compound having both a functional group capable of reacting with a hydroxyl group and a hydrolyzable silyl group include 3-isocyanatopropyltriethoxysilane.

  The amount of the carboxyl group introduced into the polyester resin having a carboxyl group and a hydrolyzable silyl group thus prepared is that the heat storage material microcapsules having good storage stability can be obtained. A range of 0.01 to 5.0 mol per 1000 g of the polymer is preferable, a range of 0.02 to 4.0 mol is more preferable, and a range of 0.03 to 3.0 mol is particularly preferable.

  The amount of the hydrolyzable silyl group introduced into the polyester resin is 0% per 1000 g of the polyester resin because a microcapsule having excellent durability can be obtained and thickening and gelation hardly occur in the preparation process. The range of 0.01 to 1.5 mol is preferable, the range of 0.02 to 1.3 mol is more preferable, and the range of 0.05 to 1.0 mol is particularly preferable.

  The number average molecular weight of the polyester resin is preferably in the range of 2,000 to 150,000, more preferably in the range of 3,000 to 100,000, since a heat storage material microcapsule with good storage stability can be obtained. And particularly preferably within the range of 4,000 to 50,000.

In the present invention, the number average molecular weights of vinyl polymers, polyurethane polymers, polyester resins and the like are determined by gel 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% by weight tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 μl)

  The resin (A1) used in the present invention preferably has an affinity for the aliphatic hydrocarbon heat storage material (B) because the heat storage material microcapsules can be prepared without problems such as particle aggregation.

  The affinity of the resin (A1) with the aliphatic hydrocarbon heat storage material (B) is greatly influenced by the solubility parameter of the resin (A1). The solubility parameter of the resin (A1) can be determined by the following method.

  0.5 g of the resin (A1) is weighed into a 100 ml Meyer flask, and 10 ml of tetrahydrofuran (THF) is added to dissolve the resin (A1). While the dissolved solution is maintained at a liquid temperature of 25 ° C. and stirred with a magnetic stirrer, hexane is added dropwise using a 50 ml burette, and the amount of drop (vh) at the point where the solution becomes cloudy (turbid point) is obtained. .

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

From vh and vd, the solubility parameter value δ of the resin (A1) is calculated using the equation shown by SUH, CLARKE [J. Polym. Sci. A-1, Vol. 5, 1671-1681 (1967)]. It 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 working volume of THF (10 ml). ]
δ _h , δ _d , δ _t ; SP value of hexane, deionized water, THF V _h , V _d , V _t ; molecular volume of hexane, deionized water, THF (ml / mol)

  As the value of the solubility parameter of the resin (A1), there is sufficient affinity between the resin (A1) and the aliphatic hydrocarbon heat storage material (B), and the resin (A1) And the aliphatic hydrocarbon heat storage material (B) can be prevented, so that a heat storage material microcapsule having excellent mechanical strength can be produced. Therefore, it is preferably in the range of 6.5 to 9.0. More preferably, it is in the range of 7.0 to 9.0. Among the resins (A1) having a solubility parameter value within the above range, a vinyl polymer is preferable because the solubility parameter can be easily adjusted.

  Examples of the aliphatic hydrocarbon heat storage material (B) used in the present invention include, for example, aliphatic hydrocarbons having 10 to 20 carbon atoms, paraffin wax (separated from vacuum distilled distillate using petroleum or natural gas as a raw material) Produced at a normal temperature; wax solid at normal temperature; about 20 to 40 carbon atoms), microcrystalline wax (wax solid at normal temperature separated from refined distillation residue or heavy distillate using petroleum as a raw material; Typical examples thereof include aliphatic hydrocarbons having 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 (B), both paraffin wax and microcrystalline wax have high heat storage capacity, excellent performance as heat storage materials, high safety, and melting points according to the intended use. It is particularly preferable because it is easily available.

  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.

  These aliphatic hydrocarbon heat storage materials (B) can be used in a mixture 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 organic solvent (C) used in the present invention is an organic solvent that can dissolve the resin (A1) and the aliphatic hydrocarbon heat storage material (B) into an organic solvent solution. Although it may consist of only an organic solvent or a mixed organic solvent composed of two or more organic solvents, among them, the resin (A1) and the aliphatic hydrocarbon heat storage material (B) Resin to be used among alcohols, esters, glycol ethers, aromatic organic solvents, aliphatic organic solvents, and alicyclic organic solvents having 4 or more alkyl groups because of their high affinity It is preferable to select appropriately according to the type. In addition, when using a vinyl polymer as said resin (A1), it is especially preferable to use the organic solvent formed by containing an aromatic organic solvent and a C4-C8 alcohol organic solvent.

  Examples of the organic solvent (C) include alkyl alcohols having 4 or more carbon atoms in the alkyl group, 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; 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, glycol ethers such as propylene glycol diethyl ether; benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene Exxon 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 alicyclic hydrocarbons.

  The resin (A1) and the aliphatic hydrocarbon heat storage material (B) are used in a weight ratio (A1 / B) of the resin (A1) and the aliphatic hydrocarbon heat storage material (B) of 5/95 to 5/95. A range of 50/50 is preferable, and a range of 10/90 to 30/70 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.

  Further, the amount of the organic solvent (C) used may be an amount that can maintain the dissolved state of the resin (A1) and the aliphatic hydrocarbon heat storage material (B) at room temperature or under heating. Although not limited, the range of 50-200 is preferable with respect to a total of 100 parts by weight of the resin (A1) and the aliphatic hydrocarbon heat storage material (B), and more preferably in the range of 80-120 parts by weight.

  In order to manufacture the heat storage material microcapsules by the manufacturing method of the present invention, the resin (A1) having an acid group and a hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) are dissolved in the organic solvent (C). The organic solvent solution and the basic compound (D) are mixed to neutralize the acid group in the resin (A1), and the resin (A2) having the neutralized acid group and hydrolyzable silyl group After that, the mixture is further mixed with water for phase inversion emulsification, and after hydrolyzing and condensing the hydrolyzable silyl group in the resin (A2), the organic solvent (C) may be removed.

  The organic solvent solution may be a solution in which the resin (A1) having an acid group and a hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) are dissolved in the organic solvent (C). (1) The resin (A1), the heat storage material (B), and the organic solvent (C) are preferably mixed under heating to mix the resin (A1) and the heat storage material (B) with an organic solvent (C ), (2) the resin solution in which the resin (A1) is dissolved in the organic solvent (C), the heat storage material (B), and, if necessary, the organic solvent (C), A solution in which the heat storage material (B) is dissolved by mixing under heating, and (3) the resin (A1) in the heat storage material solution in which the heat storage material (B) is dissolved in the organic solvent (C). After the synthesis, if necessary, the same or different heat storage material (B) and / or organic solvent (C Add the include solutions and the like obtained.

  Among these organic solvent solutions (1) to (3), when a vinyl polymer is used as the resin (A1), the organic solvent solution (2) such as a vinyl heavy polymer obtained by a solution radical polymerization method is used. The combined solution, the heat storage material (B), and, if necessary, the organic solvent (C) (which may be the same as or different from those used in the solution radical polymerization) are preferably mixed under heating, preferably In the solution in which the heat storage material (B) is dissolved and the organic solvent solution in (3), for example, the heat storage material solution in which the heat storage material (B) is dissolved in the organic solvent (C), After synthesizing the vinyl polymer by solution radical polymerization, if necessary, the same or different heat storage material (B) and / or organic solvent (C) is added, and the added heat storage material (B) is added. An organic solvent solution obtained by dissolution is preferred. In addition, since the mixed state of the vinyl polymer and the aliphatic hydrocarbon heat storage material (B) is particularly good and the particles are less likely to aggregate during phase inversion emulsification, the organic solvent solution of (3) Most preferred.

  In addition, in the organic solvent solution of (3), the heat storage material used when solution radical polymerization of a vinyl monomer is performed in the heat storage material solution in which the heat storage material (B) is dissolved in the organic solvent (C). As usage-amount of (B), it is preferable that it is 30-100 weight% with respect to the whole quantity of a thermal storage material (B), and it is more preferable that it is 30-80 weight%.

  The organic solvent solution and the basic compound (D) are mixed to neutralize the acid group in the resin (A1), thereby obtaining a resin (A2) having a neutralized acid group and a hydrolyzable silyl group. Then, as a method for further phase inversion emulsification by mixing with water, the basic compound (D) is made into an aqueous solution of the basic compound (D) and then mixed with an organic solvent solution, and the acid group in the resin (A1) Neutralization and phase inversion emulsification by mixing with water may be performed at the same time, but it is easy to produce microcapsules containing the aliphatic hydrocarbon heat storage material (B), and excellent storage stability and durability. Since a microcapsule is obtained, an organic solvent solution and a basic compound (D) are mixed to neutralize an acid group in the resin (A1) to have a neutralized acid group and a hydrolyzable silyl group. After the resin (A2), a method of mixing with water and emulsifying the phase inversion is preferable.

  In addition, as a method of mixing the resin (A1) with fat after neutralizing the resin (A1) to obtain a resin (A2) having a neutralized acid group and a hydrolyzable silyl group, Examples thereof include a method of adding water to the organic solvent solution of the group hydrocarbon-based heat storage material (B) with stirring, a method of sequentially adding the organic solvent solution to water with stirring, and the like. At this time, the hydrolysis condensation of the hydrolyzable silyl group in the resin (A2) may be partially started.

  Examples of the basic compound (D) include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol; ammonia, lithium hydroxide, hydroxide Inorganic basic substances such as sodium and potassium hydroxide; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide are included.

  The addition amount of the basic compound (D) needs to be appropriately set according to the amount of acid groups contained in the resin (A1), but is generally 0.2 to 2 with respect to 1 mol of acid groups. 0.0 mol, preferably 0.3 to 1.5 mol, particularly preferably 0.5 to 1.3 mol of basic compound (D) may be added. When the acid group is neutralized, if less than an equivalent amount of the basic compound (D) is added to the acid group, the acid group is partially neutralized. It has a hydrated acid group and a hydrolyzable silyl group. And when an excess basic compound (D) is added exceeding an equivalent with respect to an acid group, the resin (A2) obtained has a neutralized acid group and a hydrolyzable silyl group.

  The phase inversion emulsification by mixing with water described above is usually performed at 40 to 95 ° C., preferably 60 to 90 ° C., more preferably 70 to 85 ° C., so that the inside of this temperature range can be maintained. It is preferable to appropriately set the temperature of the organic solvent solution of the resin (A2) having the acid group and hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) and the temperature of water.

  The amount of water used in the phase inversion emulsification may be equal to or greater than the amount at which phase inversion emulsification of the organic solvent solution of the resin (A2) and the aliphatic hydrocarbon heat storage material (B) occurs in water, and is not particularly limited. However, since a heat storage material microcapsule dispersion having excellent dispersion stability is obtained, it is preferably in the range of 100 to 400 parts by weight, more preferably in the range of 150 to 250 parts by weight with respect to 100 parts by weight of the organic solvent solution. preferable.

  Hydrolysis condensation of the hydrolyzable silyl group in the resin (A2) may be partially initiated during the phase inversion emulsification, and may continue as it is after phase inversion emulsification. A method of promoting the hydrolysis-condensation reaction by addition or the like is preferable because it is simple and efficient.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate; Titanate esters such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1, Compounds containing basic nitrogen atoms such as 4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; tetramethylammonium Quaternary compounds such as salt, tetrabutylammonium salt, dilauryldimethylammonium salt, etc. Quaternary ammonium salts having chloride, bromide, carboxylate, hydroxide, etc. as counter anions; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate, Examples thereof include tin carboxylates such as tin stearate. These catalysts can be used alone or in combination of two or more.

  The catalyst is preferably used in a range of 0.0001 to 10 parts by weight, more preferably in a range of 0.0005 to 3 parts by weight with respect to 100 parts by weight of the resin (A2). It is particularly preferable to use in the range of 0.001 to 1 part by weight.

  The heat storage material microcapsule dispersion obtained in this manner is used after removing a part or all of the organic solvent (C), and the obtained heat storage material microcapsule dispersion is mixed with a heat medium or a refrigerant as necessary. Is done. The heat storage material microcapsule dispersion is used as a heat storage material microcapsule that is solidified by removing not only the organic solvent (C) but also water.

  The means for removing the organic solvent (C) from the heat storage material microcapsule dispersion is not particularly limited, and various methods such as distillation can be used. Among them, the removal method by vacuum distillation is preferable.

  The heat storage material microcapsules dispersed in the heat storage material microcapsule dispersion of the present invention thus obtained can prevent particle aggregation at the time of standing, so that the diffraction particle size distribution measuring device Mastersizer 2000 manufactured by Malvern, UK It is preferable that the average particle diameter measured by 1 is 0.1-20 micrometers, and it is more preferable that it is 0.5-10 micrometers.

  The means for removing the organic solvent (C) and water from the heat storage material microcapsule dispersion and solidifying it is not particularly limited, and is dried at room temperature, forced heating, vacuum drying, freeze drying, spray drying, Various methods such as pressure filtration and suction filtration can be used, and two or more methods may be used in combination. Among them, the spray drying method has a high processing capacity per unit time, and the organic solvent can be removed in one step. It is recommended because solid particles can be recovered.

  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. When the particle size distribution of the obtained heat storage material microcapsules is adjusted and classification for removing coarse particles and fine particles is necessary, a commercially available general classifier can also be used.

  As the heat source gas, an inert gas is desirable. In particular, it is desirable to use nitrogen gas from the viewpoint of cost. Furthermore, 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.

  Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, “part” and “%” are all based on weight unless otherwise specified.

  Moreover, the melting temperature, solidification temperature, heat storage amount, and heat history durability of the heat storage material microcapsules in the examples were determined as follows.

  The prepared heat storage material microcapsule dispersion was measured with a differential scanning calorimeter DSC822e manufactured by METTLER TOLEDO. When DSC was measured at a sample amount of 5 mg and a heating rate of 5 ° C./min, The endothermic peak temperature of the heat capacity curve due to the melting behavior of the heat storage material encapsulated in the capsule 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 at the time of cooling The heat release peak temperature was defined as the solidification temperature, and the heat storage amount of the heat storage material microcapsules in the dispersion was calculated from the integrated value of the difference between the heat absorption peak and the baseline of the heat capacity curve at the time of temperature increase and temperature decrease.

  Furthermore, the heat history durability in the example is obtained by collecting 5 g of the obtained dispersion liquid of the heat storage material microcapsules and putting it in a thermostatic bath capable of temperature control, and a temperature range between 25 ° C. and 95 ° C. as the temperature range sandwiching the phase change temperature. The amount of heat storage after changing the temperature to ° C. and giving 50 temperature changes was measured, and the ratio to the amount of heat storage before giving the temperature change was shown as the heat history durability. The temperature change at this time is 1 hour for raising the temperature from 25 ° C to 95 ° C, holding for 30 minutes at 95 ° C, 1 hour for lowering the temperature from 95 ° C to 25 ° C, and holding for 30 minutes at 25 ° C. Went as. It shows that it is excellent in the retention of the amount of heat storage after giving a temperature change, so that a numerical value is large.

Example 1
In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet, 940 parts of “FNP-0090” (Nippon Seiki Co., Ltd., paraffin wax, melting point 90 ° C.) and “FT-105” as a heat storage material [Nippon Seiki Co., Ltd. paraffin wax, melting point 105 ° C.] 54 parts and n-butanol 860 parts as a solvent were added and heated to 100 ° C. To this, 60 parts of styrene, 60 parts of methyl methacrylate, 390 parts of stearyl methacrylate, 60 parts of acrylic acid, 60 parts of silane coupling agent KBE503 having a triethoxysilyl group manufactured by Shin-Etsu Chemical Co., Ltd., and Japan as a polymerization initiator A mixture consisting of 8 parts of Oil and Fats Perbutyl-O was added dropwise over 2 hours. After completion of dropping, the polymerization reaction was continued for 6 hours to obtain a uniform solution in which the heat storage material and the acrylic resin were dissolved.

  426 parts of additional heat storage material “FNP-0090”, 1,200 parts of xylene and 490 parts of normal propyl cellosolve are added to the obtained uniform solution, and the temperature is raised to 100 ° C. to completely dissolve “FNP-0090”. It was confirmed that the solution was homogeneous. After neutralizing by adding 72 parts of dimethylethanolamine, 7,900 parts of warm water and 1,900 parts of ethylene glycol were continuously added while maintaining the temperature at 80 ° C. or higher where no paraffin wax was precipitated, and phase-inversion emulsification was performed. confirmed. Furthermore, 20 parts of SCAT1 [Butyl tin catalyst manufactured by Sansha Co., Ltd.] was added to mix the silyl group of KBE503 to form a capsule film, and mixed for 2 hours. Next, a heat storage material microcapsule dispersion was obtained by removing almost all of xylene and n-butanol by distillation under reduced pressure.

  The average particle size of this heat storage material microcapsule dispersion (measured by a diffraction type particle size distribution measuring device Mastersizer 2000 manufactured by Malvern, UK) was 1.50 μm, and the non-volatile content was 30.2%. The heat storage amount (and peak temperature) of the heat storage material microcapsule calculated from the DSC measurement result is 43.6 J / g (melting temperature 90 ° C.) at the time of temperature increase, 144.4 J / g (solidification temperature 88 ° C.) at the time of temperature decrease, and thermal history. The durability was 97%.

Example 2
In addition to 940 parts of “FNP-0090” and 54 parts of “FT-105”, 710 parts of “FNP-0090” are used as an initial charge heat storage material, and the amount of additional heat storage material “FNP-0090” used is 426. Except having changed into the part, it carried out similarly to Example 1, and obtained the thermal storage material microcapsule dispersion liquid. . This heat storage material microcapsule dispersion had an average particle size of 1.54 μm and a non-volatile content of 30.4%. The heat storage amount of the heat storage material microcapsule calculated from the DSC measurement result is 143.4 J / g (melting temperature 90 ° C.) at the time of temperature increase, 97.3 J / g (solidification temperature 88 ° C.) at the time of temperature decrease, and the heat history durability is 98%. Met.

Example 3
840 parts and 580 parts of heat storage material as “Hi-Mic-1090” (Micro Crystalline Wax, melting point 88 ° C., manufactured by Nippon Seiki Co., Ltd.), 940 parts of “FNP-0090” and “FT-105” "Hi-Mic-1090" (Nihon Seiki Co., Ltd. microcrystalline wax, melting point 88 ° C) 710 parts is used in place of 54 parts, and the additional heat storage material "FNP-0090" is used in an amount of 710 parts. A heat storage material microcapsule dispersion was obtained in the same manner as in Example 1 except that the change was made. . This heat storage material microcapsule dispersion had an average particle size of 1.46 μm and a non-volatile content of 30.8%. The heat storage amount of the heat storage material microcapsule calculated from the DSC measurement result is 148.1 J / g (melting temperature 90 ° C.) at the time of temperature increase, 106.5 J / g (solidification temperature 88 ° C.) at the time of temperature decrease, and the heat history durability is 96%. Met.

Claims (8)

An organic solvent solution in which an acid group and a hydrolyzable silyl group-containing resin (A1) and an aliphatic hydrocarbon heat storage material (B) are dissolved in an organic solvent (C) and a basic compound (D) are mixed. After neutralizing the acid group in the resin (A1) to obtain a resin (A2) having a neutralized acid group and a hydrolyzable silyl group, the resin is mixed with water to undergo phase inversion emulsification, A method for producing a heat storage material microcapsule, comprising removing the organic solvent (C) after hydrolyzing and condensing a hydrolyzable silyl group in the resin (A2). The method for producing a heat storage material microcapsule according to claim 1, wherein the resin (A1) is a resin having a solubility parameter value of 6.5 to 9.0. The method for producing a heat storage material microcapsule according to claim 2, wherein the resin (A1) is a vinyl copolymer. The method for producing a heat storage material microcapsule according to claim 3, wherein the organic solvent (C) is an organic solvent containing an aromatic organic solvent and an alcohol organic solvent having 4 to 8 carbon atoms. Synthesis of a vinyl polymer by solution radical polymerization of a vinyl monomer in the organic solvent solution in a heat storage material solution in which the aliphatic hydrocarbon heat storage material (B) is dissolved in the organic solvent (C) 4. An organic solvent solution obtained by conducting the step, wherein the vinyl polymer having an acid group and a hydrolyzable silyl group and the aliphatic hydrocarbon heat storage material (B) are dissolved in the organic solvent (C). The manufacturing method of the thermal storage material microcapsule of description. The method for producing a heat storage material microcapsule according to claim 3, wherein the acid group is a carboxyl group. The method for producing a heat storage material microcapsule according to any one of claims 1 to 6, wherein the aliphatic hydrocarbon heat storage material (B) has a melting point of 60 to 150 ° C. The thermal storage material microcapsule produced by the manufacturing method described in any one of Claims 1-7.