JP2006045492A - Heat storage insulator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat storage insulator that has an excellent heat storage/insulation properties, can keep a comfortable environment with little temperature fluctuation in the space against the change of outer air temperature, and is useful in saving energy. <P>SOLUTION: The heat storage insulator is a layered material comprised of a heat reservoir, that is prepared by supporting a heat storage material on a porous body, and a heat insulator, wherein the heat reservoir is preferably a product prepared by supporting a heat storage material and a layered clay mineral on a porous body. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat storage heat insulator having high heat storage properties and heat insulation properties.

  As a technique for controlling thermal energy, there are a heat storage technique, a heat insulation technique, and the like, which are attracting attention as one of the techniques for solving recent energy problems.

  Thermal storage technology is a technology that stores and uses solar energy, geothermal heat, and other natural energy, as well as heat from air conditioners, etc., and heat insulation technology cuts off heat from the outside and keeps the heat from escaping from the inside. Technology.

  For example, in the residential field, the use of such heat storage technology and heat insulation technology can store heat using cheap nighttime power, use it as a multipurpose heat source, reduce power consumption during the day, and Examples include materials used in energy-saving houses that can block the influence of temperature and reduce fluctuations in room temperature.

  For example, Patent Document 1 describes a body panel of a building in which a heat insulating material is arranged on the outdoor side and a latent heat storage material is arranged on the indoor side, so as to save energy of cooling and heating energy in a house. Yes. In patent document 1, what sealed the latent heat storage material in the casing and the heat insulating material are laminated | stacked.

  Further, Patent Document 2 describes a structure of a fuselage that combines a heat insulating material layer on the outdoor side and a heat storage material layer made of a latent heat storage material on the indoor side. By reducing the amount and maintaining a comfortable indoor environment, the energy required for air conditioning is reduced. In Patent Literature 2, a latent heat storage material that is microencapsulated is used as the heat storage material layer.

JP-A-61-122354 JP 2003-349993 A

  By the way, as a heat storage material used for the heat storage technology, a sensible heat storage material and a latent heat storage material can be cited, and in particular, a lot of latent heat storage materials using latent heat due to phase change of a substance are employed (the above-mentioned Patent Document 1). In Patent Document 2, a latent heat storage material is also used.)

  This latent heat storage material uses the property of storing heat (heat storage) when a substance changes phase from solid to liquid, and releasing (dissipating heat) when changing phase from liquid to solid, and stores and releases heat. In general, many phase change (solid-liquid change) occurs in a temperature range of 15 ° C to 50 ° C. Therefore, it is necessary to handle it as a liquid. As a method of using the liquid, it is common to enclose it in a liquid state in a sealed laminate sheet or plastic case, or to encapsulate it.

  However, as a heat storage technique, (1) a latent heat storage material sealed in a casing (for example, Patent Document 1) or (2) a latent heat storage material encapsulated (for example, Patent Document 2). When used, the following problems occurred.

  (1) When using what sealed the latent heat storage material in the casing, it is limited to the size of a casing and processing, such as cutting, is impossible because a latent heat storage material leaks out. In addition, construction by nailing or the like is impossible because the latent heat storage material leaks out. Furthermore, when fixed in the vertical direction, the latent heat storage material is biased toward the bottom, and the latent heat storage material cannot be effectively used.

  (2) When the encapsulated latent heat storage material is used, effective heat conduction to the latent heat storage material itself is hindered by the capsule, so that the heat storage performance is not sufficiently exhibited and the space due to the influence of the outside air temperature There is a problem that relaxation of temperature change cannot be expected. Furthermore, the content of the latent heat storage material is small and sufficient heat storage performance may not be exhibited.

  In order to solve the above-described problems, the present invention has been intensively studied. As a result, a heat storage insulator in which a heat storage material in which a heat storage material (a) is supported on a porous body (c) and a heat insulator are laminated is a heat storage material. There is no leakage, excellent workability and workability, excellent heat storage and heat insulation, and it is possible to maintain a comfortable environment with little variation in space temperature against changes in outside air temperature, and to save energy. As a result, the present invention has been completed.

That is, the present invention has the following characteristics.
1. A heat storage heat insulator in which a heat storage body and a heat insulator are laminated, wherein the heat storage body is a porous body (c) carrying the heat storage material (a).
2. As the heat storage body, a porous body (c) in which a heat storage material (a) and a layered clay mineral (b) are supported is used. The thermal storage insulator according to 1.
3. 1. A material obtained by mixing 0.5 to 50 parts by weight of layered clay mineral (b) with respect to 100 parts by weight of heat storage material (a) is used. The thermal storage insulator according to 1.
4). As the heat storage body, a porous body (c) further supported by a heat conductive substance (d) is used. To 3. A thermal storage insulator according to any one of the above.
5. 3. A material obtained by mixing 5 to 200 parts by weight of the heat conductive substance (d) with respect to 100 parts by weight of the heat storage material (a) is used. The heat storage body as described in 4.
6). The porous body (c) was formed by the reaction between the compound (c-1) containing a reactive functional group and the compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group. 1. It is characterized by being To 5. A thermal storage insulator according to any one of the above.
7). The heat storage body uniformly mixes the heat storage material (a), the compound (c-1) containing a reactive functional group and the compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group. And obtained by reacting the component (c-1) and the component (c-2). Or 6. The thermal storage insulator according to 1.
8). The heat storage body can react with the heat storage material (a), the layered clay mineral (b) and / or the heat conductive material (d), the compound (c-1) containing a reactive functional group, and the reactive functional group. 1. A compound obtained by uniformly mixing a compound (c-2) containing a reactive functional group and reacting the component (c-1) and the component (c-2). To 6. A thermal storage insulator according to any one of the above.
9. The heat storage material is a heat storage material (a), a nonionic surfactant (e) having a hydrophilic / lipophilic balance (HLB value) of 10 or more, a compound (c-1) containing a reactive functional group, and the reactive functional group. The compound (c-2) containing a reactive functional group capable of reacting with a group is mixed, the heat storage material (a) is dispersed in a colloidal form, and the component (c-1) and the component (c-2) are reacted. 1. It is obtained by the following. Or 6. The thermal storage insulator according to 1.
10. The heat storage material is a heat storage material (a), a layered clay mineral (b) and / or a heat conductive substance (d), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant (e), A compound (c-1) containing a reactive functional group and a compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group are mixed, and the heat storage material (a) is dispersed in a colloidal form. And obtained by reacting the component (c-1) and the component (c-2). To 6. A thermal storage insulator according to any one of the above.
11. The layered clay mineral (b) is an organically treated layered clay mineral. 2 to 10. A thermal storage insulator according to any one of the above.
12 The content of the heat storage material (a) in the heat storage body is 40% by weight or more. To 11. A thermal storage insulator according to any one of the above.
13. 1. The heat storage material (a) is an organic latent heat storage material. To 12. A thermal storage insulator according to any one of the above.
14 The thermal conductivity of the heat insulator is less than 0.1 W / (m · K). To 13. A thermal storage insulator according to any one of the above.

Even if the heat storage insulator of the present invention has a high heat storage material content, the heat storage material does not leak over time. Furthermore, even if the heat storage body is cut, the heat storage material does not leak from the cut surface, and it is excellent in workability, and since the heat storage material does not leak due to nailing or the like, it is excellent in installation workability.
In addition, since it exhibits excellent heat storage and heat insulation properties, it is possible to maintain a comfortable environment with little variation in space temperature against changes in outside air temperature, and energy saving can be achieved.

  Hereinafter, the present invention will be described in detail together with the best mode for carrying out the invention.

  The present invention relates to a heat storage material in which a heat storage material and a heat insulator are stacked by supporting a heat storage material (hereinafter also referred to as “(a) component”) on a porous body (hereinafter also referred to as “component (c)”). It is an insulator.

  Although it will not specifically limit as (a) component if it is a heat storage material, Latent heat storage materials, such as an inorganic latent heat storage material and an organic latent heat storage material, etc. are mentioned.

  Examples of the inorganic latent heat storage material include hydrates such as sodium sulfate decahydrate, sodium carbonate decahydrate, sodium hydrogen phosphate dodecahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, etc. Examples include salts.

  Examples of the organic latent heat storage material include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, long chain fatty acid esters, fatty acid triglycerides, polyether compounds, and the like, and one or more of these heat storage materials are used. Can be used.

  In the present invention, an organic latent heat storage material can be particularly preferably used. Organic latent heat storage materials are preferred because they have a high boiling point and are less likely to volatilize, so there is almost no volume change (thinning) during the heat storage body molding and the heat storage performance lasts for a long time. Furthermore, when an organic latent heat storage material is used, it is easy to set the phase change temperature according to the application. For example, by mixing two or more organic latent heat storage materials having different phase change temperatures, the phase change temperature can be easily set. Can be set.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used. Specifically, n-decane (melting point −30 ° C.), n-undecane (melting point −25 ° C.), n-dodecane (melting point -8 ° C), n-tridecane (melting point -5 ° C), n-tetradecane (melting point 8 ° C), pentadecane (melting point 10 ° C), n-hexadecane (melting point 17 ° C), n-heptadecane (melting point) 22 ° C), n-octadecane (melting point 28 ° C), n-nonadecane (melting point 32 ° C), icosane (melting point 36 ° C), docosan (melting point 44 ° C), and a mixture thereof. Etc.

  As the long chain alcohol, for example, a long chain alcohol having 8 to 36 carbon atoms can be used. Specifically, capryl alcohol (melting point: 7 ° C.), lauryl alcohol (melting point: 24 ° C.), myristyl alcohol (melting point: 38 ° C.) ), Stearyl alcohol (melting point: 58 ° C.), and the like.

  As the long chain fatty acid, for example, a long chain fatty acid having 8 to 36 carbon atoms can be used. Specifically, octanoic acid (melting point: 17 ° C.), decanoic acid (melting point: 32 ° C.), dodecanoic acid (melting point: 44 ° C.). ), Fatty acids such as tetradecanoic acid (melting point 50 ° C.), octadecanoic acid (melting point 70 ° C.), hexadecanoic acid (melting point 63 ° C.), and the like.

  As the long-chain fatty acid ester, for example, a long-chain fatty acid ester having 8 to 36 carbon atoms can be used. Specifically, methyl laurate (melting point 5 ° C.), methyl myristate (melting point 19 ° C.), palmitic acid Examples include methyl (melting point: 30 ° C.), methyl stearate (melting point: 38 ° C.), butyl stearate (melting point: 25 ° C.), and methyl arachidate (melting point: 45 ° C.).

  Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and medium-chain fatty acid triglycerides and long-chain fatty acid triglycerides that are refined processed products thereof.

  Examples of the polyether compound include diethylene glycol, triethylene glycol, tetraethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, polypropylene glycol, polyethylene glycol, polypropylene glycol diacrylate, and ethyl ethylene glycol.

  In the present invention, as the heat storage material, in particular, an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and a long chain fatty acid ester having 8 to 36 carbon atoms. It is preferable to use an aliphatic hydrocarbon having 8 to 36 carbon atoms and a long chain fatty acid ester having 8 to 36 carbon atoms. Among them, it is preferable to use a long-chain fatty acid ester having 8 to 36 carbon atoms, preferably a long-chain fatty acid ester having 15 to 22 carbon atoms. Such a long-chain fatty acid ester has a high latent heat and has a practical temperature range. Since it has a phase change temperature (melting point), it is easy to use for various applications.

Moreover, when mixing and using 2 or more types of organic latent heat storage materials, it is preferable to use a compatibilizing agent. By using a compatibilizing agent, the compatibility between the organic latent heat storage materials can be improved.
Examples of the compatibilizing agent include fatty acid triglycerides, nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less), and one or two of these. The above can be mixed and used.

  As described above, the fatty acid triglyceride is a substance that is also used as an organic latent heat storage material. Such fatty acid triglycerides are particularly preferable because they can further improve the compatibility between the organic latent heat storage materials and have excellent heat storage properties. Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and fatty acid triglycerides such as caprylic acid triglyceride, palmitic acid triglyceride, and stearic acid triglyceride, which are refined processed products thereof. More than seeds can be used.

  Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less) include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, Sorbitan sesquioleate, sorbitan trioleate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, glycerol monostearate, glycerol monostearate, glycerol monooleate, stearic acid Examples include glyceryl, glyceryl caprylate, sorbitan stearate, sorbitan oleate, sorbitan sesquioleate, and coconut fatty acid sorbitan.

  The mixing ratio of the compatibilizer and the component (a) is usually about 0.1 to 20 parts by weight (preferably 0.5 to 10 parts by weight) of the compatibilizer with respect to 100 parts by weight of the component (a). And it is sufficient.

In the present invention, it is particularly preferable to use a mixture of component (a) and layered clay mineral (hereinafter also referred to as “component (b)”).
By mixing the (b) component and the (a) component, the (a) component enters between the layers of the (b) component, and the (a) component is easily held between the (b) component layers.
Furthermore, it is preferable that the component (b) is an organically treated layered clay mineral. In such a case, the component (a) easily enters the layer between the components (b), and the component (a) is the component (b). The structure is more easily held between layers.

By mixing the component (b) and the component (a), the viscosity of the component (a) is increased as a result, and the component (a) is more stably supported in the component (c) described later. Is done. Therefore, it is possible to prevent the component (a) from leaking to the outside of the heat storage body, and to obtain a heat storage body excellent in heat storage performance and excellent in workability and workability.
Furthermore, when an organic latent heat storage material is used as the component (a), the component (b) hardly reacts with the organic latent heat storage material and does not affect the melting point of the organic latent heat storage material or other various physical properties. Since the performance as a heat storage material can be exhibited efficiently and the phase change temperature (melting point) can be easily set, it is preferable.

  The interval between the bottom surfaces of the component (b) is preferably about 13.0 to 30.0 mm (preferably 15.0 to 26.0 mm). By being in such a range, the component (a) is more easily penetrated between layers of the component (b). The bottom surface interval is a value calculated from (001) reflection in the X-ray diffraction pattern.

The viscosity at the time of mixing the component (a) and the component (b) may be about 0.5 to 20.0 Pa · s. The viscosity is a value measured with a B-type rotational viscometer at a temperature of 23 ° C. and a relative humidity of 50% RH.
Moreover, what is necessary is just to make TI value at the time of (a) component and (b) component mixing into about 4.0-9.0. In addition, TI value is a value calculated | required by following formula 1 using a B-type rotational viscometer.
TI value = η1 / η2 (Formula 1)
(However, η1: Viscosity at 2 rpm (Pa · s: guide value for the second rotation), η2: Viscosity at 20 rpm (Pa · s: Guide value for the fourth rotation))

  By setting such viscosity and TI value, the component (a) is easily supported stably in the heat storage body during the manufacture of the heat storage body, and the component (a) is included in the heat storage body after the heat storage body is manufactured. Is easily held for a long time. Therefore, it is possible to prevent the component (a) from leaking to the outside of the heat storage body, and to obtain a heat storage body that is more excellent in heat storage property and more excellent in workability and workability.

  Examples of the component (b) include smectite, vermiculite, kaolinite, allophane, mica, talc, halloysite, and sepiolite. In addition, swellable fluorine mica, swellable synthetic mica, and the like can be used.

Examples of the organic treatment include ion exchange (intercalation) of a cation existing between layers of a layered clay mineral with a long-chain alkylammonium ion or the like.
In the present invention, smectite and vermiculite are particularly preferably used because they are easily organically treated. Furthermore, among the smectites, montmorillonite is particularly preferably used, and in the present invention, organically treated montmorillonite can be particularly preferably used.

Specifically, as an organically treated montmorillonite,
Hojun Co., Ltd., Esben C, Esben E, Esben W, Esben P, Esven WX, Esven NX, Esven NZ, Esven N-400, Organite, Organite D, Organite T (trade name)
TIXOGEL MP, TIXOGEL VP, TIXOGEL VP, TIXOGEL MP, TIXOGEL EZ 100, MP 100, TIXOGEL UN, TIXOGEL DS, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A )
BENTONE 34, 38, 52, 500, 1000, 128, 27, SD-1, SD-3 (trade names) manufactured by Elementis Japan
Etc.

  The mixing ratio of component (a) and component (b) is usually 0.5 to 50 parts by weight (preferably 1 to 30 parts by weight) of component (b) with respect to 100 parts by weight of component (a). More preferably, it may be about 3 to 15 parts by weight. When the amount is less than 0.5 parts by weight, the component (a) may easily leak from the component (c). When the amount is more than 50 parts by weight, the viscosity of the component (a) becomes too high, and the supporting / holding step on the component (c) may be difficult.

Further, in the present invention, a thermally conductive substance (hereinafter also referred to as “component (d)”) can be mixed with the component (a). By mixing a heat conductive substance, the movement of heat in the heat storage body can be made smooth, the thermal efficiency of the heat storage material can be improved, and more excellent heat storage performance can be obtained.
Examples of the thermally conductive material include metals such as copper, iron, zinc, beryllium, magnesium, cobalt, nickel, titanium, zirconium, molybdenum, tungsten, boron, aluminum, gallium, silicon, germanium, tin, and alloys thereof. Or metal oxides containing these metals, metal nitrides, metal carbides, metal phosphides and other metal compounds, and scaly graphite, massive graphite, earth graphite, fibrous graphite, etc. One kind or a mixture of two or more kinds can be used.

The thermal conductivity of the thermally conductive material is preferably 1 W / (m · K) or more, more preferably 3 W / (m · K) or more, and further preferably 5 W / (m · K) or more. By mixing a heat conductive material having such a heat conductivity, the heat efficiency of the heat storage material can be improved more efficiently.
Moreover, it is preferable to use a heat conductive substance as microparticles | fine-particles, and it is preferable that an average particle diameter is 1-100 micrometers, Furthermore, it is preferable that it is 5-50 micrometers.

  The mixing ratio of the component (a) and the component (d) is usually 5 to 200 parts by weight (preferably 10 to 80 parts by weight, more preferably 100 parts by weight of the component (a). May be about 20 to 60 parts by weight). When the amount is less than 5 parts by weight, it is difficult to improve the heat storage performance. When the amount is more than 200 parts by weight, the viscosity becomes high and it may be difficult to efficiently carry the component (c).

  In the present invention, it is preferable to mix the component (a) with the component (b) or the component (d), and it is preferable to mix the component (b) and the component (d).

  The component (c) is a component that supports and holds the component (a) (component (b), component (d) if necessary).

  The shape of the component (c) is not particularly limited as long as the component (a) (and the component (b), the component (d)) can be supported and held. For example, the particle aggregation type porous material, the sponge type porous material, the three-dimensional shape What has shape, such as a stitch structure type porous body, etc. are mentioned. In the present invention, in particular, a three-dimensional stitch structure type porous body is preferably used because the component (a) (and the component (b), the component (d)) is more easily supported and held.

  The component (c) can be used without any particular limitation, such as an inorganic porous material, an organic porous material, etc., but the component (a) (and the component (b), the component (d)) can be more easily supported and retained. From the above, an organic porous material is preferably used. Furthermore, the organic porous body can also prevent cracking and shape change of the heat storage body due to volume shrinkage due to phase change (particularly, change from liquid to solid) of the component (a).

  Examples of the resin component that forms such an organic porous material include acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, and acetic acid. Solvents such as vinyl resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / veova resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, etc. Soluble type, NAD type, water soluble type, water dispersion type, solventless type, etc., or synthetic rubber such as chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber Of these, among these Or more can be used species or two or.

  Further, in the present invention, among the resin components, either one liquid type or two liquid type can be used, but the two liquid type is more preferable. For example, a compound containing a reactive functional group (hereinafter referred to as “component (c-1)”) and a compound containing a reactive functional group capable of reacting with the reactive functional group (hereinafter referred to as “(c-2)”. A two-component type consisting of “component”) is preferably used.

  Such reactive functional group combinations include hydroxyl group and isocyanate group, hydroxyl group and carboxyl group, hydroxyl group and imide group, hydroxyl group and aldehyde group, epoxy group and amino group, epoxy group and carboxyl group, carboxyl group. Group and carbodiimide group, carboxyl group and oxazoline group, carbonyl group and hydrazide group, carboxyl group and aziridine group, and the like.

Examples of the compound containing a hydroxyl group include:
A hydroxyl group-containing monomer;
Polyhydric alcohols;
Polyester polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, polyether polyol, polycaprolactone polyol, polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, epoxy polyol, alkyd polyol, fluorine-containing polyol, Polyols such as silicon-containing polyols;
Cellulose and / or derivatives thereof, polysaccharides such as amylose;
Etc.

  In the present invention, it is particularly preferable to use one or more selected from polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, celluloses and derivatives thereof, and by using such a compound containing a hydroxyl group, It can be suitably used because it forms a simple crosslinked structure, has good compatibility with the component (a), and easily suppresses leakage of the component (a) from the heat storage element.

  Specifically, examples of the hydroxyl group-containing monomer include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) ) -3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono ( And (meth) acrylate.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,3-tetra Methylenediol, 1,4-tetramethylenediol, 1,6-hexanediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, trimethylpentanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, cyclohexanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexamethylenediol, 3-methyl-1 , 5-pentamethylenediol, 2 4-diethyl-1,5-pentamethylenediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, metaxylene glycol, paraxylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate Glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, cyclohexanedimethanol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol and sorbitol) Etc.), pentaerythritol, dipentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane and the like.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. Thing etc. are mentioned.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, maleic anhydride, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid;
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid;
Examples include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, terephthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, aromatic dicarboxylic acid such as trimellitic acid, and the like.

In the ring-opening polymer of the cyclic ester, examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.
In the reaction product of the three types of components, those exemplified above can be used as the polyhydric alcohol, polyvalent carboxylic acid, and cyclic ester.

In the present invention, the polyester polyol is particularly preferably a condensation polymerization product of a polyhydric alcohol and a polycarboxylic acid. For example, as the polyhydric alcohol, 2,4-diethyl-1,5-pentamethylenediol, 3-methyl It is preferable to use adipic acid or the like as the polyvalent carboxylic acid such as -1,5-pentamethylenediol and 2-butyl-2-ethyl-1,3-propanediol.
The manufacturing method of polyester polyol can be performed by a conventional method, and a known curing agent, curing catalyst or the like may be used as necessary.

  The acrylic polyol can be obtained, for example, by homopolymerizing or copolymerizing an acrylic monomer having one or more hydroxyl groups in one molecule, or by copolymerizing another copolymerizable monomer. it can.

As an acrylic monomer having one or more hydroxyl groups in one molecule, for example,
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- (Meth) acrylic acid esters such as 2-hydroxybutyl and (meth) acrylic acid-4-hydroxybutyl;
(Meth) acrylic acid monoesters of triols such as glycerin and trimethylolpropane;
Monoethers of the above (meth) acrylic acid esters and polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol;
Adducts of glycidyl (meth) acrylate with monobasic acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid;
An adduct obtained by ring-opening polymerization of the (meth) acrylic acid ester and a lactone such as ε-caprolactam or γ-valerolactone;
Can be obtained by homopolymerization or copolymerization thereof.

As other copolymerizable monomers,
Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, cinnamic acid;

  Aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, (meth) acrylic Acid-N-methylaminoethyl, (meth) acrylic acid-Nt-butylaminoethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (Meth) acrylic acid-N, N-diethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (meth) acrylic acid-N, N-diethylaminopropyl, N- [2- (meth) acryloyloxy Ethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [ -(Meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine and other amino group-containing monomers ;

  (Meth) acrylic acid glycidyl, diglycidyl fumarate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, (meth) acrylic acid-ε-caprolactone-modified glycidyl, An epoxy group-containing monomer such as (meth) acrylic acid-β-methylglycidyl;

  (Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-monoalkyl (meth) acrylamide, N-isobutoxymethylacrylamide, N, N-dialkyl (meth) acrylamide, 2- (dimethylamino) ) Amide group-containing monomers such as ethyl (methacrylate), N- [3- (dimethylamino) propyl] (meth) acrylamide and vinylamide;

Alkoxysilyl group-containing monomers such as (meth) acrylic acid trimethoxysilylpropyl and (meth) acrylic acid triethoxysilylpropyl;
Hydrolyzable silyl group-containing monomers such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ- (meth) acrylopropyltrimethoxysilane;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;
Oxazoline group-containing monomers such as vinyloxazoline and 2-propenyl 2-oxazoline

Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-t-butyl , (Meth) acrylic acid-sec-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid Octyl, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, trifluoroethyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, (meta ) Octyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Dodecenyl acid, Otadecyl (meth) acrylate, Cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, Phenyl (meth) acrylate, Isobornyl (meth) acrylate, Benzyl (meth) acrylate (Meth) acrylate monomers such as 2-phenylethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 4-methoxybutyl (meth) acrylate;

Vinylidene halide monomers such as vinylidene fluoride;
Aromatic vinyl monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Other monomers such as ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl ether, vinyl ketone, silicone macromer;
Etc., and one or more of these can be used.

  The polymerization method is not particularly limited, and a known block polymerization, suspension polymerization, solution polymerization, dispersion polymerization, emulsion polymerization, oxidation-reduction polymerization, etc. may be used, and an initiator, a chain transfer agent, or the like, if necessary. These additives may be added. For example, the monomer component can be obtained by solution polymerization in the presence of a known radical polymerization initiator such as a peroxide or an azo compound.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

  In the ring-opening polymer of the cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.

  In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxyl groups in the molecule (particularly at the terminal), and having a number average molecular weight of 500 or more. Can be used. The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene) may be used, and diene (for example, butadiene, isoprene, etc.) may be used.

  Examples of the polyether polyol include monomers such as an ethylene oxide-propylene oxide copolymer in addition to a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether. Examples include (alkylene oxide-other alkylene oxide) copolymers containing a plurality of alkylene oxides as components.

  The hydroxyl value of such a polyol is not particularly limited, but may be about 20 to 150 KOHmg / g (preferably 25 to 120 KOHmg / g, more preferably 30 to 80 KOHmg / g).

  The molecular weight of the polyol is not particularly limited, but is preferably 500 to 10,000, and more preferably 1000 to 4000. If it is such molecular weight, the bridge | crosslinking structure which can suppress the leakage of a thermal storage material can be obtained by the combination with the compound containing an isocyanate group, the compound containing a carboxyl group, etc. If the molecular weight is too small, the heat storage material may easily leak. If the molecular weight is too large, the heat storage material may not be sufficiently retained.

  Cellulose and / or derivatives thereof include cellulose acetates such as cellulose, cellulose acetate, cellulose diacetate, and cellulose triacetate, and celluloses such as methylcellulose, ethylcellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate. Examples include esters, cellulose ethers such as ethyl cellulose, benzyl cellulose, cyanoethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, and the like.

Cellulose and / or derivatives thereof have a hydroxyl group, but a portion of the hydroxyl group is preferably substituted with an alkoxyl group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). .
Specifically, the substitution degree is preferably 1.8 to 2.8, more preferably 2.2 to 2.6. The degree of substitution means a ratio in which three hydroxyl groups present in the glycolose unit constituting cellulose are substituted with alkoxyl groups and the like, and the degree of substitution is 3 when 100% substitution is performed.
By controlling the degree of substitution within such a range, interaction with the component (a) described later can be improved, and the component (a) can be retained in the porous body for a long period of time.
When the degree of substitution is less than 1.8, the interaction with the component (a) may be reduced, and the component (a) may not be sufficiently retained in the porous body. On the other hand, when the ratio is larger than 2.8, the hydroxyl group in cellulose is decreased, and a three-dimensional crosslinked structure having sufficient strength may not be obtained.

  The molecular weight of cellulose and / or a derivative thereof is not particularly limited, but is preferably 1000 to 30000, and more preferably 5000 to 20000. If it is such molecular weight, the bridge | crosslinking structure which can suppress the leakage of a thermal storage material most can be obtained. If the molecular weight is too small, the heat storage material may easily leak. If the molecular weight is too large, the heat storage material may not be sufficiently retained.

  Examples of the compound containing an isocyanate group include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate. (HMDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1, 5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl capro Over DOO, lysine diisocyanate - DOO, dimer acid diisocyanate, aliphatic diisocyanates such as norbornene diisocyanate;

1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl- 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, dicyclohexylmethane diisocyanate Alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate and hydrogenated xylylene diisocyanate;

m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4, 4′-diphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2, 2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'- Diiso Aneto, dianisidine diisocyanate, aromatic diisocyanates such as tetramethylene diisocyanate;

1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate-1- Araliphatic diisocyanates such as methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene;
And these isocyanate group-containing compounds derivatized by allohanation, biuretization, dimerization (uretidione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, etc., and mixtures thereof, and these isocyanates Examples thereof include a copolymer of a group-containing compound and the above-described copolymerizable monomer.

  In the present invention, it is particularly preferable to use an aliphatic diisocyanate, and HMDI and a derivative thereof are particularly preferable.

Examples of the compound containing a carboxyl group include the polyvalent carboxylic acid and the carboxyl group-containing monomer described above, a polymer obtained by homopolymerizing or copolymerizing a carboxyl group-containing monomer, or other copolymerizable monomers. And a copolymer obtained by copolymerizing these monomers.
Examples of the other copolymerizable monomers include the hydroxyl group-containing monomer, amino group-containing monomer, epoxy group-containing monomer, amide group-containing monomer, alkoxysilyl group-containing monomer, Hydrolyzable silyl group-containing monomer, nitrile group-containing monomer, methylol group-containing monomer, oxazoline group-containing monomer, acrylate ester monomer, vinylidene halide monomer, aromatic vinyl And other monomers.

  Examples of the compound containing an epoxy group include an epi-bis type bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, and a bisphenol S type epoxy compound obtained by a condensation reaction such as bisphenol A and epichlorohydrin. Are generally used, and hydrogenated epoxy compounds, 3,4-epoxyvinylcyclohexane, vinylcyclohexene monoepoxide alicyclic epoxy compounds, phenol novolac epoxy compounds, bisphenol A novolac epoxy compounds, cresol novolacs Type epoxy compound, diaminodiphenylmethane type epoxy compound, β-methyl epichloro type epoxy compound, n-butyl glycidyl ether, allyl glycidyl ether, 2 Glycidyl ether type epoxy compounds such as ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, diglycidyl ether type epoxy compounds such as diglycidyl ether, glycidyl (meth) acrylate, (meth) acrylic acid 3,4-epoxy Cyclohexyl, (meth) acrylic acid-ε-caprolactone-modified glycidyl, glycidyl ester type epoxy compound such as (meth) acrylic acid-β-methylglycidyl, polyglycol ether type epoxy compound, glycol ether type epoxy compound, urethane having urethane bond Rubber-modified epoxy compounds containing modified epoxy compounds, amine-modified epoxy compounds, fluorinated epoxy compounds, polybutadiene or acrylonitrile-butadiene copolymer rubber Compounds, flame retardant epoxy compounds such as glycidyl ether of tetrabromobisphenol A, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- ( And epoxy group-containing silicon compounds such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

The epoxy equivalent of the compound containing an epoxy group is not particularly limited, but is preferably 100 g / eq or more and 400 g / eq or less (preferably 150 g / eq or more and 350 g / eq or less), and one or more of these is preferable. Can be used.
Particularly in the present invention, a compound containing an epoxy group of 100 g / eq or more and less than 250 g / eq (preferably 120 g / eq or more and 230 g / eq or less, more preferably 150 g / eq or more and 200 g / eq or less), and an epoxy equivalent of 250 g. It is preferable to use together a compound containing an epoxy group of / eq or more and 400 g / eq or less (preferably 280 g / eq or more and 350 g / eq or less). By including such a compound containing two or more types of epoxy groups, both excellent curability and flexibility can be achieved. Moreover, compatibility with (a) component can be adjusted.
Furthermore, the epoxy resin of the present invention preferably has two or more epoxy groups in one molecule. By having two or more, the curability and the reaction rate can be improved, the crosslinking density can be increased, and the strength of the resulting porous body can be increased.

As a compound containing an amino group,
Aliphatic amino group-containing compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine;
Mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4- Aminocyclohexyl) alicyclic amino group-containing compounds such as methane, polycyclohexylpolyamine, DBU;
Aromatic amino group-containing compounds such as metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone;
aliphatic aromatic amino group-containing compounds such as m-xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol;

3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, An amino group-containing compound having an ether bond such as polyoxyethylenediamine;
Hydroxyl and amino group-containing compounds such as diethanolamine and triethanolamine;
Acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride;
Polyamideamines such as polyamides obtained by reacting dimer acids with polyamines such as diethylenetriamine and triethylenetetramine, and polyamides using polycarboxylic acids other than dimer acids;
Imidazoles such as 2-ethyl-4-methylimidazole;
Polyoxypropylene amines such as polyoxypropylene diamine and polyoxypropylene triamine;
Epoxy-modified amine obtained by reacting an epoxy compound with the amines, modified amines such as Mannich-modified amine, Michael addition-modified amine, ketimine and aldimine obtained by reacting the amines with formalin and phenols; 2, 4 , 6-tris (dimethylaminomethyl) phenol 2-amine hexanoate and other amine salts.

  As a combination of the component (c-1) and the component (c-2), in the present invention, a compound containing a hydroxyl group and a compound containing an isocyanate group, a compound containing an epoxy group and a compound containing an amino group, etc. A combination is preferred, and a combination of a compound containing a hydroxyl group and a compound containing an isocyanate group is particularly preferred. Such a combination is preferable because the crosslinking reaction is likely to proceed under mild conditions and the adjustment of the crosslinking density and the like is easy.

Moreover, the mixing ratio of the component (c-1) and the component (c-2) is not particularly limited, and may be set as appropriate according to the application.
For example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the NCO / OH ratio is usually 0.1 to 1.8, preferably 0.2 to 1.5, more preferably 0.3. What is necessary is just to set in the range used as -1.3.
By being within such a range of the NCO / OH ratio, the strength of the heat storage body can be strengthened, and a uniform and dense cross-linked structure with no leakage of the heat storage material can be obtained.
When the NCO / OH ratio is less than 0.1, the crosslinking rate is low, and sufficient physical properties such as curability, durability, and strength may not be ensured, and the heat storage material is likely to leak. When the NCO / OH ratio is larger than 1.8, unreacted isocyanate remains, adversely affects various physical properties of the heat storage body, the heat storage body is easily deformed, and the heat storage material is likely to leak.

Moreover, in reaction of (c-1) component and (c-2) component, a hardening reaction can also be advanced rapidly using a reaction accelerator.
For example, in the reaction of a compound containing a hydroxyl group and a compound containing an isocyanate group, as a reaction accelerator, for example, triethylamine, triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylaminoethanol, dimeramine amine, dimer acid polyamidoamine, etc. Amines of
Tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, tin octate;
Metal carboxylates such as iron naphthenate, cobalt naphthenate, manganese naphthenate, zinc naphthenate, iron octylate, cobalt octylate, manganese octylate, zinc octylate;
Carboxylates such as dibutyltin thiocarboxylate, dioctyltin thiocarboxylate, tributylmethylammonium acetate, trioctylmethylammonium acetate;
Aluminum compounds such as aluminum trisacetylacetate;
1 type, or 2 or more types can be used.

  The reaction accelerator is usually mixed at a ratio of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the compound containing a hydroxyl group. When the reaction accelerator is less than 0.01 part by weight, the curability and strength of the heat storage body become insufficient, and the swelling tends to occur easily. When the amount is more than 10 parts by weight, the weather resistance, discoloration resistance and the like tend to decrease.

  As components for forming the porous body (c), in addition to the above components, pigments, aggregates, plasticizers, antiseptics, antifungal agents, algaeproofing agents, antifoaming agents, foaming agents, leveling agents, pigment dispersants, You may contain additives, such as an antisettling agent, a sagging inhibitor, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer.

  What is necessary is just to manufacture a porous body by a well-known method using the said component.

  As a method for producing the heat storage body of the present invention, the porous body is loaded with the component (a) (component (b), component (d) as required) by the dipping method, pressure reduction / pressure injection method, etc., Moreover, the method of mixing and carrying | supporting (a) component (and (b) component, (d) component) previously at the time of porous body manufacture etc. is mentioned.

  In the present invention, a method in which the (a) component (and (b) component, (d) component) is mixed and supported in advance during the production of the porous body is preferred. In such a method, the (a) component ( And (b) component and (d) component) can be further prevented from leaking, which is preferable.

  Specifically, first, the component (a) (and component (b), component (b), component (d)) and the resin component are mixed, and then the resin component is cured to obtain component (a) (and component (b). A heat storage body in which the component (component (d)) is carried on a porous body is obtained.

For example,
(I) Component (a) (optionally (b) component, (d) component), (c-1) component and (c-2) component are uniformly mixed, and (c-1) component and (c) -2) A method of obtaining a heat storage body by reacting components,
(Ii) (a) component (component (b), component (d) as required) and nonionic surfactant (hereinafter referred to as “(e) component”) having a hydrophilic / lipophilic balance (HLB value) of 10 or more. (C-1) component and (c-2) component are mixed, (a) component is dispersed in a colloidal form, and (c-1) component and (c-2) component are reacted. The method of obtaining a thermal storage body, etc. are mentioned.

In the method (i), the (a) component (the (b) component, the (d) component), the (c-1) component, and the (c-2) component are uniformly mixed to obtain a compatible state. . Next, by reacting the component (c-1) and the component (c-2), a heat storage body in which the component (a) (and the component (b), the component (d)) is supported on the porous body is obtained. is there.
In this process, microphase separation accompanying the change from the compatible state to the incompatible state occurs, and a densely packed three-dimensional stitch structure type porous body composed of the components (c-1) and (c-2) is formed. It seems to be done.
The three-dimensional stitch structure type porous body is in a state where the component (a) (and the components (b) and (d)) are supported, and a heat storage body is formed.

In particular, when the component (b) is mixed with the component (a), the viscosity of the component (a) is adjusted to prevent the component (a) supported on the porous body from leaking outside. it can. Therefore, it is preferable because a high heat storage material content can be achieved.
Furthermore, by appropriately setting the forming component of the porous body, the interaction with the component (c) works, and the component (a) can be further prevented from leaking to the outside.
Further, if the porous body is a three-dimensional stitch structure type porous body, the component (a) can be further prevented from leaking to the outside because of its dense structure.

In the production of such a three-dimensional stitch structure type porous body, it is preferable that the compatibilizer described above is further mixed and produced. The compatibilizing agent can improve not only the compatibility between the components (a) but also the compatibility between the component (a) and the resin component (component (c-1), component (c-2), etc.). Therefore, a denser three-dimensional stitch structure type porous body is formed, and the leakage of the component (a) (and the components (b) and (d)) from the porous body can be further prevented.
Examples of the compatibilizing agent include fatty acid triglycerides and nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10, but the compatibility between the component (a) and the resin component may be used. In particular, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 is preferred.

  In the method (i), the reaction temperature is preferably equal to or higher than the melting point of the component (a). Although specific reaction temperature changes with kinds of (a) component, it is about 20 to 100 degreeC normally. (A) By making it react more than melting | fusing point of a component, it will be in a compatible state and the outstanding thermal storage body is formed. Moreover, what is necessary is just to make reaction time into about 0.2 to 10 hours normally.

In the method (i), for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, but is 500 to 10,000. It is desirable that it is 1000-3000. With such a molecular weight, it can be easily melt-mixed with the component (a), and a compatible state can be easily produced. Therefore, a more excellent three-dimensional crosslinked structure can be obtained, and an excellent heat storage body can be obtained.
Furthermore, the mixing ratio of the compound containing a hydroxyl group and the compound containing an isocyanate group is not particularly limited and may be set as appropriate, but the NCO / OH ratio is 0.1 to 1.8, preferably 0.8. 2 to 1.7, more preferably 0.3 to 1.6, and more preferably 0.5 to 1.5, whereby a more excellent three-dimensional crosslinked structure can be obtained, and an excellent heat storage body can be obtained. Obtainable.

  In the method (ii), the component (a) (component (b), component (d) if necessary), component (e), component (c-1) and component (c-2) are mixed. , (C-1) component and (c-2) component are dispersed in a colloidal form. Next, by reacting the component (c-1) and the component (c-2), a heat storage body in which the component (a) (and the component (b), the component (d)) is supported on the porous body is obtained. is there.

  In such a method, the component (e) can create a state in which the component (a) is dispersed in a fine colloidal form in the component (c-1) and / or the component (c-2). By reacting the component (c-1) and the component (c-2) in such a state, the component (a) is contained in the component (c) composed of the component (c-1) and the component (c-2). A finely dispersed heat storage element can be produced.

  As a specific method of the production method of the present invention, for example, (a) component, (e) component, (c-1) component and (c-2) component are mixed, and (c-1) component and (c- 2) Method of reacting components, or (a) component, (e) component, (c-1) component (or (c-2) component) are mixed, and (c-2) component (or (c-) 1) The method of making it react by adding component) etc. are mentioned.

The heat storage body obtained by such a manufacturing method can increase the content of the component (a), exhibits excellent heat storage properties, and has a high content of the component (a). The component (a) does not leak over time. Furthermore, even if the heat storage body is cut, the (a) component does not leak from the cut surface and is excellent in workability, and since the (a) component does not leak due to nailing or the like, the mounting workability is excellent.
Furthermore, since the component (a) is finely and uniformly dispersed, the shape change of the heat storage body itself due to the volume change accompanying the solid-liquid change of the component (a) can be reduced.

  What is necessary is just to select suitably as (e) component with (a) component, (c-1) component, and (c-2) component. Component (e) has a hydrophilic / lipophilic balance (HLB value) of 10 or more (preferably more than 10 and 20 or less, more preferably 11 or more and 19 or less, more preferably 12 or more and 18 or less, and most preferably 13 or more and 17 or less). It is a nonionic surfactant, and if it is such a range, since an organic latent heat storage material is easy to disperse | distribute colloidally especially, it is preferable.

As the component (e), for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monooleate,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether,
Polyoxyethylene sorbitol fatty acid esters such as tetraoleic acid polyoxyethylene sorbit,
Polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate,
Examples include polyoxyethylene hydrogenated castor oil and polyoxyethylene coconut oil fatty acid sorbitan.

  In particular, as the component (a), an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and a long chain fatty acid ester having 8 to 36 carbon atoms are used. In such a case, it is preferable to use a nonionic surfactant having a long-chain alkyl group having 8 to 36 carbon atoms in the structure of the component (e). In particular, the effects of the present invention can be further enhanced by selecting those having a similar number of carbon atoms in the long-chain alkyl groups of the component (a) and the component (e), or the similar ones.

The mixing ratio of the component (e) and the component (a) may be appropriately set depending on the component (a), the component (c-1), and the component (c-2), but is usually 100 parts by weight of the component (a). The component (e) may be about 0.01 to 30 parts by weight (preferably 0.1 to 20 parts by weight).
When the component (e) is less than 0.01 parts by weight, the component (a) and the component (c-1) and / or the component (c-2) are easily separated or easily cause a creaming phenomenon, and efficiently. The colloidal dispersion may not occur and the effects of the present invention may not be obtained. When the amount is more than 30 parts by weight, physical properties such as water resistance of the obtained heat storage may be adversely affected.

  In the above production method, in the state before the reaction, the component (a) has a colloidal shape with a particle size of about 10 μm to 1000 μm (preferably 50 μm to 900 μm, more preferably 100 μm to 800 μm, more preferably 200 μm to 700 μm). It is characterized by being in a dispersed state. By reacting the component (c-1) and the component (c-2) from such a state, a heat storage body in which the component (a) is finely dispersed can be obtained.

In the state before the reaction, the temperature in the system is preferably equal to or higher than the melting point of the component (a). Specifically, it is usually about 20 ° C. to 80 ° C., and at such a temperature, the component (a) is easily dispersed in a colloidal state, which is preferable.
The particle size is a value measured using an optical microscope (BHT-364M, manufactured by Olympus Optical Co., Ltd.).

  In such a production method, the specific reaction temperature varies depending on the type of component (a), but is usually about 20 ° C to 80 ° C. Above the melting point of the component (a), the component (a) tends to be in a colloidal state, so that an excellent heat storage body is formed. Moreover, reaction time should just be normally about 0.2 to 5 hours.

In such production, for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, and should be selected within a wide range. In general, it is preferably 500 to 10,000, more preferably 1000 to 3000. With such a molecular weight, the component (a) can be dispersed in a finer colloidal form, and a heat storage body with a higher component content (a) can be obtained. Therefore, the heat storage body which is excellent in heat storage property and can further reduce the shape change of the heat storage body itself due to the volume change accompanying the solid-liquid change of the component (a) can be obtained.
Furthermore, the mixing ratio of the compound containing a hydroxyl group and the compound containing an isocyanate group is not particularly limited and may be set as appropriate, but the NCO / OH ratio is 0.1 to 1.8, preferably 0.8. A more excellent heat storage body can be obtained by being 2 to 1.7, more preferably 0.3 to 1.6, and more preferably 0.5 to 1.5.

  In the method of mixing and supporting the component (a) (and component (b), component (d)) in advance during the production of the porous body, the isocyanate group, carboxyl group, imide are used as the compound containing a reactive functional group. When a compound containing a group or an aldehyde group is used, the use of a long-chain alcohol or a polyether compound as a heat storage material is excluded. When a compound containing a hydroxyl group, an epoxy group, a carbodiimide group, an oxazoline group, or an aziridine group is used as a compound containing a reactive functional group, the use of long chain fatty acids as a heat storage material is excluded.

  In the production of the heat storage body in the present invention, in addition to the above components, pigment, aggregate, plasticizer, preservative, antifungal agent, antialgae, antifoaming agent, foaming agent, leveling agent, pigment dispersant, anti-settling agent Additives such as an agent, an anti-sagging agent, a lubricant, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer can also be contained.

  Although the thickness of a thermal storage body is not specifically limited, Usually, about 1 mm-30 mm, Furthermore, about 2 mm-20 mm are preferable.

  The heat storage material content of the heat storage material of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, and most preferably 65% by weight or more.

The heat insulator of the present invention is not particularly limited, but the thermal conductivity is less than 0.1 W / (m · K) (more preferably 0.08 W / (m · K) or less, and still more preferably 0.05 W / (m · K). It is preferable that it has the heat insulation property of K) or less). When the thermal conductivity is less than 0.1 W / (m · K), it has excellent heat insulating properties.
Examples of such a heat insulator include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, etc., or a composite thereof. Etc. Moreover, you may use a commercially available heat insulator.

The heat storage insulator of the present invention is not particularly limited, and the heat storage member and the heat insulator may be laminated by a known method.
For example, a method of sticking the heat storage body and the heat insulating body obtained by the manufacturing method described above with a known adhesive or adhesive tape, or the heat storage body forming component ((a) component (necessary) directly on the heat insulating body (B) component, (d) component), resin components ((c-1) component, (c-2) component, etc.), (e) component, etc.) are applied and formed according to the above.
In the latter case, the heat storage body can be formed by applying the heat storage body forming component to the heat insulator by a known method such as spray coating, roller coating, brush coating, trowel coating, or pouring.

  In addition, the heat storage insulator may be composed of two layers of a heat storage body / heat insulation body, or a three-layer structure including a heat storage body / heat storage body / heat insulation body, a heat storage body / heat insulation body / heat storage body, or more. But you can. Moreover, 1 type may each be sufficient as a heat insulating body and a thermal storage body, and 2 or more types may be used for it. Even in the case of three or more layers, the layers may be stacked by the same method as that described above.

  Although the shape of a thermal storage heat insulator is not specifically limited, It is preferable that it is a sheet form. In the case of a sheet shape, the thickness of the heat storage insulator may be appropriately set depending on the application, but each heat storage body is usually about 1 to 30 mm (preferably 2 to 20 mm), and each heat insulator is usually 1 to 30 mm ( Preferably, it may be about 2 to 20 mm).

  The heat storage insulator of the present invention is particularly preferably flexible. In the present invention, a heat storage body having flexibility and a heat insulator having flexibility may be appropriately selected and laminated. By having flexibility, even if it is a curved part or a part having unevenness, it is possible to stack the heat storage insulation without gaps, and it is excellent in air tightness and can further improve heat storage and heat insulation performance. .

  The heat storage heat insulator of the present invention can be suitably used mainly as an inner wall material, an outer wall material, a ceiling material, a floor material, or an inner / outer material of a building such as a house, or an interior material of a vehicle or the like. Furthermore, the heat storage insulator of the present invention can be applied to thermoelectric conversion systems, refrigeration / freezers, cooler boxes, heat insulation sheets, electrical products, OA equipment and other daily products, machines, equipment and other industrial products, plants, tanks, and the like. . It can also be used by being bonded to various base materials.

  In this invention, according to the use to be used, a heat storage material can be set suitably. For example, when used as an interior / exterior material for a building, a latent heat storage material having a melting point of about 15 ° C. to 30 ° C. may be used. In addition, when used as an interior material such as a vehicle, the one having a melting point of the latent heat storage material of about 15 ° C. to 30 ° C. When using as a refrigerator, the one having a melting point of the latent heat storage material of about −10 ° C. to 5 ° C. When using as a freezer, what the melting | fusing point of a latent-heat storage material has -30 degreeC-about -10 degreeC should just be used, respectively.

  Applicable base materials include nonwoven fabric, woven fabric, paper, synthetic paper, wood, particle board, ceramic paper, metal plate, metal foil, synthetic resin plate, plastic film, concrete, mortar, gypsum board, calcium silicate plate, Examples thereof include cement-based plates, ALC plates, siding plates, extrusion-molded plates, rigid foam plates, glass, glass cloth, fired tiles, porcelain tiles, and meshes.

  When laminating the heat storage heat insulator of the present invention on such a base material, it may be laminated so that the base material surface and the heat insulator side are in contact with each other, or laminated so that the base material surface and the heat storage material side are in contact with each other. May be. In this invention, it is preferable to laminate | stack so that a heat insulating body may exist in space outer side, and a thermal storage body may exist in space inner side. By laminating in this way, excellent heat storage and heat insulation properties can be obtained, and temperature changes in the space can be mitigated, which is preferable.

Examples of the laminating method include a method of sticking with a known adhesive or adhesive tape, a method of fixing by nailing, and the like. Moreover, it can cut | disconnect with a cutter etc. according to a use application, can match a magnitude | size, and can laminate | stack easily.
In the present invention, the component (a) does not leak out even when fixing by nailing or cutting with a cutter or the like. Therefore, it has excellent heat storage and heat insulation properties, can maintain a comfortable environment with little variation in space temperature against changes in outside air temperature, and can efficiently save energy.

  In addition, when the base material itself is a heat insulator having heat insulating performance, by a method of sticking only the heat storage body to the base material with a known adhesive or adhesive tape, a method of fixing by nailing, etc. Even if they are laminated, the effects of the present invention can be obtained.

In the present invention, the thermal conductivity is further 10.0 W / (m · K) or more (preferably 20.0 W / (m · K) or more, more preferably 100 W / (m · K) or more on the heat storage surface side. Is preferably laminated. Laminating the thermal conductivity body is preferable because the heat transfer speed is high and the thermal efficiency of the heat storage body is improved.
As a material having a thermal conductivity of 10.0 W / (m · K) or more, for example, a steel plate made of a metal material such as copper, aluminum, iron, brass, zinc, magnesium, nickel, or the like, or these metal materials are used. Examples of the coating film or sheet include. In the present invention, an aluminum plate can be particularly preferably used.
Although it does not specifically limit as thickness of a thermal conductivity body, Usually, it is preferable that it is about 5-1000 micrometers.

  In addition, the heat conductivity in this invention is the value measured using the heat conductivity meter (The Kyoto Electronics Industry Co., Ltd. product, Chemtherm.QTM-D3 (brand name)).

In the present invention, any surface material can be provided on the inner surface side of the space.
As the surface material, inorganic board such as calcium silicate board and gypsum board, wood material such as pine, lawan, beech, hinoki, plywood, coating material, sheet material, wallpaper, etc. can be used. A seed or two or more kinds can be laminated and used.

  The coating material is not particularly limited as long as it is usually used for building coating, and for example, those specified in JIS K 5663 “Synthetic Resin Emulsion Paint” can be suitably used. Although it does not specifically limit as a dry film thickness of a coating material, It is preferable that it is 200 micrometers or less.

  Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.

Example 1
Using the raw materials shown in Table 1, the heat storage material A, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A are uniformly mixed at a temperature of 23 ° C. in the blending amounts shown in Table 2, and the reaction accelerator A is added sufficiently. Stir. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a 5 mm thick heat accumulator. The NCO / OH ratio was 1.0.
The PET film surface of the obtained heat storage body and polyurethane foam (250 mm × 170 mm × 25 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.

  The following test was done about the obtained test body.

(Heat storage material leakage evaluation test 1)
The obtained test specimen was allowed to stand for 72 hours in an atmosphere of 10 ° C. or 50 ° C., and then transferred to an environment at a temperature of 23 ° C. and a relative humidity of 50% RH (hereinafter also referred to as “standard state”). The leakage of heat storage material was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Heat storage material leakage evaluation test 2)
The obtained specimen was allowed to stand for 72 hours in an atmosphere of 10 ° C. or 50 ° C. and then transferred to an environment of a temperature of 30 ° C. and a relative humidity of 50% RH, and leakage of the heat storage material from the specimen was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Heat storage property test)
Using DSC220CU (manufactured by Seiko Instruments Inc.), the phase change temperature (° C.) and the latent heat (kJ / kg) of the obtained specimen were measured by differential scanning calorimetry (DSC measurement). As measurement conditions, aluminum was used as a reference, and the temperature was measured in a temperature range of 10 ° C./min and −20 to 60 ° C. The results are shown in Table 3.

(Workability test 1)
In the standard state, the obtained specimen was cut with a cutter knife, and leakage of the heat storage material from the cut surface was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Workability test 2)
Under an environment of a temperature of 30 ° C. and a relative humidity of 50% RH, the obtained specimen was cut with a cutter knife, and leakage of the heat storage material from the cut surface was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Workability test 1)
In the standard state, the obtained specimen was nailed and the leakage of the heat storage material due to the nail was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Workability test 2)
The obtained specimen was nailed in an environment of a temperature of 30 ° C. and a relative humidity of 50% RH, and the leakage of the heat storage material due to the nail was observed. The evaluation is as follows. The results are shown in Table 3.
◎: Leak was not found ○: Leak was hardly seen ×: Leak was seen

(Heat storage insulation performance evaluation test)
A test body was installed on the four side surfaces of a simple box with outer dimensions of 330 mm x 330 mm x 225 mm made of 25 mm polystyrene foam so that the heat storage surface was inside the box, and a 5 mm calcium silicate board was installed as a surface material. did. Only the calcite board was installed on the lower surface, and only the polystyrene foam was used on the upper surface. In addition, a thermocouple was installed in the center of the box internal space for temperature measurement.
This test body box was installed in a thermostat, the temperature in the thermostat was regarded as the outside air temperature, and the temperature in the test box was regarded as the room temperature, and the following experiment was performed.
Assuming a winter heating operation, hold the box for 3 hours in a thermostat set at 20 ° C, then close the box top and lower the temperature in the thermostat to 5 ° C. The box internal space temperature change was measured over time. The results are shown in FIG.
FIG. 1 also shows the results of a thermal storage insulation performance evaluation test using only 10 mm polyurethane foam in place of the test body of Example 1 (thermal storage thermal insulation) (Comparative Example 1).
As shown in FIG. 1, when a heat storage insulator is applied, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and the heat storage and heat insulation properties. Excellent results were obtained.

(Example 2)
Using the raw materials shown in Table 1, the heat storage material A, the mixture of the organically treated layered clay mineral A, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A are uniformly mixed at a temperature of 23 ° C. in the blending amounts shown in Table 2. After adding the reaction accelerator A and stirring sufficiently, it was poured into a 250 mm × 170 mm × 5 mm formwork covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded. And obtained a heat storage.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3 and FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 2, it is hardly affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

The viscosity of the mixture of the heat storage material A and the organically treated layered clay mineral A was 3.4 Pa · s. The TI value was 7.9.
The viscosity is a value determined by measuring the viscosity at a temperature of 23 ° C., a relative humidity of 50% RH, and 20 rpm (guide value for the fourth rotation) with a BH viscometer.
The TI value is a value obtained by Equation 1 using a TI value: BH viscometer at a temperature of 23 ° C. and a relative humidity of 50% RH.
TI value = η1 / η2 (Formula 1)
(However, η1: Viscosity at 2 rpm (Pa · s: guide value for the second rotation), η2: Viscosity at 20 rpm (Pa · s: Guide value for the fourth rotation))

(Example 3)
Using the raw materials shown in Table 1, the mixture of the heat storage material B, the heat storage material C, the organically treated layered clay mineral B, the hydroxyl group-containing compound B, and the isocyanate group-containing compound B are mixed at the temperatures shown in Table 2. Mix evenly at 35 ° C, add reaction accelerator A, stir well, then pour into a 250 mm x 170 mm x 5 mm mold with a 50 µm polyethylene terephthalate film (PET film), and cure at 50 ° C for 180 minutes And demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 3, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

  The viscosity of the mixture of the heat storage material B and the organically treated layered clay mineral B was 2.5 Pa · s. The TI value was 6.8.

Example 4
Using the raw materials shown in Table 1, the mixture of the heat storage material A and the organically treated layered clay mineral B, the hydroxyl group-containing compound C, and the isocyanate group-containing compound B are uniformly mixed at a temperature of 23 ° C. in the blending amounts shown in Table 2. After adding the reaction accelerator A and stirring sufficiently, it was poured into a 250 mm × 170 mm × 5 mm formwork covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded. And obtained a heat storage.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 4, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage and heat insulation properties. Results were obtained.

  The viscosity of the mixture of the heat storage material A and the organically treated layered clay mineral B was 2.6 Pa · s. The TI value was 6.8.

(Example 5)
Using the raw materials shown in Table 1, the heat storage material A, the mixture of the organically treated layered clay mineral B, the hydroxyl group-containing compound C, the isocyanate group-containing compound B, and the heat conductive material in the blending amounts shown in Table 2 Mix evenly at a temperature of 23 ° C., add reaction accelerator A, stir well, and then pour into a 250 mm × 170 mm × 5 mm mold with a 50 μm polyethylene terephthalate film (PET film), and 180 minutes at 50 ° C. It was cured and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
Moreover, the thermal storage heat insulation performance evaluation test was done by the method similar to Example 1 supposing the heating operation of winter. The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 5, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

  The viscosity of the mixture of the heat storage material A, the organically treated layered clay mineral B, and the heat conductive material was 3.1 Pa · s. The TI value was 6.9.

(Example 6)
Using the raw materials shown in Table 1, the heat storage material A, the hydroxyl group-containing compound C, the isocyanate group-containing compound B, and the heat conductive material are uniformly mixed at a temperature of 23 ° C. in the blending amounts shown in Table 2, and a reaction accelerator. After adding A and stirring sufficiently, it was poured into a 250 mm × 170 mm × 5 mm formwork covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body. .
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
Moreover, the thermal storage heat insulation performance evaluation test was done by the method similar to Example 1 supposing the heating operation of winter. The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 6, it is not easily affected by the outside air temperature, and there is less variation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

  In addition, the viscosity of the mixture of the heat storage material A and the heat conductive material was 2.4 Pa · s. The TI value was 6.5.

(Example 7)
Using the raw materials shown in Table 1, the mixture of the heat storage material A, the heat storage material B, and the organically treated layered clay mineral B, the hydroxyl group-containing compound C, and the isocyanate group-containing compound B are mixed at the blending amounts shown in Table 2. Mix evenly at 35 ° C, add reaction accelerator A, stir well, then pour into a 250 mm x 170 mm x 5 mm mold with a 50 µm polyethylene terephthalate film (PET film), and cure at 50 ° C for 180 minutes And demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 7, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and excellent heat storage properties and heat insulation properties. Results were obtained.

  In addition, the viscosity of the mixture of the heat storage material A, the heat storage material B, and the organically treated layered clay mineral B was 2.6 Pa · s. The TI value was 6.7.

(Example 8)
Using the raw materials shown in Table 1, the heat storage material A, the heat storage material B, the compatibilizer A, the organically treated layered clay mineral B, the hydroxyl group-containing compound C, and the isocyanate group in the blending amounts shown in Table 2 The containing compound B was uniformly mixed at a temperature of 35 ° C., the reaction accelerator A was added, and after sufficient stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold with a 50 μm polyethylene terephthalate film (PET film). It was cured at 180 ° C. for 180 minutes and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 8, it is not easily affected by the outside air temperature, and there is less fluctuation in the indoor temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

  In addition, the viscosity of the mixture of the heat storage material A, the heat storage material B, the compatibilizer A, and the organically treated layered clay mineral B was 2.4 Pa · s. The TI value was 6.6.

Example 9
Using the raw materials shown in Table 1, the heat storage material A, the heat storage material B, the compatibilizer B, the organically treated layered clay mineral B, the hydroxyl group-containing compound C, and the isocyanate group in the blending amounts shown in Table 2 The containing compound B and the heat conductive material are uniformly mixed at a temperature of 35 ° C., the reaction accelerator A is added, the mixture is sufficiently stirred, and then a 250 mm × 170 mm × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film). Poured in, cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
Moreover, the thermal storage heat insulation performance evaluation test was done by the method similar to Example 1 supposing the heating operation of winter. The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 9, it is hardly affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

  The viscosity of the mixture of the heat storage material B and the organically treated layered clay mineral B was 2.9 Pa · s. The TI value was 7.1.

(Example 10)
Using the raw materials shown in Table 1, the heat storage material B, the surfactant A, the hydroxyl group-containing compound A, and the reaction accelerator A are mixed at a temperature of 35 ° C. in the blending amounts shown in Table 2, and the heat storage material B is colloidal. (Average particle diameter of 180 μm), and after adding the isocyanate group-containing compound A and stirring sufficiently, the mixture was poured into a 250 mm × 170 mm × 5 mm formwork covered with a 50 μm polyethylene terephthalate film (PET film). It was cured at 180 ° C. for 180 minutes and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 10, it is hardly affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

(Example 11)
Using the raw materials shown in Table 1, the heat storage material B, the surfactant A, the organically treated layered clay mineral B, the hydroxyl group-containing compound A, and the reaction accelerator A at a temperature of 35 ° C. in the blending amounts shown in Table 2 After mixing, the heat storage material B was dispersed in a colloidal form (average particle size 420 μm), and then the isocyanate group-containing compound A was added and stirred sufficiently, and then a 50 μm polyethylene terephthalate film (PET film) was laid 250 mm × 170 mm × It was poured into a 5 mm mold, cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 11, it is hardly affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

(Example 12)
Using the raw materials shown in Table 1, the heat storage material A, the surfactant B, the organically treated layered clay mineral B, the hydroxyl group-containing compound C, and the reaction accelerator A at a temperature of 23 ° C. in the blending amounts shown in Table 2 After mixing, the heat storage material A was dispersed in a colloidal form (average particle size: 500 μm), and then the isocyanate group-containing compound B was added and stirred well, and then a 50 μm polyethylene terephthalate film (PET film) was laid on the plate 250 mm × 170 mm × It was poured into a 5 mm mold, cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
Moreover, the thermal storage heat insulation performance evaluation test was done by the method similar to Example 1 supposing the heating operation of winter. The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 12, it is not easily affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

(Example 13)
Using the raw materials shown in Table 1, the heat storage material A, the heat storage material B, the surfactant A, the organically treated layered clay mineral B, the hydroxyl group-containing compound A, and the reaction accelerator A in the blending amounts shown in Table 2 Mixing at a temperature of 35 ° C. to disperse the heat storage materials A and B in a colloidal form (average particle size 480 μm), then adding the isocyanate group-containing compound A and stirring sufficiently, then a 50 μm polyethylene terephthalate film (PET film). It was poured into a laid 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage and insulation performance evaluation test, as shown in FIG. 13, it is not easily affected by the outside air temperature, and there is little fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage and heat insulation properties. Results were obtained.

(Example 14)
Using the raw materials shown in Table 1, with the compounding amounts shown in Table 2, heat storage material A, heat storage material B, surfactant A, compatibilizer A, organically treated layered clay mineral B, hydroxyl group-containing compound A, The reaction accelerator A is mixed at a temperature of 35 ° C., the heat storage materials A and B are dispersed in a colloidal form (average particle diameter 600 μm), and then the isocyanate group-containing compound A is added and sufficiently stirred, and then a 50 μm polyethylene terephthalate film It was poured into a 250 mm × 170 mm × 5 mm formwork laid with (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage body.
The obtained heat storage body and polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) were laminated with an adhesive to obtain a test body.
About the obtained test body, the heat storage material leakage evaluation test 1 and 2 similar to Example 1, the heat storage physical property test, the workability test 1 and 2, and the workability test 1 and 2 were performed. The results are shown in Table 3.
In addition, assuming a heating operation in winter, a heat storage insulation performance evaluation test was performed in the same manner as in Example 1 except that the box upper surface was opened in a thermostat set at 25 ° C. and maintained for 3 hours. . The results are shown in FIG.

  In the heat storage insulation performance evaluation test, as shown in FIG. 14, it is hardly affected by the outside air temperature, and there is less fluctuation in the room temperature compared to polyurethane foam alone (Comparative Example 1), and it has excellent heat storage properties and heat insulation properties. Results were obtained.

(Comparative Example 1)
In place of the heat storage insulator obtained in Example 1, only polyurethane foam (250 mm × 170 mm × 5 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm) was used, and the same as in Example 1 A workability test, a workability test, and a heat storage insulation performance evaluation test were performed. Moreover, the thermal storage heat insulation performance evaluation test in Examples 2-8 was also performed.
The results are shown in Table 3 and FIGS.

(Comparative Example 2)
Heat storage material microcapsule aqueous dispersion containing heat storage material A shown in Table 1 (solid content 50%, heat storage material content 40% by weight, capsule component: melamine resin) 35 parts by weight, water 25 parts by weight, calcined gypsum 40 The slurry mixed with parts by weight was poured into a 250 mm × 170 mm × 5 mm mold, dried at 50 ° C. for 12 hours, and demolded to obtain a test specimen. About the obtained test body, the heat storage material leak evaluation test similar to Example 1, the heat storage physical property test, the workability test, and the workability test were done. The results are shown in Table 3.

(Comparative Example 3)
The heat storage material A shown in Table 1 was laminated with a sheet of aluminum-deposited polyethylene terephthalate (250 mm × 170 mm × 5 mm) to obtain a test body. About the obtained test body, the heat storage material leak evaluation test similar to Example 1, the heat storage physical property test, the workability test, and the workability test were done. The results are shown in Table 3.
However, since the heat storage physical property test cannot be directly measured, it was converted from the physical property value of the heat storage material based on the thermal conductivity and weight of the sheet.

(Comparative Example 4)
The heat storage material A shown in Table 1 encapsulated with gelatin (particle size 3 mm, heat storage material content 70%) was packed in a polyethylene terephthalate case of 250 mm × 170 mm × 5 mm to obtain a test specimen. About the obtained test body, the heat storage material leak evaluation test similar to Example 1, the heat storage physical property test, the workability test, and the workability test were done. The results are shown in Table 3.
However, since the heat storage physical property test cannot be directly measured, it was converted from the physical property values of the heat storage material based on the thermal conductivity and weight of the case of the gelatin coating and polyethylene terephthalate.

  The heat storage heat insulator of the present invention is suitably used mainly as an inner wall material, an outer wall material, a ceiling material, a floor material or other interior / exterior material of a building such as a house, or an interior material of a vehicle or the like. Furthermore, the heat storage insulator of the present invention can be applied to thermoelectric conversion systems, refrigeration / freezers, cooler boxes, heat insulation sheets, electrical products, OA equipment and other daily products, machines, equipment and other industrial products, plants, tanks, and the like. .

It is a heat storage insulation performance evaluation test figure of only Example 1 and a polyurethane foam (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 2 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 3 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 4 and a polyurethane foam only (comparative example 1). It is a thermal storage heat insulation performance evaluation test figure of Example 5 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 6 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 7 and only polyurethane foam (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 8 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 9 and only polyurethane foam (comparative example 1). It is a thermal storage heat insulation performance-evaluation test figure of Example 10 and a polyurethane foam only (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 11 and only polyurethane foam (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 12 and only polyurethane foam (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 13 and only polyurethane foam (comparative example 1). It is a heat storage insulation performance evaluation test figure of Example 14 and a polyurethane foam only (comparative example 1).

Claims (14)

A heat storage heat insulator in which a heat storage body and a heat insulator are laminated,
A heat storage insulator, wherein the heat storage body is a porous body (c) carrying the heat storage material (a).   The heat storage insulator according to claim 1, wherein the heat storage body is a porous body (c) in which a heat storage material (a) and a layered clay mineral (b) are supported.   The heat storage insulator according to claim 2, wherein 0.5 to 50 parts by weight of the layered clay mineral (b) is mixed with 100 parts by weight of the heat storage material (a).   The heat storage insulator according to any one of claims 1 to 3, wherein the heat storage body is a porous body (c) further carrying a heat conductive substance (d).   The heat storage body according to claim 4, wherein the heat storage material (a) is mixed with 5 to 200 parts by weight of the heat conductive substance (d) with respect to 100 parts by weight.   The porous body (c) was formed by the reaction between the compound (c-1) containing a reactive functional group and the compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group. The thermal storage insulator according to any one of claims 1 to 5, wherein the thermal storage insulator is a thing.   The heat storage body uniformly mixes the heat storage material (a), the compound (c-1) containing a reactive functional group and the compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group. And (c-1) component and (c-2) component are made to react, The thermal storage heat insulator of Claim 1 or Claim 6 characterized by the above-mentioned.   The heat storage body can react with the heat storage material (a), the layered clay mineral (b) and / or the heat conductive material (d), the compound (c-1) containing a reactive functional group, and the reactive functional group. A compound (c-2) containing a reactive functional group is uniformly mixed, and the compound (c-1) and the component (c-2) are reacted with each other. The thermal storage heat insulator according to claim 6.   The heat storage material is a heat storage material (a), a nonionic surfactant (e) having a hydrophilic / lipophilic balance (HLB value) of 10 or more, a compound (c-1) containing a reactive functional group, and the reactive functional group. The compound (c-2) containing a reactive functional group capable of reacting with a group is mixed, the heat storage material (a) is dispersed in a colloidal form, and the component (c-1) and the component (c-2) are reacted. The heat storage insulator according to claim 1 or 6, wherein the heat storage insulator is obtained.   The heat storage material is a heat storage material (a), a layered clay mineral (b) and / or a heat conductive substance (d), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant (e), A compound (c-1) containing a reactive functional group and a compound (c-2) containing a reactive functional group capable of reacting with the reactive functional group are mixed, and the heat storage material (a) is dispersed in a colloidal form. The heat storage insulator according to any one of claims 2 to 6, wherein the heat storage insulator is obtained by reacting the components (c-1) and (c-2).   The heat storage insulator according to any one of claims 2 to 10, wherein the layered clay mineral (b) is an organically treated layered clay mineral.   The content rate of the thermal storage material (a) in a thermal storage body is 40 weight% or more, The thermal storage heat insulating body in any one of Claims 1-11 characterized by the above-mentioned.   The heat storage insulator according to any one of claims 1 to 12, wherein the heat storage material (a) is an organic latent heat storage material. The thermal storage thermal insulator according to any one of claims 1 to 13, wherein the thermal conductivity of the thermal insulator is less than 0.1 W / (m · K).

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