JP2006046886A - Floor heating structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor heating structure that excels in workability and installation ease, has appreciable heat storage performance, reduces power consumption and can maintain a comfortable living environment. <P>SOLUTION: A heat storage layer supporting a heat storage medium (a) in a porous body (c), a surface heating layer and a flooring layer are laminated. The heat storage layer preferably supports the heat storage medium (a) and a layered clay mineral (b) in the porous body (c). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a floor heating structure used for floor heating in a house or the like.

With the recent increase in the residential environment, the number of homes with floor heating systems in which heat sources such as heating wires and hot water pipes are installed on the floor is increasing rapidly.
The floor heating system warms an indoor space with heat generated by a heat source such as a heating wire or a hot water pipe. In particular, when a heating wire is used, a large amount of power is consumed for the heat generation.

  One solution to this problem is a thermal storage floor heating system in which a thermal storage material is introduced into the floor heating system.

The heat storage materials are classified into sensible heat storage materials and latent heat storage materials, but in the heat storage type floor heating system, in particular, many latent heat storage materials using latent heat due to phase change of substances are employed.
The latent heat storage material uses the property of storing 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.

  When such a latent heat storage material is introduced into a floor heating system, for example, power consumption can be suppressed by storing heat using inexpensive nighttime power and gradually dissipating heat during the day. Moreover, since the temperature can be kept constant for a long time once warmed up, it is possible to reduce power consumption and maintain a comfortable living environment.

  As a floor heating system using a latent heat storage material, for example, Patent Document 1 describes using a casing latent heat storage material.

  However, since the latent heat storage material undergoes a phase change (solid-liquid change), a sturdy casing that can withstand volume changes associated with the phase change is required. This casing provides effective heat conduction to the latent heat storage material itself. There is a possibility that the heat storage performance may not be sufficiently exhibited. Furthermore, it is limited to the size of the casing size, and processing such as cutting is impossible because the latent heat storage material leaks out. In addition, construction by nailing or the like is impossible because the latent heat storage material leaks out.

JP 2001-304596 A

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, by using a heat storage layer in which the heat storage material (a) is supported on the porous body (c), the workability and workability are excellent. In addition, the present inventors have found that a floor heating structure having excellent heat storage performance, suppressing power consumption and maintaining a comfortable living environment can be obtained, and the present invention has been completed.

That is, the present invention includes the following features.
1. A floor heating structure in which a heat storage layer in which a heat storage material (a) is supported on a porous body (c), a planar heating layer, and a floor material layer are laminated.
2. As the heat storage layer, a porous body (c) in which a heat storage material (a) and a layered clay mineral (b) are supported is used. The floor heating structure described in 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 floor heating structure described in 1.
4). As the heat storage layer, a porous body (c) further supporting a heat conductive substance (d) is used. To 3. The floor heating structure 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 floor heating structure described in 1.
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. The floor heating structure according to any one of the above.
7). The heat storage layer 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 floor heating structure described in 1.
8). The heat storage layer 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. The floor heating structure according to any one of the above.
9. The heat storage layer comprises a heat storage material (a), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant (e), 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 floor heating structure described in 1.
10. The heat storage layer 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. The floor heating structure according to any one of the above.
11. 1. The layered clay mineral (b) is an organically treated layered clay mineral. To 10. The floor heating structure according to any one of the above.
12 The content of the heat storage material (a) in the heat storage layer is 40% by weight or more. To 11. The floor heating structure according to any one of the above.
13. 1. The heat storage material (a) is an organic latent heat storage material. To 12. The floor heating structure according to any one of the above.

  The floor heating structure of the present invention exhibits excellent heat storage properties, suppresses power consumption, and can maintain a comfortable living environment. Moreover, even if the heat storage layer has a high heat storage material content rate, the heat storage material does not leak over time, and even if the heat storage layer is cut, the heat storage material does not leak from the cut surface, and is excellent in workability. Moreover, since the heat storage material does not leak due to nailing or the like, the mounting workability is excellent.

  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 floor heating structure in which a heat storage layer, a planar heating layer, and a flooring layer are laminated.

  The heat storage layer of the present invention is one in which a heat storage material (hereinafter also referred to as “(a) component”) is supported on a porous body (hereinafter also referred to as “(c) component”).

  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 layer 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-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.), docosane (melting point 44 ° C.), and mixtures thereof N-paraffin, paraffin wax, etc. comprised by these.

  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 is used at a practical temperature. Since it has phase change temperature (melting | fusing point) in a certain 25 to 40 degreeC area | region, it is preferable.

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 layer, and to obtain a heat storage layer having excellent heat storage properties and excellent 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 a viscosity and TI value, the component (a) is easily supported stably in the heat storage layer during the manufacture of the heat storage layer, and in the heat storage layer after the heat storage layer is manufactured (a ) The component is easily retained for a long time. Therefore, it is possible to prevent the component (a) from leaking to the outside of the heat storage layer, and to obtain a heat storage layer that is more excellent in heat storage properties 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 part 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 the heat conductive substance, the heat transfer in the heat storage layer 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 substance 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.

  In addition, the component (c) can be used without any particular limitation, such as an inorganic porous material or an organic porous material. However, the component (a) (and the components (b) and (d)) can be more easily supported and retained. From the standpoint, an organic porous material is preferably used. Furthermore, the organic porous body can also prevent cracking and shape change of the heat storage layer due to volume shrinkage due to phase change (particularly change from liquid to solid) of 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 cross-linked structure, has good compatibility with the component (a), and easily suppresses leakage of the component (a) from the heat storage layer.

  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 layer 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 layer, the heat storage layer is easily deformed, and the heat storage material is liable 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 layer become insufficient and swelling tends to occur. 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, Additives such as anti-settling agents, anti-sagging agents, dehydrating agents, matting agents, flame retardants, ultraviolet absorbers and light stabilizers may be mixed.

  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 layer of the present invention, a method of supporting the component (a) (component (b), component (d) if necessary) by the dipping method, pressure reduction / pressure injection method, or the like on the porous body, Moreover, the method etc. which mix and carry | support the (a) component ((b) component, (d) component as needed) previously are mentioned at the time of porous body manufacture.

  In the present invention, a method in which the component (a) (component (b), component (d)) is mixed and supported in advance during the production of the porous body is preferable. Leakage of components (and component (b) and component (d)) can be further prevented, 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). The heat storage layer in which the component (component (d)) is supported on the 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 for obtaining a heat storage layer 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. Examples include a method for obtaining a heat storage layer.

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, the (c-1) component and the (c-2) component are reacted to obtain a heat storage layer in which the (a) component (and (b) component, (d) component) is supported on the porous body. 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 component (b) and the component (d)) is supported, and a heat storage layer 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 above melting | fusing point of a component, it will be in a compatible state and the outstanding thermal storage layer 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 layer 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, more preferably 0.5 to 1.5, whereby a more excellent three-dimensional crosslinked structure can be obtained, and an excellent heat storage layer 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, the (c-1) component and the (c-2) component are reacted to obtain a heat storage layer in which the (a) component (and (b) component, (d) component) is supported on the porous body. 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 layer 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 layer 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 layer 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 layer 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 layer 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 layer 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 layer 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 layer having a higher component content (a) can be obtained. Therefore, it is possible to obtain a heat storage layer that is excellent in heat storage properties and can further reduce the shape change of the heat storage layer itself due to the volume change accompanying the solid-liquid change of the component (a).
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 layer can be obtained by being 2 to 1.7, more preferably 0.3 to 1.6, 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 layer 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 layer 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 layer 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 planar heating layer of the present invention is not particularly limited, and a known planar heating element may be used.
As the planar heating element, for example, a nichrome wire meandering and disposed on the surface of the insulator, an electric resistance heating element and an electrode laminated, a PTC planar heating element, and the like can be cited. In the present invention, a laminate of an electric resistance heating element and an electrode, or a PTC planar heating element can be suitably used.

The electric resistance heating element is not particularly limited as long as the electric resistance value is 1 × 10 ³ Ω · cm or less (preferably 1 × 10 ² Ω · cm or less). Those consisting of are preferred. When the electric resistance value of the electric resistance heating element is larger than 1 × 10 ³ Ω · cm, the power consumption is increased, which is not preferable.

Resin components include acrylic resin, polyester resin, acrylic silicon resin, silicon resin, urethane resin, epoxy resin, polyvinyl alcohol resin, butyral resin, amino resin, phenol resin, fluororesin, synthetic rubber, etc., or a composite resin of these Etc.
In the present invention, for example, urethane resin, epoxy resin, acrylic resin, silicon resin, phenol resin, synthetic rubber and the like are preferably used as the flexible resin.

  Examples of conductive powder include graphite powder, scaly graphite, flake graphite, carbon powder such as carbon nanotube, graphitized fiber, carbon fiber such as fiber carrying graphite, silver, gold, copper, nickel, aluminum Metal fine particles such as zinc, platinum, palladium, iron, etc., conductive fibers in which conductive components such as these metal fine particles are supported on the fiber surface, and metal fine particles on the surface of powder such as mica, mica, talc, titanium oxide In addition, a conductive powder supported on a conductive oxide, or a conductive oxide such as fluorine-doped tin oxide, tin-doped indium oxide, antimony-doped tin oxide, or conductive zinc oxide can be used.

The electric resistance heating element can be manufactured by mixing the conductive powder so as to be uniformly dispersed in the resin and then forming it into a film or sheet by a known method.
The mixing amount of the conductive powder is not particularly limited, but it may be mixed so that the electric resistance value of the electric resistance heating element can be adjusted to 1 × 10 ³ Ω · cm or less, and the solid content of the resin component is 100 parts by weight. And 10 parts by weight or more and 300 parts by weight or less (preferably 30 parts by weight or more and 100 parts by weight or less).

In addition to the resin component, if necessary, the electrical resistance value can be reduced to 1 × 10 ³ Ω · cm or less. Additives such as an agent, a curing agent, a curing catalyst, a film increasing aid, and a solvent can also be added.

  The thickness of the electric resistance heating element is preferably 3 mm or less. If it is thicker than 3 mm, the flexibility is lowered, and temperature unevenness is likely to occur in the electric resistance heating element, which may make it difficult to achieve a uniform temperature.

  The electrode is not particularly limited as long as the electric resistance value is lower than that of the electric resistance heating element. Preferably, an electrode made of metal fine particles and / or a paste in which these metal fine particles are mixed can be used. Although it does not specifically limit as metal microparticles, Silver, copper, gold | metal | money, platinum, etc. can be used.

  The electrode can be laminated on the electric resistance heating element by a known method. For example, it can be laminated by spraying, roller, brush coating, dip coating, sputtering, vapor deposition, screen printing method, doctor blade method and the like.

The PTC sheet heating element uses PTC (Positive temperature Coefficient) characteristics, and is formed by printing a special heating ink exhibiting PTC characteristics on a resin film such as a polyester film or a PET film. can do. As a material for the special heat-generating ink, barium titanate-based ceramics that are made into a semiconductor by doping a small amount of rare earth elements such as yttrium, antimony, and lanthanum are used.
Such a PTC planar heating element quickly rises in temperature when energized due to the PTC characteristics, reaches a predetermined temperature, and can control and maintain the temperature itself, so there is no need to use a sensor controller.

  Further, since the PTC sheet heating element is a printing method using the special heating ink, the PTC sheet heating element can be formed thin, and thus can be reduced in weight and thickness. Furthermore, this PTC planar heating element has a low resistance value from when the power is turned on until it reaches a predetermined temperature, so that power consumption required for temperature rise can be suppressed. Therefore, it can be heated efficiently.

As the flooring layer of the present invention, resin tile and resin sheet such as vinyl chloride and polyolefin, wood material such as single board, plywood and particle board, fiber material, ceramic material such as porcelain tile, marble, granite, terrazzo, etc. Stone materials, concrete materials such as mortar, natural resin tiles such as rubber and linoleum, natural resin sheets, and the like can be used. Tatami mats, carpets, carpets, flooring materials, etc. can also be used as the flooring layer. In the present invention, those having heat resistance are more preferable.
The thickness of the flooring layer is usually 1 to 20 mm, preferably about 2 to 15 mm.

The floor heating structure of the present invention can be used in any case such as new construction or renovation.
The method for forming the floor heating structure of the present invention is not particularly limited, and a heat storage layer, a planar heating layer, and a floor material layer may be laminated by a known method.

As a laminating method, for example, a floor heating panel composed of a heat storage layer, a planar heating layer, and a flooring layer is prepared in advance, and a method of laminating on a base material (concrete, mortar, etc.) or existing flooring, The method of laminating | stacking a heat storage layer, a planar heat_generation | fever layer, a flooring layer in order on a base material or the existing flooring etc. is mentioned.
Specifically, on the heat storage layer obtained by the manufacturing method described above, a sheet heating layer and a flooring layer are sequentially stuck with a known adhesive or adhesive tape to produce a floor heating panel, And a method of laminating on an existing flooring via a known adhesive or adhesive tape, and the above-mentioned heat storage layer forming component ((a) component (and (b) component) directly on an existing base material or flooring , (D) component), resin components ((c-1) component, (c-2) component, etc.), (e) component, etc.) are applied to form a heat storage layer, on which a planar heating layer, The method of laminating | stacking a flooring layer in order is mentioned.
In the latter case, the heat storage layer can be formed by applying a heat storage layer forming component to a substrate or existing flooring by a known method such as spray coating, roller coating, brush coating, trowel coating, or pouring.

The thickness of the floor heating structure is not particularly limited, but in the present invention it is particularly preferably 5 to 50 mm, and preferably about 10 to 40 mm. By reducing the thickness to about 5 to 50 mm and reducing the weight, it can be easily constructed. In particular, in renovation, the comfortable living space can be maintained without being compressed after the construction.
Moreover, since this invention floor heating structure has the outstanding thermal storage performance, even if thickness is as thin as 5-50 mm, it can suppress power consumption and can maintain a comfortable living environment.

In the present invention, a heat insulating layer can be further laminated.
By laminating the heat insulating layer, it is possible to moderate the external temperature change and to efficiently heat the heat generated by the planar heat generating layer to the outside and to warm the floor surface efficiently.

  Although it does not specifically limit as a location which laminates | stacks a heat insulation layer, Between a base material or the existing flooring and a thermal storage layer is preferable. Moreover, although a heat insulation layer can be newly laminated | stacked, you may use the heat insulation layer which already exists.

  Although it does not specifically limit as a heat insulation layer, Thermal conductivity is less than 0.1 W / (m * K) (More preferably, 0.08 W / (m * K) or less, More preferably, 0.05 W / (m * K) It is preferable that it has the heat insulation property of the following). When the thermal conductivity is less than 0.1 W / (m · K), it has excellent heat insulating properties.

  Examples of such a heat insulating layer include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, and the like, or a composite thereof. Etc. Moreover, you may use a commercially available heat insulation layer.

  The thickness of the heat insulating layer is usually preferably 1 mm or more and 30 mm or less.

Furthermore, in the present invention, a heat transfer layer can be laminated. Although it does not specifically limit as a location which laminates | stacks a heat-transfer layer, Between a thermal storage layer and a planar heating layer, and between a planar heating layer and a flooring layer is preferable.
By laminating the heat transfer layer, the heat generated from the planar heat generating layer is easily transferred to the heat storage layer and the floor material layer, and the floor surface can be efficiently heated.

  Examples of the heat transfer layer include a steel plate made of a metal material such as copper, aluminum, iron, brass, zinc, magnesium, nickel, or a coating film or sheet containing these metal materials. In the present invention, an aluminum plate can be particularly preferably used.

  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.

(Manufacture of heat storage layer)
Heat storage layer 1: Using the raw materials shown in Table 1, the heat storage material A, the hydroxyl group-containing compound, and the isocyanate group-containing compound are uniformly mixed at a temperature of 40 ° C. in the blending amounts shown in Table 2, and a reaction accelerator is added. Stir well. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), demolded, and cured at 50 ° C. for 180 minutes to obtain a heat storage layer 1 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Thermal storage layer 2: Using the raw materials shown in Table 1, the thermal storage material A, hydroxyl group-containing compound, organically treated layered clay mineral, and isocyanate group-containing compound are uniformly mixed at a temperature of 40 ° C. in the blending amounts shown in Table 2. Then, a reaction accelerator was added and sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 2 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Heat storage layer 3: Using the raw materials shown in Table 1, the heat storage material A, the hydroxyl group-containing compound, the isocyanate group-containing compound, the organically treated layered clay mineral, and the thermal conductive material at the blending amount shown in Table 2 are set to a temperature of 40. The mixture was uniformly mixed at 0 ° C., a reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 3 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Heat storage layer 4: Using the raw materials shown in Table 1, the heat storage material A, the hydroxyl group-containing compound, the isocyanate group-containing compound, and the heat conductive material are uniformly mixed at a temperature of 40 ° C. in the blending amounts shown in Table 2, and the reaction An accelerator was added and stirred well. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 4 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Thermal storage layer 5: Using the raw materials shown in Table 1, with the compounding amounts shown in Table 2, thermal storage material A, hydroxyl group-containing compound, organically treated layered clay mineral, thermal conductive material, compatibilizing agent, isocyanate group-containing The compound was uniformly mixed at a temperature of 40 ° C., a reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 5 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Heat storage layer 6: Heat storage material A, heat storage material B, hydroxyl group-containing compound, organically treated layered clay mineral, compatibilizing agent, isocyanate group-containing compound using the raw materials shown in Table 1 and in the amounts shown in Table 2 Were uniformly mixed at a temperature of 40 ° C., a reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 6 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Heat storage layer 7: Using the raw materials shown in Table 1, the heat storage material A, the surfactant, the hydroxyl group-containing compound, and the isocyanate group-containing compound are mixed at a temperature of 40 ° C. in the blending amounts shown in Table 2, and the heat storage material A is obtained. The mixture was dispersed in a colloidal form (average particle size: 190 μm), a reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), demolded, and cured at 50 ° C. for 180 minutes to obtain a heat storage layer 7 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Thermal storage layer 8: Using the raw materials shown in Table 1, the thermal storage material A, the surfactant, the hydroxyl group-containing compound, the organically treated layered clay mineral, and the isocyanate group-containing compound at a temperature of 40 ° C. in the blending amounts shown in Table 2. The heat storage material A was dispersed in a colloidal form (average particle size: 440 μm), a reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 300 mm × 180 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 8 having a thickness of 5 mm. The NCO / OH ratio was 1.0.

  Thermal storage layer 9: thermal storage material microcapsule aqueous dispersion containing the thermal storage material A shown in Table 1 (solid content 50%, thermal storage material content 40% by weight, capsule component: melamine resin) 35 parts by weight and water 25 parts by weight The slurry mixed with 40 parts by weight of calcined gypsum was poured into a 300 mm × 180 mm × 5 mm mold, dried at 50 ° C. for 12 hours, and demolded to obtain a heat storage layer 9 having a thickness of 5 mm.

  Heat storage layer 10: The heat storage material A shown in Table 1 was laminated with an aluminum-deposited polyethylene terephthalate sheet (300 mm × 180 mm), and demolded to obtain a heat storage layer 10 having a thickness of 5 mm.

  Heat storage layer 11: Heat storage material A shown in Table 1 encapsulated with gelatin (particle size 3 mm, heat storage material content 70%) is packed into a 300 mm × 180 mm × 5 mm polyethylene terephthalate case, demolded and thickened A 5 mm heat storage layer 11 was obtained.

(Heat storage material leakage evaluation test 1)
The obtained heat storage layer was allowed to stand in an atmosphere of 10 ° C. or 50 ° C. for 72 hours, and then transferred to an environment of 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 heat storage layer 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 heat storage layer 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 heat storage layer 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)
In an environment of a temperature of 30 ° C. and a relative humidity of 50% RH, the obtained heat storage layer 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 heat storage layer was nailed, and leakage of the heat storage material due to the nail driving 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 heat storage layer was nailed, and leakage of the heat storage material due to the nail driving 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

Example 1
On the plywood (300 × 180 mm, thickness 5 mm), the heat storage layer 1, the planar heat generation layer, and the flooring layer were sequentially stacked to prepare a test plate.
The flooring layer was a plywood (300 × 180 mm, thickness 5 mm), and the sheet heating layer was a silicon rubber heater (300 × 180 mm, thickness 2 mm) in which a nichrome wire meandered in silicon rubber.
As shown in Fig. 1, polystyrene foam with a thickness of 25mm is installed on the side and top surface so that the inner dimension is 300x180x200mm, and the floor material layer side of the test plate is installed on the bottom side. Thus, a test body box was produced.
Furthermore, in order to measure the floor surface temperature, the floor back surface temperature, and the space temperature (the temperature in the box), as shown in FIG. A thermocouple was installed. As shown in FIG. 1, a temperature controller (thermostat) was attached to the floor surface in order to keep the surface temperature constant.
This test body box was installed in a thermostat and the following experiment was conducted.
The temperature in the thermostat was set to 10 ° C. and left for 15 hours. Thereafter, the planar heating layer was heated for 180 minutes while the temperature in the thermostatic chamber was set to 10 ° C. The floor surface was set to be constant at 30 ° C. by a temperature controller (thermostat).
As the floor heating performance evaluation, the temperature of each part 60 minutes after the heating of the planar heating layer was measured. Moreover, after heating for 180 minutes, the heating was stopped and the temperature of each part 60 minutes after the stop was measured. The results are shown in Table 4.

(Example 2)
The test was performed in the same manner as in Example 1 except that the heat storage layer 2 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Example 3)
The test was performed in the same manner as in Example 1 except that the heat storage layer 3 was used instead of the heat storage layer 1. The results are shown in Table 4.

Example 4
A test was performed in the same manner as in Example 1 except that the heat storage layer 4 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Example 5)
The test was performed in the same manner as in Example 1 except that the heat storage layer 5 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Example 6)
The test was performed in the same manner as in Example 1 except that the heat storage layer 6 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Example 7)
The test was performed in the same manner as in Example 1 except that the heat storage layer 7 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Example 8)
The test was performed in the same manner as in Example 1 except that the heat storage layer 8 was used instead of the heat storage layer 1. The results are shown in Table 4.

(Comparative Example 1)
A backup material with a thickness of 5 mm is provided on a plywood (300 x 180 mm, thickness 5 mm), and a sheet heating layer and a flooring layer are stacked on top of each other, and the thickness is between the plywood and the sheet heating layer. A test plate provided with a 5 mm air layer was produced.
The test was performed in the same manner as in Example 1 except that this test plate was used. The results are shown in Table 4.

(Comparative Example 2)
A 5 mm polyurethane foam was provided on a plywood (300 × 180 mm, thickness 5 mm), and a sheet heating layer and a flooring layer were sequentially stacked thereon to prepare a test plate.
The test was performed in the same manner as in Example 1 except that this test plate was used. The results are shown in Table 4.

2 is a cross-sectional view of a test specimen box used in Example 1. FIG.

Explanation of symbols

1: Thermal storage layer 1
2: sheet heating layer 3: flooring layer 4: plywood 5: polystyrene foam 6: thermocouple 7: temperature controller (thermostat)

Claims (13)

  A floor heating structure in which a heat storage layer in which a heat storage material (a) is supported on a porous body (c), a planar heating layer, and a floor material layer are laminated.   The floor heating structure according to claim 1, wherein the heat storage layer is a porous body (c) in which a heat storage material (a) and a layered clay mineral (b) are supported.   The floor heating structure 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 floor heating structure according to any one of claims 1 to 3, wherein the heat storage layer uses a porous body (c) further carrying a heat conductive substance (d).   The floor heating structure 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 floor heating structure according to any one of claims 1 to 5, wherein the floor heating structure is a thing.   The heat storage layer 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. The floor heating structure according to claim 1 or 6, wherein the floor heating structure is obtained by reacting the components (c-1) and (c-2).   The heat storage layer 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 floor heating structure according to claim 6.   The heat storage layer comprises a heat storage material (a), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant (e), 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 floor heating structure according to claim 1 or 6, wherein the floor heating structure is obtained.   The heat storage layer 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 floor heating structure according to any one of claims 2 to 6, wherein the floor heating structure is obtained by reacting the components (c-1) and (c-2).   The floor heating structure according to any one of claims 2 to 10, wherein the layered clay mineral (b) is an organically treated layered clay mineral.   The floor heating structure according to any one of claims 1 to 11, wherein the content of the heat storage material (a) in the heat storage layer is 40% by weight or more. The floor heating structure according to any one of claims 1 to 12, wherein the heat storage material (a) is an organic latent heat storage material.

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