JP2008069344A - Thermal storage material microcapsule - Google Patents

Abstract

An object of the present invention is to provide a heat storage material microcapsule with reduced odor.
In a heat storage material microcapsule in which a heat storage material is encapsulated with a film made of a resin obtained by reacting a polyvalent isocyanate compound and a polyvalent amine compound, at least one modified aliphatic compound is used as the polyvalent amine compound. A heat storage material microcapsule using a polyamine compound.
[Selection figure] None

Description

  The present invention relates to a microcapsule including a heat storage material.

  In recent years, it has been required to save energy by effectively using thermal energy. As an effective method, a method of storing heat by using latent heat accompanying a phase change of a substance has been considered. Compared to the method using only sensible heat without phase change, it can store a large amount of heat energy in a narrow temperature range including the melting point, thus not only reducing the capacity of the heat storage material but also reducing the amount of heat storage. There is an advantage that heat loss can be suppressed to a small amount because a large temperature difference does not occur for a large amount.

  The heat storage material that uses latent heat repeats melting (liquid) and solidification (solid), so the liquid heat storage material is sealed in a sealed container or a matrix of polymer or inorganic material so that it does not flow out. It is necessary to use it while absorbing it. For this reason, the heat exchange efficiency is often lowered or the use is limited. In order to efficiently use the heat storage material in a wide range of applications, a method of encapsulating the heat storage material has been proposed. By encapsulating the heat storage material, it is possible to keep the appearance state constant regardless of the phase state of the heat storage material.

  The microcapsule dispersion liquid in which the heat storage material microcapsules are dispersed in the medium can be handled as a liquid regardless of the phase state of the heat storage material. A microcapsule solid material that has been dried by removing the medium from the microcapsule dispersion can always be handled as a solid state.

  Examples of the film of the heat storage material microcapsule include an amino resin using an in-situ method, and among them, a melamine resin obtained by an addition condensation method of melamine and formalin. However, although various methods for treating unreacted formalin remaining in the resin have been proposed (see, for example, Patent Document 1), it is difficult to remove completely, or the treated product is colored or smelled. Sometimes occurred.

On the other hand, the heat storage material microcapsule which has microcapsule membranes, such as polyurea and a polyurethane urea manufactured without using formalin, is proposed (for example, refer to patent documents 2-3). In these patent documents, it is described that aromatic, aliphatic and alicyclic polyvalent amines such as ethylenediamine and diethylenetriamine can be used at the time of film formation. However, the heat storage material microcapsule dispersion produced using these polyvalent amines has a problem that odor is generated. In addition, although it is described that a ketimine compound that is a compound that liberates amine potentially can be used, the odor of the heat storage material microcapsule dispersion has been a problem due to the influence of the polyvalent amine compound regenerated during the reaction. . The odor of the heat storage material microcapsule dispersion has been a health and safety problem when the heat storage material microcapsules are manufactured, when the heat storage material microcapsule solids are manufactured, and when the heat storage material microcapsules are used.
JP 2002-38136 A JP 2003-3158 A JP 2004-269574 A

  The subject of this invention is providing the thermal storage material microcapsule which reduced the odor.

（一般式（Ｉ）中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄は、各々独立して、水素原子または有機残基を表す。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄のうち、少なくとも２つは水素原子である。ただし、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄の全てが同時に水素原子であることはない。Ｒ₅は二価の有機基を表す。ｍは１〜２０の整数を表す。ｍが２以上のとき、複数のＲ₄は同一でも、異なっていてもよい。ｍが２以上のとき、複数のＲ₅は同一でも、異なっていてもよい。）
（４）多価イソシアネート化合物のイソシアネート基に対する多価アミン化合物のアミノ基（但し、第１級アミノ基と第２級アミノ基）のモル比率が０．３〜２．０である上記（１）記載の蓄熱材マイクロカプセル。 As a result of intensive studies, the present inventors have found the following invention.
(1) In a heat storage material microcapsule in which a heat storage material is encapsulated by a film made of a resin obtained by reacting a polyvalent isocyanate compound and a polyvalent amine compound, at least one modified aliphatic polyamine as the polyvalent amine compound Thermal storage material microcapsule characterized by using a compound,
(2) The heat storage material microcapsule according to (1), wherein the content ratio of the modified aliphatic polyamine compound to the total amount of the polyvalent amine compound is 50 to 100% by mass,
(3) The heat storage material microcapsule according to (1) or (2), wherein the modified aliphatic polyamine compound is a compound represented by the general formula (I),

(In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or an organic residue. Among R ₁ , R ₂ , R ₃ and R ₄ , at least Two are hydrogen atoms, provided that R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen atoms at the same time, R ₅ represents a divalent organic group, m is 1-20. Represents an integer. When m is 2 or more, the plurality of R ₄ may be the same or different. When m is 2 or more, the plurality of R ₅ may be the same or different.)
(4) The above (1), wherein the molar ratio of the amino group (primary amino group and secondary amino group) of the polyvalent amine compound to the isocyanate group of the polyvalent isocyanate compound is 0.3 to 2.0. The heat storage material microcapsule described.

  The heat storage material microcapsule of the present invention is a heat storage material microcapsule in which a heat storage material is encapsulated with a film made of a resin obtained by reacting a polyvalent isocyanate compound and a polyvalent amine compound. A heat storage material microcapsule using a modified aliphatic polyamine compound. By using the modified aliphatic polyamine compound, the odor of the heat storage material microcapsule dispersion can be suppressed, and the health and safety problems during production and use can be improved.

  The microencapsulation method used in the present invention is generally referred to as an interfacial polymerization method. Specifically, a heat storage material in which an oil-soluble reactive compound (compound A) soluble in a heat storage material to be a core material is dissolved, and a surfactant and a compound having active hydrogen (compound B) are continuously dissolved. Disperse in the aqueous phase in the form of microdroplets. Subsequently, heating and stirring are performed, and the compound A and the compound B, which are dissolved in the heat storage material phase and the water phase, are polymerized at the interface between the heat storage material phase and the water phase, and are insoluble in water and oil. A film is formed and microcapsules are obtained. As specific coatings, polyester, polyamide, polyurea, and polyurethane coating microcapsules are known, but the strength and elasticity that can withstand multiple expansion and contraction of the heat storage material during phase change, and coating A microcapsule having a polyurea or polyurethaneurea resin film is preferably used as a heat storage material microcapsule as a film having physical and chemical strength that can withstand the process and impregnation process. In the heat storage material microcapsule of the present invention, a polyvalent isocyanate compound is used as the compound A, and a polyvalent amine compound is used as the compound B.

  In the present invention, at least one modified aliphatic polyamine compound is used as the polyvalent amine compound. The modified aliphatic polyamine compound is selected from an active hydrogen derived from a partial amino group of the aliphatic polyamine compound and, for example, an epoxy compound, an unsaturated compound containing a double bond, a methylol compound, a carboxylic acid compound, and a thiourea compound. It can be obtained by reacting with at least one compound. By this reaction, the active hydrogen derived from the amino group is substituted with an aliphatic substituent or an aromatic substituent, and the odor can be reduced. The modified aliphatic polyamine compound according to the present invention has at least two active hydrogens derived from amino groups.

  Examples of the aliphatic polyamine compound constituting the modified aliphatic polyamine compound include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethyl- 2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3'-iminobis (propylamine) ), 3,3′-methyliminobis (propylamine), bis (3-aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine, bisaminomethylnorbornane, Screw (4- Minocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminocyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5 , 5] Undecane. Examples of the aliphatic polyamine having an aromatic substituent include m-xylylenediamine and tetrachloro-p-xylylenediamine.

In the present invention, a more preferred modified aliphatic polyamine compound is a compound represented by the general formula (I). R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an organic residue. At least two of R ₁ , R ₂ , R ₃ , and R ₄ are necessarily hydrogen atoms and serve as reaction points with the polyvalent isocyanate compound. However, R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen atoms at the same time. The organic residue is a group derived from at least one compound selected from an epoxy compound, an unsaturated compound containing a double bond, a methylol compound, a carboxylic acid compound, and a thiourea compound.

Specific examples of the organic residue in R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group, alkenyl group, hydroxyalkyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylalkyl group, polyoxyalkylene group, cyano An alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, etc. can be mentioned. More preferred specific examples are those having 1 to 1 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, and n-hexyl group. 22 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 22 carbon atoms such as vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group; hydroxymethyl group, hydroxyethyl group, hydroxypropyl An aromatic ring having 6 to 12 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a thiophene ring, a furan ring, a pyrrole ring, a pyrazole ring, a pyridine ring, and a pyran ring; Heterocycle: methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, n-propoxycal A carbon number of 2 which may be substituted such as nyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc. -22 linear or branched alkoxycarbonyl group; methoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, n-propoxycarbonylethyl group, n-propoxycarbonylpropyl group, isopropoxycarbonylmethyl Group, linear or branched alkoxycarbonylalkyl group having 3 to 22 carbon atoms such as isopropoxycarbonylethyl group, polyoxyethylene group, polyoxypropylene group, polyoxyethylene and polyoxypropylene Include cyanoethyl group; polyoxyalkylene groups such as copolymerized group. Among these, a hydroxyalkyl group and a polyoxyalkylene group are preferable.

Specific examples of R ₅ include an alkylene group having 1 to 12 carbon atoms, a cycloalkylalkylene group having 6 to 12 carbon atoms, an arylalkylene group having 7 to 14 carbon atoms, and a cycloalkylene group having 5 to 8 carbon atoms. It is done. Among these, a C2-C5 alkylene group is preferable.

  The amine value of the modified aliphatic polyamine compound is preferably 20 to 2000 mgKOH / g, and more preferably 50 to 1500 mgKOH / g. When the amine value remaining in the modified aliphatic polyamine compound is less than 20 mgKOH / g, the crosslinking density may be lowered and the heat resistance of the capsule may be deteriorated. When it is higher than 2000 mgKOH / g, the crosslinking density increases too much, the flexibility of the capsule film is insufficient, and the phase change repeated durability may deteriorate.

  Commercially available modified aliphatic polyamine compounds include “Fujicure”, “Tomide” (Fuji Kasei Kogyo Co., Ltd.), “Adeka Hardener” (Adeka Co., Ltd.), “Rakkamide” (Dainippon Ink Chemical Co., Ltd.), “Kaya Hard” "Nippon Kayaku Co., Ltd.", "React" (Sanyo Kasei Kogyo Co., Ltd.), "JER Cure" (Japan Epoxy Resin Co., Ltd.), "Daito Kral" (Daito Sangyo Co., Ltd.), "Three Bond 2100 Series" (Three Bond) Etc.).

  By using the modified aliphatic polyamine compound, in addition to the effect that the odor of the heat storage material microcapsule dispersion is reduced, the effect that the phase change repetition durability of the heat storage material microcapsule itself is improved is exhibited. In the heat storage material microcapsule, volume fluctuation occurs when the heat storage material contained therein repeats melting (liquid) and solidification (solid). It is presumed that the organic residue contained in the modified aliphatic polyamine compound expands and contracts the heat storage material microcapsule film so as to absorb the volume fluctuation, and the durability against repeated phase change is improved.

  The polyvalent isocyanate compound according to the present invention is a compound having at least two isocyanate groups and is preferably soluble in a heat storage material serving as a core material. Specific examples include m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, toluene-2,4,6-triisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2, 4'-diisocyanate, naphthalene-1,5-diisocyanate, m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis Isocyanate monomers such as (isocyanatomethyl) cyclohexane, norbornane diisocyanate, and isophorone diisocyanate. Further, isocyanate oligomers or isocyanate polymers such as polymethylene polyphenyl polyisocyanate are also included. Furthermore, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of tolylene diisocyanate and hexanetriol, burette adducts of hexamethylene diisocyanate, isocyanate monomers, isocyanate oligomer or isocyanate polymer polyol modified products and carbodiimide modified products, etc. Is mentioned. These can also be used in combination. When an aromatic isocyanate is used, a capsule film resin that is thermally or chemically stable can be obtained. On the other hand, when an aliphatic isocyanate is used, it is possible to obtain a capsule film resin that does not easily yellow or does not yellow. In applications where discoloration is hated, heat storage material microcapsules using aliphatic isocyanates can be suitably used. The polyvalent isocyanate compound is added in the range of 1 to 50% by mass with respect to the heat storage material.

  In combination with the modified aliphatic polyamine compound, a low molecular weight polyamine compound or a high molecular amine compound can also be used as a copolymerization component. The low molecular weight polyamine compound that can be used is a low molecular compound having at least two primary amino groups and / or secondary amino groups. Specific examples of the low molecular weight polyamine compound include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, tris (2-aminoethyl) amine, o-phenylenediamine, p-phenylenediamine, Aromatic amines such as diaminonaphthalene and xylylenediamine can be exemplified. Specific examples of the polymeric amine compound include polyethyleneimine and derivatives thereof, polypropyleneamine, polyvinylamine and derivatives thereof, polyallylamine and derivatives thereof, polyetheramine, poly-L-lysine, poly-L-ornithine and the like. Can do.

  In the present invention, the content ratio of the modified aliphatic polyamine compound with respect to the total amount of the polyvalent amine compound is preferably 50 to 100% by mass, and more preferably 65 to 100% by mass. If the content ratio of the modified aliphatic polyamine compound is less than 50% by mass, the odor may be difficult to reduce.

  The molar ratio of the amino group of the polyvalent amine compound to the isocyanate group of the polyvalent isocyanate compound (however, the primary amino group and the secondary amino group) is preferably from 0.01 to 20, 10 is more preferable. When the molar ratio is less than 0.01, the heat resistance and solvent resistance of the heat storage material microcapsules may be insufficient. When the molar ratio exceeds 20, the dispersion stability of the dispersion liquid of the heat storage material microcapsules may be inferior or the liquid viscosity may become too high. Furthermore, when used for applications exposed to high temperatures and high humidity, the molar ratio is preferably 0.3 to 2.0, and more preferably 0.5 to 1.5. When the molar ratio is less than 0.3, heat resistance and solvent resistance of the heat storage material microcapsule after being exposed to high temperature and high humidity may be insufficient, and when the molar ratio exceeds 2.0. When exposed to high temperature or high humidity, the heat storage material microcapsules may change color (mainly yellow).

  The heat storage material encapsulated in the heat storage material microcapsule of the present invention is used for the purpose of storing heat using latent heat accompanying phase transition, and any compound having a melting point or a freezing point can be used. Specific heat storage materials include tetradecane, hexadecane, octadecane, and paraffin wax and other aliphatic hydrocarbon compounds (paraffinic compounds), fatty acids such as palmitic acid and myristic acid, and aromatic hydrocarbons such as benzene and p-xylene. Compounds, ester compounds such as isopropyl palmitate, butyl stearate, stearyl stearate and the like, and compounds such as alcohols such as stearyl alcohol, preferably a compound having a heat of fusion of about 80 kJ / kg or more, chemically and physically A stable material is used. Two or more of these may be used in combination, and a supercooling inhibitor, a specific gravity adjuster, a deterioration inhibitor and the like may be added as necessary. It is also possible to use a mixture of two or more heat storage materials having different melting points.

  In the heat storage material microcapsule of the present invention, the mixing ratio (mass basis) of the microcapsule film / heat storage material is 2/98 to 50/50, more preferably 5/95 to 30/70. When the blending ratio of the microcapsule film is less than 2% by mass, the heat storage material may not be completely covered and the heat storage material may leak out. When the blending ratio of the microcapsule film exceeds 50% by mass, the heat storage material microcapsules have a small amount of heat of fusion, and thus a sufficient heat storage effect may not be exhibited.

  The volume average particle diameter of the heat storage material microcapsules of the present invention is preferably in the range of 0.2 to 50 μm, more preferably in the range of 0.5 to 20 μm. When the particle diameter is larger than 50 μm, the mechanical shearing force may be extremely weak, and when the particle diameter is smaller than 0.2 μm, the fracture may be suppressed, but the film thickness may be reduced and the heat resistance may be poor. The volume average particle diameter described in the present invention represents the average particle diameter of the microcapsule particles in terms of volume, and in principle, particles having a fixed volume are sieved in order from the smallest, and the particles corresponding to 50% of the volume. Means the particle size at the time of separation. The volume average particle size can be measured by actual measurement by microscopic observation, but can be automatically measured by using a commercially available electrical or optical particle size measuring device.

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

  Hereinafter, the present invention will be described in more detail by way of examples. The parts and percentages in the examples are based on mass unless otherwise specified.

(Examples 1-20)
Heat storage material microcapsule dispersions were produced with the formulations shown in Tables 1 to 4. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 50 degreeC using the emulsifier, and prepared the emulsion. After adding the aqueous solution of the polyamine solution to this emulsion, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a heat storage material microcapsule dispersion.

(Examples 21 to 25)
A heat storage material microcapsule dispersion was prepared with the formulation shown in Table 5. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 40 degreeC using the emulsifier, and prepared the emulsion. After adding an aqueous solution of a polyamine solution to this emulsion, the mixture was heated and stirred at 70 ° C. for 2 hours to obtain a dispersion liquid of heat storage material microcapsules.

(Comparative Examples 1-3)
A heat storage material microcapsule dispersion was prepared with the formulation shown in Table 6. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 50 degreeC using the emulsifier, and prepared the emulsion. After adding the aqueous solution of the polyamine solution to this emulsion, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a heat storage material microcapsule dispersion.

(Comparative Example 4)
A heat storage material microcapsule dispersion was prepared with the formulation shown in Table 6. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 40 degreeC using the emulsifier, and prepared the emulsion. After adding an aqueous solution of a polyamine solution to this emulsion, the mixture was heated and stirred at 70 ° C. for 2 hours to obtain a dispersion liquid of heat storage material microcapsules.

(Examples 26 to 32)
Heat storage material microcapsule dispersions were produced with the formulations shown in Tables 7-8. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 50 degreeC using the emulsifier, and prepared the emulsion. After adding the aqueous solution of the polyamine solution to this emulsion, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a heat storage material microcapsule dispersion.

(Examples 33-61)
Heat storage material microcapsule dispersions were produced with the formulations shown in Tables 9-12. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 50 degreeC using the emulsifier, and prepared the emulsion. After adding the aqueous solution of the polyamine solution to this emulsion, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a heat storage material microcapsule dispersion.

(Comparative Examples 5-7)
A heat storage material microcapsule dispersion was prepared with the formulation shown in Table 13. What mixed uniformly the heat storage material, the supercooling inhibitor, and the polyvalent isocyanate compound was added in the emulsifier aqueous solution, and it stirred and emulsified at 50 degreeC using the emulsifier, and prepared the emulsion. After adding the aqueous solution of the polyamine solution to this emulsion, the mixture was heated and stirred at 80 ° C. for 2 hours to obtain a heat storage material microcapsule dispersion.

  The following evaluation was performed with respect to the obtained heat storage material microcapsules, and the results are shown in Tables 14 to 15.

[Volume average particle diameter of heat storage material microcapsules]
The volume average particle size was measured using a particle size measuring device Multisizer II type manufactured by Coulter USA.

[Heat history durability (phase change repeated durability)]
Take 5g of dispersion of microcapsules of heat storage material, heat at 100 ° C for 2 hours, evaporate the water of the medium, put the dried product in a thermostatic chamber where the temperature can be controlled, and adjust the phase change temperature. The temperature range between 0 ° C. and 100 ° C. was measured as the temperature range to be sandwiched, and the heat storage amount after repeating 300 times was measured, and the ratio with the heat storage amount before giving the temperature change was defined as heat history durability. One temperature change is a cycle in which the temperature is raised for 1 hour, held at 100 ° C. for 30 minutes, the temperature is lowered for 1 hour, and kept at 0 ° C. for 30 minutes.

  The amount of heat stored was determined by the amount of heat of fusion measured with a differential scanning calorimeter. Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer, USA), heat storage material microcapsules were measured at a sample amount of 2 ± 0.2 mg, a heating rate of 10 ° C./min, and a cooling rate of 10 ° C./min. The integrated value of the difference between the endothermic peak and the baseline of the heat capacity curve at the time of temperature rise was defined as the heat of fusion.

[Odor]
The heat storage material microcapsule dispersion was held at 50 ° C. and a relative humidity of 95% for 6 hours, and then its odor was evaluated. The evaluation was performed by 10 monitors, and the maximum number of evaluations determined by each person was used as the evaluation result. The evaluation standards for odor are as follows.
A: No odor is felt.
○: A slight odor is felt.
Δ: Odor is felt.
X: Feels odor. Furthermore, irritation is felt in the eyes and throat.

  The heat storage material microcapsule dispersion using the modified aliphatic polyamine compound shown in Examples 1 to 61 is compared with the heat storage material microcapsule dispersion using the aliphatic polyamine compound shown in Comparative Examples 1 to 7, It was confirmed that the odor was greatly reduced. In addition, the heat storage material microcapsules using the modified aliphatic polyamine compounds of Examples 1 to 61 were compared with the heat storage material microcapsules using the aliphatic polyamine compounds shown in Comparative Examples 1 to 7, and repeated phase change durability. It was considered that this was because the modified aliphatic polyamine compound efficiently absorbed the volume change of the heat storage material during the phase change repetition.

  Examples 5, 30 to 32, and Comparative Example 1 are heat storage material microcapsules in which a modified aliphatic polyamine compound / aliphatic polyamine compound (mass ratio) was changed from 0/100 to 100/0 as a polyvalent amine compound. is there. It was confirmed that the higher the content ratio of the modified aliphatic polyamine compound in the polyvalent amine compound, both the odor and the phase change repeated durability were improved.

  When Examples 6, 7, and 20 were blended so that the molar ratio of the amino group of the polyvalent amine compound to the isocyanate group of the polyvalent isocyanate compound was 1.3 or more, the modified aliphatic polyamine compound was a hydroxyalkyl group. In Example 6 and Example 20 containing a polyoxyalkylene group, it was confirmed that the odor was suppressed.

  The following evaluation was performed on the heat storage material microcapsules obtained in Examples 1 to 61, and the results are shown in Tables 16 to 17.

[Heat resistance after storage at high temperature and high humidity]
2 g of the heat storage material microcapsule dispersion was collected in an aluminum cup having a bottom inner diameter of 5 cm, heated at 100 ° C. for 2 hours to evaporate the water of the medium, and the mass W1 of the obtained dried product was measured. Furthermore, mass W2 after heat-treating at 200 degreeC for 3 hours was measured in the air atmosphere using the forced circulation type thermostat dryer. Here, the percentage of the value obtained by dividing the mass reduction amount (W1-W2) by the mass W1 before the heat treatment was defined as the thermal reduction rate A.
Thermal reduction rate A (%) = (W1-W2) / W1 × 100

Next, 2 g of the heat storage material microcapsule dispersion was collected in an aluminum cup having a bottom inner diameter of 5 cm, heated at 100 ° C. for 2 hours to evaporate the water of the medium, and the mass W3 of the obtained dried product was measured. Subsequently, the dried product as it is in the aluminum cup is stored for 10 days in a constant temperature and humidity chamber at a temperature of 80 ° C. and a relative humidity of 90%. The mass W4 after heat treatment at 200 ° C. for 3 hours was measured. The percentage of the value obtained by dividing the mass reduction amount (W3-W4) by the mass W3 before the heat treatment was defined as the thermal reduction rate B.
Thermal reduction rate B (%) = (W3-W4) / W3 × 100

Here, a value obtained by dividing the thermal reduction rate B by the thermal reduction rate A was defined as a thermal reduction rate fluctuation ratio (thermal reduction rate B / thermal reduction rate A), which was used as an index of heat resistance after storage at high temperature and high humidity. The evaluation criteria are as follows.
○: Thermal reduction rate fluctuation ratio is less than 2 Δ: Thermal reduction rate fluctuation ratio is 2 or more and less than 3 ×: Thermal reduction rate fluctuation ratio is 3 or more

[Moist heat yellowing]
Dilute the heat storage material microcapsule dispersion with water so that the capsule solids concentration is 10%, soak cotton cloth (weighing 120 g / m ² , exposed) in this diluted dispersion, pull it up, and the amount of liquid adhered The excess liquid was squeezed out between two rubber roll pairs to 120 ± 10 g / m ^2, and then dried at 100 ° C. for 10 minutes to obtain a capsule-impregnated cloth. Next, the capsule-impregnated cloth and the control raw cotton cloth are hung with a stand and a clip inside a thermo-hygrostat maintained at a temperature of 60 ° C. and a relative humidity of 90%, and held for 72 hours. Wet heat test was performed. Capsule-impregnated fabric after wet heat test and control raw cotton fabric were measured in a L ^* a ^* b ^* mode at 2 ° light source C using a color difference meter (SpectreEye, manufactured by Gretag Macbeth, Switzerland) The difference between the b ^* value of the impregnated fabric and the b ^* value of the control untreated cotton fabric was taken as Δb ^* , and the degree of wet heat yellowing was determined based on the magnitude of this Δb ^* value. The evaluation criteria for wet heat yellowing are as follows.
○: Δb ^* is less than 4 Δ: Δb ^* is 4 or more and less than 6 ×: Δb ^* is 6 or more

  From the results of Table 16 and Table 17, when the molar ratio of the amino group of the polyvalent amine compound to the isocyanate group of the polyvalent isocyanate compound is 0.3 to 2.0, heat resistance after wet heat yellowing and storage at high temperature and high humidity The property was good. In particular, the evaluation results were excellent when the molar ratio was 0.5 to 1.5. In Examples 4, 13, 23, 37, 45, 53 and 54 in which the molar ratio exceeded 2.0, wet heat yellowing tended to decrease. On the other hand, in Example 61 where the molar ratio was less than 0.3, the heat resistance after storage at high temperature and high humidity tended to decrease.

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

Claims (4)

  In a heat storage material microcapsule in which a heat storage material is encapsulated with a film made of a resin obtained by reacting a polyvalent isocyanate compound and a polyvalent amine compound, at least one modified aliphatic polyamine compound is used as the polyvalent amine compound. A heat storage material microcapsule characterized by that.   The heat storage material microcapsule according to claim 1, wherein the content ratio of the modified aliphatic polyamine compound to the total amount of the polyvalent amine compound is 50 to 100% by mass. The heat storage material microcapsule according to claim 1 or 2, wherein the modified aliphatic polyamine compound is a compound represented by the general formula (I).

(In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or an organic residue. Among R ₁ , R ₂ , R ₃ and R ₄ , at least Two are hydrogen atoms, provided that R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen atoms at the same time, R ₅ represents a divalent organic group, m is 1-20. Represents an integer. When m is 2 or more, the plurality of R ₄ may be the same or different. When m is 2 or more, the plurality of R ₅ may be the same or different.)   The heat storage material according to claim 1, wherein the molar ratio of the amino group of the polyvalent amine compound to the isocyanate group of the polyvalent isocyanate compound (provided that the primary amino group and the secondary amino group) is 0.3 to 2.0. Micro capsule.