JP5719578B2 - Floor heating structure - Google Patents

Description

  The present invention relates to a floor heating structure.

Conventionally, a floor heating system having a heating element has been provided with a temperature control device such as a temperature sensor, and the floor surface temperature is kept substantially constant around a predetermined temperature.
That is, a cycle is repeated in which heat is generated by the heating element until the predetermined temperature is reached (power ON), heat generation is stopped when the predetermined temperature is reached (power OFF), and heat is generated when the temperature falls to the predetermined temperature (power ON). As a result, the floor temperature is kept substantially constant around a predetermined temperature.

  Many of these floor heating systems have a structure in which a floor material layer is laminated on a heating element, and in order to minimize the error between the temperature detected by the temperature sensor and the sensory temperature, the temperature sensor The installation location is often installed near the floor layer or near the heating element.

  In recent years, in floor heating systems having a heating element, those having a heat storage body have appeared (for example, Patent Documents 1 and 2). By storing a part of heat from the heating element in the heat storage body, this can be maintained for a long time near a predetermined temperature even after the power is turned off. If such a heat storage type floor heating system is used, the power ON / OFF cycle can be reduced, and heat storage by midnight power can also be used. As a result, the power consumption can be suppressed, which plays a major role in the energy saving effect. Can be fulfilled.

Japanese Patent No. 3138959 Japanese Patent No. 3620461

  However, in the floor heating systems such as Patent Documents 1 and 2, since the temperature sensor and the heating element are arranged near the floor (for example, Patent Document 1 FIG. 1 and Patent Document 2 FIG. 5), the heat from the heating element. Before the temperature is sufficiently stored in the heat storage body, the temperature sensor detects and the power ON / OFF temperature control device operates, and the heat storage effect may not be sufficiently exhibited.

  In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, on the upper side of the specific heat storage layer, on the lower side of the heat storage layer of the floor heating structure in which the planar heating element and the flooring layer are sequentially laminated. By installing a temperature sensor for temperature control, the floor surface temperature can be kept close to the specified temperature for a long time without introducing a complicated temperature control device, and the heat storage effect by the heat storage layer is sufficient Since it can be demonstrated and has excellent sustainability of the heat storage effect, it has been found that the power ON-OFF cycle is reduced and it has a great effect on energy saving, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. On the upper side of the heat storage layer is a floor heating structure in which a planar heating element and a flooring layer are laminated in order,
The heat storage layer is an organic latent heat storage material (a), an organically treated layered clay mineral (b), a polyol having 3 or more OH groups in one molecule and a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less. (C-1), containing an isocyanate compound (c-2), wherein the mixing ratio of (c-1) and (c-2) is 1.5 or more and 8.0 or less in terms of the NCO / OH ratio,
A floor heating structure in which a temperature sensor for temperature control is installed only below the heat storage layer.
2. The heat storage layer is an organic latent heat storage material (a), an organically treated layered clay mineral (b), a polyol having 3 or more OH groups in one molecule and a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less. (C-1), an isocyanate compound (c-2), and a nonionic surfactant (d), and the mixing ratio of (c-1) and (c-2) is 1.5 or more in NCO / OH ratio. It is 8.0 or less. The floor heating structure described in 1.
3. The nonionic surfactant (d) is a nonionic surfactant (d) having at least two or more OH groups in one molecule, and the total amount of (c-1) and (d) and (c -2) is an NCO / OH ratio of 1.0 or more and less than 1.5. The floor heating structure described in 1.
4). 1. A heat-resistant layer is laminated between the heat storage layer and the planar heating element. To 3. The floor heating structure according to any one of the above.
5). 1. The thickness of the heat storage layer is 1 mm or more and 20 mm or less. To 4. The floor heating structure according to any one of the above.

  The floor heating structure of the present invention can maintain the floor surface temperature near a predetermined temperature for a long time, and can sufficiently exhibit the heat storage effect by the heat storage layer and has excellent sustainability of the heat storage effect. This has a great effect on energy saving.

1 is a cutaway view of a test body box used in Example 1. FIG. 3 is a cross-sectional view of a test specimen box used in Comparative Example 1. FIG. 6 is a cross-sectional view of a specimen box used in Comparative Example 2. FIG. 4 is a temperature change graph of the floor surface of Example 1, Comparative Example 1 and Comparative Example 2.

1: heat storage layer 2: heat-resistant layer 3: planar heating layer 4: flooring layer 5: plywood 6: polystyrene foam 7: temperature sensor 8: temperature controller 9: thermocouple

  Hereinafter, modes for carrying out the present invention will be described.

<Floor heating structure>
In the floor heating structure of the present invention, a sheet heating element and a floor material layer are sequentially laminated on the upper side of the heat storage layer, and a temperature sensor for temperature control is installed on the lower side of the heat storage layer. It is.
In addition, the temperature sensor is connected to a temperature control device that controls the heat generated by the planar heating layer, and the temperature detected by the temperature sensor is transmitted to the temperature control device to control the heating by the planar heating layer. (Power ON-OFF).
As the temperature sensor and the temperature control device, known ones may be used, and the temperature control device only needs to be located at an easy-to-operate place such as the upper side or the wall surface of the flooring layer.
With such a floor heating structure, it is possible to keep the floor surface temperature close to a predetermined temperature for a long time without introducing a complicated temperature control device, and to store heat by using a specific heat storage layer described later. The heat storage effect by the layer can be sufficiently exerted, and the heat storage effect has excellent sustainability. The power ON-OFF cycle is reduced, and a great effect is achieved for energy saving.
If both the temperature sensor and the planar heating element are on the upper side of the heat storage layer, there is immediate effect, but the temperature control program operates without sufficient heat storage in the heat storage layer, and the heat storage effect cannot be fully demonstrated. . When the planar heating element is under the heat storage layer or inside the heat storage layer, it lacks immediate effect.

<Heat storage layer>
The heat storage layer of the present invention comprises an organic latent heat storage material (hereinafter also referred to as “(a) component”), an organically treated layered clay mineral (hereinafter also referred to as “(b) component”), and one molecule. A polyol having 3 or more OH groups therein and a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less (hereinafter also referred to as “component (c-1)”) and an isocyanate compound (hereinafter referred to as “(c -2) also referred to as “component”.).

  Examples of the component (a) include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, long chain fatty acid esters, polyether compounds, fatty acid triglycerides, and the like, and one or more of these are used. Can do.

  Since the component (a) has a high boiling point and is excellent in compatibility with the component (c-1) and / or the component (c-2), the component (a) is volatilized from the obtained heat storage layer. It is hard to do. Therefore, there is almost no volume change (thinning) at the time of forming the heat storage layer, and the heat storage performance is maintained for a long time, which is preferable. Furthermore, when an organic latent heat storage material is used, it is easy to set the phase change temperature according to the application. For example, by mixing two or more organic latent heat storage materials having different phase change temperatures, the phase change temperature can be easily set. Can be set.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used. Specifically, n-decane (melting point −30 ° C.), n-undecane (melting point −25 ° C.), n-dodecane (melting point -8 ° C), n-tridecane (melting point -5 ° C), pentadecane (melting point 6 ° C), n-tetradecane (melting point 8 ° C), n-hexadecane (melting point 17 ° C), n-heptadecane (melting point) 22), n-octadecane (melting point 28 ° C), n-nonadecane (melting point 32 ° C), eicosane (melting point 36 ° C), docosan (melting point 44 ° C), and mixtures thereof. Etc.

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

  As the long chain fatty acid, for example, a long chain fatty acid having 8 to 36 carbon atoms can be used. Specifically, octanoic acid (melting point: 17 ° C.), decanoic acid (melting point: 32 ° C.), dodecanoic acid (melting point: 44 ° C.). ), Fatty acids such as tetradecanoic acid (melting point 50 ° C.), hexadecanoic acid (melting point 63 ° C.), octadecanoic acid (melting point 70 ° 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 polyether compound include diethylene glycol, triethylene glycol, tetraethylene glycol, triethylene glycol monomethyl ether, polypropylene glycol, polyethylene glycol, polypropylene glycol diacrylate, and ethylethylene glycol.

  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.

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

The component (b) used in the present invention is an organically treated layered clay mineral that is used by mixing with the component (a). By mixing the component (b) and the component (a), the component (a) enters between the layers of the component (b). Since the component (b) is organically treated, the (a) component is likely to enter the (b) component layer, and the (a) component is easily retained between the (b) component layers. Yes.
By mixing the component (b) and the component (a), as a result, the viscosity of the component (a) is increased, and the component (a) is supported and retained in the component (c) described later. You can continue. 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.
The component (b) hardly reacts with the component (a) and does not affect the melting point of the organic latent heat storage material and other various physical properties. Therefore, the performance of the component (a) as a heat storage material can be efficiently exhibited, and the phase change temperature (melting point) can be easily set.

  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 using a B-type rotational viscometer at a temperature of 23 ° C., a relative humidity of 50% RH, and 20 rpm.
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 carried in the component (c) described later, and the component (a) is easily held in the component (c). 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.

The component (b) is not particularly limited as long as it is an organically treated layered clay mineral.
Examples of the layered clay mineral 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,
Hosung's Esben, Esven C, Esben E, Esben W, Esben P, Esben WX, Esven NX, Esven NZ, Esven N-400, Organite, Organite D, Organite T (trade name)
TIXOGEL MP, TIXOGEL VP, TIXOGEL VP, TIXOGEL MP, TIXOGEL EZ 100, MP 100, TIXOGEL UN, TIXOGEL DS, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A )
BENTONE 34, 38, 52, 500, 1000, 128, 27, SD-1, SD-3 (trade names) manufactured by Elementis Japan
Etc.

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

The component (c-1) used in the present invention has 3 or more OH groups in one molecule, and has a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less (preferably 20 KOHmg / g or more and 35 KOHmg / g or less). It is a polyol that forms a molded product (hereinafter also referred to as “component (c)”) by reacting with the component (c-2) described later, and is a component that supports and holds the component (a).
The hydroxyl value is a value calculated by a neutralization titration method.

Examples of the component (c-1) include polyester polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, polyether polyol, polycaprolactone polyol, polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, and polyoxypropylene ethylene polyol. , Epoxy polyols, alkyd polyols, fluorine-containing polyols, silicon-containing polyols, cellulose and / or derivatives thereof, polysaccharides such as amylose, and the like.
In the present invention, it is particularly preferable to use a polyether polyol, and it is more preferable to use a polyether polyol having glycerin as an initiator.

Such a component (c-1) can react with the component (c-2) to form an appropriate three-dimensional crosslinked structure, and a large amount of the component (a) is supported and retained in the crosslinked structure. A possible heat storage layer can be obtained, and the obtained heat storage layer is excellent in flexibility and can suppress the leakage of the component (a).
In a polyol having less than 3 OH groups in one molecule, it is difficult to form a three-dimensional cross-linked structure, and a large amount of component (a) may not be supported / held. Moreover, when a hydroxyl value is too high, it is difficult to contain many heat storage materials, and it may be inferior to a softness | flexibility. Moreover, when the hydroxyl value is too low, the heat storage material may not be sufficiently retained.

  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 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, cyclohexylene glycol, cyclohexanediol, cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexa Methylene All, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, meta Xylene glycol, para-xylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, bisphenols (such as bisphenol A), sugar alcohols (xylitol, sorbitol, Sucrose etc.), pentaerythritol, dipentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane and the like.

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, polycarboxylic 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 a hydroxyl group or copolymerizing another copolymerizable monomer.

Examples of the acrylic monomer having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, and (meth) acrylic. (Meth) acrylic esters such as acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid-4-hydroxybutyl, and the like (tri) (meth) acrylic such as glycerin and trimethylolpropane Acid monoesters;
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, octadecyl (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 and the like) and diene (for example, butadiene, isoprene and the like) may be used.

  Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoalkyl ether, and polyalkylene glycols such as polypropylene glycol monoalkyl ether, as well as ethylene using polyvalent amine or polyhydric alcohol as an initiator. And a copolymer obtained by ring-opening addition of at least one of oxide and propylene oxide.

  Examples of the polyvalent amine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, Tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine And naphthalenediamine.

  Examples of the polyhydric alcohol include those described above, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, Cyclohexanedimethanol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, trimethylolethane, bisphenols (such as bisphenol A), sugar alcohols (such as xylitol, sorbitol, sucrose), pentaerythritol, dipentaerythritol, 2 -Methylolpropanediol, ethoxylated trimethylolpropane and the like are preferably used.

  In the present invention, it is particularly preferable to use a polyether polyol having glycerol as an initiator as the polyol. The polyether polyol having glycerin as an initiator is excellent in compatibility with the heat storage material and easily supports and holds the heat storage material.

  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.

  In the present invention, it is particularly preferable to use a polyether polyol having glycerol as an initiator as the polyol. The polyether polyol having glycerin as an initiator is excellent in compatibility with the heat storage material and easily supports and holds the heat storage material.

The molecular weight of the polyol used in the present invention is preferably about 5000 to 8000.
The glass transition temperature of the polyol used in the present invention is not particularly limited, but is preferably about −30 ° C. to 80 ° C.

  Examples of the component (c-2) include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, araliphatic diisocyanate, and the like, and allohanated, biuretized, dimerized (uretidione), and trimerized (isocyanate). Nurate), adducts, carbodiimide reactions and the like, mixtures thereof, and copolymers with monomers copolymerizable therewith.

  Examples of the aliphatic diisocyanate 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-penta Methylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, Njiisoshiane - DOO, dimer acid diisocyanate, norbornene diisocyanate.

  Examples of the alicyclic diisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4 ′. -Methylene bis (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, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate Over doors and the like.

  Examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), naphthylene-1,4-diisocyanate, and 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'-diisocyanate, dianisidine diisocyanate, tetramethylenexylylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include 1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3. -Bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, etc. .

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

  This invention mixes (a) component, (b) component, (c-1) component, (c-2) component, and makes (c-1) component and (c-2) component react. , (C-1) and (c-2) component (hereinafter also referred to as "(c) component") in a heat storage layer containing (a) component ((b) component) Can be obtained.

Moreover, the mixing ratio of the component (c-1) and the component (c-2) is 1.5 or more and 8.0 or less, preferably more than 1.5 and 7.0 or less, more preferably 1. as NCO / OH ratio. It is set within the range of 7 to 5.0, more preferably 2.0 to 3.0.
In the present invention, when the component (a) (including the component (b)) is contained in a large amount, the component (c-1) and component (c-2) specific to the present invention are used, and the NCO / OH ratio is By setting it to 1.5 or more and 8.0 or less, even if the content of the component (a) is high, the component (a) has excellent holding power and moldability, has excellent heat storage performance and sustainability, and The present inventors have found that a heat storage layer excellent in flexibility, workability and workability can be obtained without leakage of the component (a).
When the mixing ratio of the component (c-1) and the component (c-2) and the NCO / OH ratio are less than 1.5, the holding power, flexibility, and moldability of the component (a) are reduced, and curing failure occurs. On the other hand, when the NCO / OH ratio is greater than 8.0, the holding power and moldability of the component (a) are lowered, and curing failure occurs.

  The mixing ratio of the component (a) is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 65% by weight or more with respect to the total amount of the heat storage layer. Although an upper limit is not specifically limited, It is about 90 weight% or less on manufacture.

  Furthermore, in the present invention, a nonionic surfactant (hereinafter also referred to as “component (d)”) is used together with the components (a), (b), (c-1), and (c-2). It is preferable to include.

As the component (d), 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,
Polyoxyethylene hydrogenated castor oil, polyoxyethylene coconut oil fatty acid sorbitan and the like can be mentioned, and in particular, polyoxyethylene sorbitan fatty acid ester is preferably used.

In the present invention, the component (d) preferably contains a nonionic surfactant having at least two or more OH groups in one molecule.
In the present invention, by using a nonionic surfactant having at least two or more OH groups in one molecule, the retention power and moldability of the component (a) become superior, and more excellent heat storage performance and sustainability. And a heat storage layer that is superior in flexibility, workability, and workability is obtained.

Further, as the component (d), the hydrophilic / lipophilic balance (HLB value) is 10 or more (preferably more than 10 and 20 or less, more preferably 11 or more and 19 or less, further preferably 12 or more and 18 or less, and most preferably 13 or more and 17 or less. ) Nonionic surfactants can be suitably used.
By including such component (d), separation of component (a), component (b), component (c-1), and component (c-2) can be prevented, and component (a) is uniform. Can be obtained.

In addition, when the component (d) is included, the total amount of the component (c-1) and the component (d) and the mixing ratio of the component (c-2) are 1.0 to less than 1.5 in terms of the NCO / OH ratio. Further, it is preferably 1.05 or more and 1.45 or less.
When the total amount of the component (c-1) and the component (d) and the mixing ratio of the component (c-2) and the NCO / OH ratio are less than 1.0, the holding power of the component (a), flexibility, There may be no improvement in moldability. In addition, when the NCO / OH ratio is greater than 1.5, there may be cases where the holding power and moldability of the component (a) are not improved.

The mixing ratio of the component (d) and the component (a) is usually 0.01 to 30 parts by weight (preferably 0.1 to 20 parts by weight) with respect to 100 parts by weight of the component (a). ) By being in such a range, the separation of the component (a), the component (b), the component (c-1), and the component (c-2) can be further prevented, and the component (a) is uniformly dispersed. A heat storage layer can be obtained.
When the component (d) is less than 0.01 parts by weight, the component (a) and the component (c-1) and / or the component (c-2) are separated or easily cause a creaming phenomenon. Difficult to disperse. 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 addition, when a heat storage material having a long chain alkyl group having 8 to 36 carbon atoms is used as the component (a), a nonionic property having a long chain alkyl group having 8 to 36 carbon atoms in the structure of the component (d). It is preferable to use a surfactant. In particular, the effects of the present invention can be enhanced by selecting those having similar or similar carbon numbers of the long-chain alkyl groups of the components (a) and (d).

Moreover, when mixing and using 2 or more types of (a) component, it is preferable to use a compatibilizing agent (henceforth "(e) component"). By using the component (e), the compatibility between the components (a) can be improved.
Examples of the component (e) 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). More than one species 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 that 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 sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate. And sorbitan fatty acid esters such as sorbitan tristearate, sorbitan trioleate, and sorbitan sesquioleate.

  The mixing ratio of the component (e) and the component (a) is usually 0.1 to 20 parts by weight (preferably 0.1 to 10 parts by weight) with respect to 100 parts by weight of the component (a). )

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, amines such as triethylamine, triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylaminoethanol, dimer diamine, dimer acid polyamidoamine;
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.

  What is necessary is just to mix a reaction accelerator in the ratio of 0.01-10 weight part normally with respect to 100 weight part of solid content of (c-1) component, Preferably it is 0.05-5 weight part.

  In addition to the above components, the heat storage layer of the present invention includes pigments, aggregates, viscosity modifiers, plasticizers, buffers, dispersants, crosslinkers, pH adjusters, antiseptics, antifungal agents, antibacterial agents, and algae Agent, wetting agent, antifoaming agent, foaming agent, leveling agent, pigment dispersant, anti-settling agent, anti-sagging agent, anti-freezing agent, lubricant, dehydrating agent, matting agent, UV absorber, antioxidant, light stability An additive such as an agent, fibers, a fragrance, a chemical substance adsorbent, a photocatalyst, a moisture-absorbing / releasing powder, a heat conductive substance, and a flame retardant can also be contained.

  For example, as a flame retardant, for example, phosphorus trichloride, phosphorus pentachloride, ammonium polyphosphate, amide-modified ammonium polyphosphate, melamine phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, ethylenediamine phosphate zinc salt, Phosphorus amine salts such as 1,4-butanediamine phosphate, and phosphorus compounds such as red phosphorus and phosphate esters; tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β -Chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, tri (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2 - Organophosphorus compounds such as (roxyethyl) aminomethyl phosphate and di (polyoxyethylene) hydroxymethyl phosphate; magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zinc hydroxystannate, zinc stannate, nickel oxide, Metal compounds such as cobalt oxide, iron oxide, copper oxide, molybdenum oxide, tin oxide, zinc oxide, silicon oxide, zeolite, zinc borate, sodium borate, zirconium oxide, antimony trioxide, antimony pentoxide; Examples thereof include expansive graphite such as graphite, pyrolytic graphite, and cache graphite treated with sulfuric acid, nitric acid, acetic acid, perchloric acid, perchlorate, permanganate, and the like.

  In the present invention, those containing expandable graphite are particularly preferable. As the expansive graphite, those having an expansion temperature not higher than the flash point of the latent heat storage material are preferable. For example, those having an expansion temperature of 180 ° C. or lower, 170 ° C. or lower, and 160 ° C. or lower are preferable. With such an expansion temperature, it expands below the flash point of the latent heat storage material to form a surface carbonized layer (heat insulation layer), and can prevent ignition of the latent heat storage material. Such expansive graphite is preferably one in which an organic acid such as acetic acid is inserted (treated) between the layers of natural scaly graphite. Particularly preferred are those having a particle size of 150 to 500 μm and an expansion volume of 150 to 300 ml / g.

  The mixing ratio of the component (a) and the flame retardant is usually about 5 to 100 parts by weight (preferably 10 to 50 parts by weight) of the flame retardant with respect to 100 parts by weight of the component (a).

In the method for producing a heat storage layer of the present invention, the component (a), the component (b), the component (c-1), the component (c-2), and other components as necessary are mixed, and (c-1) The component is reacted with the component (c-2).
As a manufacturing method, (a) component, (b) component, (c-1) component, (c-2) component, and other components as needed are mixed, (c-1) component and (c-2) ) Component reacting method, (a) component, (b) component, (c-1) component (or (c-2) component), and other components as necessary, and (c-2) component ( Or the method of making it react by adding (c-1) component) etc. are mentioned.
Although reaction temperature is not specifically limited, It is preferable to set it as more than the phase change temperature of (a) component, and although it changes with kinds of (a) component to be used, it may be about 20 degreeC-80 degreeC normally. Moreover, reaction time should just be normally about 0.2 to 5 hours.
Moreover, in order to accelerate | stimulate reaction, energy, such as the said reaction promoter and heat | fever, light, can be given.

When component (d) is contained, component (a), component (b), component (d), component (c-1), component (c-2), and other components as necessary are mixed. The component (a) is preferably colloidally dispersed, and the component (c-1) and the component (c-2) are reacted. Specifically, the component (a), the component (b), the component (d), the component (c-1), the component (c-2), and other components as necessary are mixed, and the component (c-1) And (c-2) component, (a) component, (b) component, (d) component, (c-1) component (or (c-2) component), and other components as necessary. The method of making it react by mixing and adding (c-2) component (or (c-1) component) is mentioned.
In such a method, a state in which the component (a) is dispersed in the form of a fine colloid in the component (c-1) and / or the component (c-2) is produced. By reacting the component with the component (c-2), a heat storage layer in which the component (a) is finely dispersed in the component (c) can be produced.
In such a manufacturing method, the content rate of (a) component can be made higher. In addition, since the component (a) is in a finely and uniformly dispersed state, there is no bias of the heat storage material even when fixed vertically, and the heat storage layer itself due to the volume change accompanying the solid-liquid change of the component (a) Since a change in shape can also be reduced, it is preferable.

  In the method of producing a state in which the component (d) is contained and dispersed in a fine colloidal state, the component (a) has a particle diameter of 10 μm to 1000 μm (preferably 50 μm to 900 μm, more preferably 100 μm to It is preferably in a state of being dispersed in a colloidal shape having a size of about 800 μm). 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.

  The particle diameter is a value measured using an optical microscope (BHT-364M, manufactured by Olympus Optical Co., Ltd.).

  The production of the heat storage layer of the present invention is not particularly limited, and may be produced by a conventional method. For example, the heat storage layer may be manufactured by extrusion molding, mold forming, etc., and heat-accumulated by forming and coating various substrates by known methods such as spray coating, roller coating, brush coating, trowel coating, pouring, etc. A layer may be produced.

<Surface heating element>
The planar heating element of the present invention is not particularly limited, and a known planar heating element can 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.

The electrical resistance heating element is not particularly limited as long as the electrical 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 silicone resin, silicone resin, urethane resin, epoxy resin, polyvinyl alcohol resin, butyral resin, amino resin, phenol resin, fluororesin, synthetic rubber, acrylic resin, silicone resin , Polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluorine resin, vinyl acetate resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicone modified Acrylic resin, ethylene / vinyl acetate / versaic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin and other solvent soluble resins, NAD resin, water soluble resin, water dispersion type Examples thereof include organic binders such as oils, solvent-free resins, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber, and composite resins of these. .
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 forming the conductive powder into a film or a 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-forming 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 utilizes 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 until it reaches a predetermined temperature after turning on the power, and can suppress power consumption required for temperature rise. Therefore, it can be heated efficiently.

<Floor material layer>
As the flooring layer of the present invention, resin tiles and resin sheets such as vinyl chloride and polyolefin, monolithic boards, flooring materials, plywood, particle boards, cork tiles and other wood materials, fiber materials, ceramic tiles and other ceramic materials Stone materials such as marble, granite, and terrazzo, 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, etc. can also be used as the flooring layer. In the present invention, those having heat resistance are more preferable.

<Method for forming floor heating structure>
As a method for forming the floor heating structure of the present invention, for example, a floor heating panel including a temperature sensor, a heat storage layer, a planar heating layer, and a floor material layer is prepared in advance, and a base material (concrete, mortar, etc.) is prepared. And a method of laminating on an existing flooring, a method of laminating a temperature sensor, a heat storage layer, a planar heating layer, and a flooring layer on a base material and an existing flooring.
Specifically, a planar heating layer is installed on the upper side of the heat storage layer obtained by the manufacturing method described above, a temperature sensor is installed on the lower side of the thermal storage layer, and a floor material layer is further installed on the upper side of the planar heating layer. Can be applied with a known adhesive or adhesive tape to produce a floor heating panel and laminated on a base material or existing flooring via a known adhesive or adhesive tape.
The temperature control device for controlling the heat generation by the planar heating layer is connected to the temperature sensor and the planar heating layer, and the temperature detected by the temperature sensor is transmitted to the temperature control device, so that the planar heating layer The temperature control device may be in a place where it can be easily operated, such as the upper side of the flooring layer or the wall surface.

  The thickness of the heat storage layer is usually about 1 mm to 20 mm, further about 2 mm to 15 mm, the thickness of the planar heating element is usually about 5 mm or less, further about 3 mm or less, and the thickness of the flooring layer is usually about 1 to 20 mm. Preferably, it may be about 2 to 15 mm. When the heat storage layer is too thick, it takes time until heat is stored in the heat storage layer, which may lack immediate effect, and may require excessive power consumption.

Further, the thickness of the entire floor heating structure is usually 40 mm or less, and in the present invention, it is particularly preferably 25 mm or less, preferably 20 mm or less, more preferably 15 mm or less. By reducing the thickness of the floor heating structure, it can be reduced in weight and can be constructed easily. Especially in renovation, it is possible to maintain a comfortable living space without being compressed after construction. it can.
In addition, since the floor heating structure of the present invention has excellent heat storage performance, even a thin film suppresses the movement of heat under the floor during floor heating operation, and the temperature of the room temperature and the floor temperature after the floor heating is stopped. Can be prevented. Therefore, the amount of power consumption can be suppressed and a comfortable living environment can be maintained.

<Heat resistant layer>
In the floor heating structure of the present invention, a heat-resistant layer can also be laminated, and it is particularly preferred to laminate between the heat storage layer and the planar heating element.
By laminating the heat-resistant layer, deformation of the heat storage layer can be suppressed against an excessive temperature rise such as a heating wire.
Examples of the heat resistant layer include a glass layer having a heat resistant temperature of 100 ° C. or higher, a metal layer, a heat resistant resin layer, and the like. In consideration of the thinness in the present invention, the thickness of the heat-resistant layer is preferably 5 mm or less.
In addition, the heat-resistant temperature as used in the field of this invention means the upper limit temperature at which a heat-resistant layer does not deform | transform. That is, when the temperature is higher than the heat resistant temperature, the heat resistant layer may be deformed.

  Examples of the glass layer include a glass plate or a glass fiber layer in which glass fibers are arranged in a mesh, spots or randomly.

  Examples of the metal layer include one or more metals selected from aluminum, gold, silver, copper, iron, chromium, zinc, magnesium, titanium, nickel, bismuth, tin, and cobalt, or oxides and chlorides of these metals. , Sulfides, carbonates, silicates, phosphates, nitrates, sulfates, and composites containing one or more selected from these.

  Examples of the heat-resistant resin layer include those in which one or more of synthetic resins such as polyethylene terephthalate and polypropylene are formed in a plate shape or a film shape.

By laminating such a heat-resistant layer, it is possible to suppress deformation and combustion of the heat storage layer accompanying an excessive increase in temperature. Furthermore, leakage of the latent heat storage material associated with deformation of the heat storage layer can be prevented.
In addition, such a heat-resistant layer also has a soaking effect that makes the entire floor surface a uniform temperature. For example, when a planar heating element is laminated on a part of the floor surface, Can be spread over the entire surface. In particular, by laminating a layer having a high thermal conductivity such as a metal layer, a more excellent soaking effect can be exhibited.
In addition, a rapid increase in temperature can be prevented by laminating a glass layer having a low thermal conductivity and a heat-resistant resin layer.
In the present invention, in addition to heat resistance, considering a soaking effect and an effect of preventing a rapid temperature rise, a heat resistant layer obtained by laminating a metal layer, a glass layer and / or a heat resistant resin layer, and further, a metal layer and a glass layer A heat-resistant layer in which is laminated can be suitably applied. Moreover, you may laminate | stack a metal layer, a glass layer, and / or a heat-resistant resin layer by two layers or 3 layers or more.

  In the present invention, when the heat-resistant layer is formed by laminating a metal layer and a glass layer and / or a heat-resistant resin layer, the heat-resistant layer is laminated so that the glass layer or the heat-resistant resin layer is laminated at least on the heat storage layer side. Are preferably laminated.

The method of laminating the heat-resistant layer is not particularly limited, but the method of laminating the heat storage layer and the heat-resistant layer in advance by the above-mentioned method, the method of laminating the heat-storage layer and then laminating the heat-resistant layer, the sheet heat generation in advance And a method of laminating a body and a heat-resistant layer by the above-described method.
The heat-resistant layer only needs to be laminated at least where the planar heating element is laminated, and may be laminated on the entire surface of the heat storage layer.

<Insulation layer>
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 heating element 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.

Example 1
On a plywood (300 × 180 mm, thickness 5 mm), a temperature sensor, a heat storage layer / heat-resistant layer, a planar heat generation layer, and a flooring layer were sequentially laminated to prepare a test specimen. The obtained heat storage layer was excellent in flexibility, and excellent in workability and workability.
Heat storage layer / heat-resistant layer: 75 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 25 mgKOH / g, molecular weight 7000, solid content 100%, OH group number: 3) 8.0 parts by weight, polyoxyethylene sorbitan monolaurate (HLB = 13.3, hydroxyl value 240 mgKOH / g) OH group number: 3) 2.0 parts by weight, isocyanurate of hexamethylene diisocyanate (NCO% 20.4%, solid content 100%) 3.0 parts by weight, dibutyltin dilaurate 1.0 part by weight at a temperature of 50 ° C. Mix evenly and stir well. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). The NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 4.0, the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 1.2.
Planar heating layer: Silicon rubber heater (300 x 180 mm, thickness 2 mm) with nichrome wire meandering in silicon rubber
Floor material layer: heat-resistant flooring (300 x 180 mm, thickness 12 mm)

(Floor heating performance evaluation)
As shown in FIG. 1, polystyrene foam having a thickness of 25 mm is installed on the side surface, top surface, and bottom surface so that the inner dimension is 300 × 180 × 200 mm, and the floor material layer side of the test specimen is on the bottom surface. The test body box was prepared.
Furthermore, in order to measure the floor surface temperature, a thermocouple was installed at the center of the floor material surface as shown in FIG. Moreover, as shown in FIG. 1, the temperature control apparatus (temperature regulator transformer) was attached to the floor surface, and it connected with the temperature sensor and the planar heating element.
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 while the temperature in the thermostat was set to 10 ° C. At this time, the temperature control device was set so that the power was turned off when the temperature detected by the temperature sensor exceeded 38 ° C., and the power was turned on when the temperature was lower than 33 ° C.
As the floor heating performance evaluation, changes in the floor surface temperature (measured by a thermocouple) were measured and shown in FIG. The measurement was performed for 6 hours.

(Example 2)
A test specimen was prepared in the same manner as in Example 1 except that the heat storage layer / heat resistant layer shown below was used. The obtained heat storage layer had good flexibility and good workability and workability.
Heat storage layer / heat-resistant layer: 75 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 25 mgKOH / g, molecular weight 7000, solid content 100%, OH group number: 3) 10.4 parts by weight, diphenylmethane diisocyanate (NCO% 31.0%, solid content 100%) 3.1 weight Part and 0.5 part by weight of dibutyltin dilaurate were uniformly mixed at a temperature of 50 ° C. and sufficiently stirred. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). Note that the NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 5.0, the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 5.0.
About floor heating performance evaluation, the result similar to Example 1 was shown.

(Example 3)
A test specimen was prepared in the same manner as in Example 1 except that the heat storage layer / heat resistant layer shown below was used. The obtained heat storage layer was particularly excellent in flexibility and excellent in workability and workability.
Heat storage layer / heat-resistant layer: 70 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 25 mgKOH / g, molecular weight 7000, solid content 100%, OH group number: 3) 12.5 parts by weight, polyoxyethylene sorbitan monolaurate (HLB = 16.7, hydroxyl value 100 mgKOH / g) OH group number: 3) 3.0 parts by weight, isocyanurate of hexamethylene diisocyanate (NCO% 20.4%, solid content 100%) 3.3 parts by weight, dibutyltin dilaurate 0.2 parts by weight at a temperature of 50 ° C. Mix evenly and stir well. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). The NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 2.8, the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 1.4.
About floor heating performance evaluation, the result similar to Example 1 was shown.

Example 4
A test specimen was prepared in the same manner as in Example 1 except that the heat storage layer / heat resistant layer shown below was used. The obtained heat storage layer was particularly excellent in flexibility and excellent in workability and workability.
Heat storage layer / heat-resistant layer: 70 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 30 mgKOH / g, molecular weight 6000, solid content 100%, number of OH groups: 3) 12.3 parts by weight, polyoxyethylene sorbitan monolaurate (HLB = 15.0, hydroxyl value 75 mgKOH / g) , OH group number: 3) 3.0 parts by weight, isocyanurate of hexamethylene diisocyanate (NCO% 16.0%, solid content 100%) 3.5 parts by weight, dibutyltin dilaurate 0.2 parts by weight at a temperature of 50 ° C. Mix evenly and stir well. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). Note that the NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 2.0, the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 1.3.
About floor heating performance evaluation, the result similar to Example 1 was shown.

(Example 5)
A test specimen was prepared in the same manner as in Example 1 except that the heat storage layer / heat resistant layer shown below was used. The obtained heat storage layer was good in workability and workability.
Heat storage layer / heat-resistant layer: 75 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 25 mgKOH / g, molecular weight 7000, solid content 100%, OH group number: 3) 7.8 parts by weight, sorbitan trioleate (HLB = 1.8, hydroxyl value 62 mgKOH / g, OH group number: 1) 3.5 parts by weight, hexamethylene diisocyanate isocyanurate (NCO% 16.0%, solid content 100%) 2.2 parts by weight and dibutyltin dilaurate 0.5 parts by weight were mixed uniformly at a temperature of 50 ° C. Stir well. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). The NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 3.0, and the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 1.4.
About floor heating performance evaluation, the result similar to Example 1 was shown.

(Comparative Example 1)
As shown in FIG. 2, the test body was produced by the same method as Example 1 except the position of the temperature sensor, and floor heating performance evaluation was performed. The results are shown in FIG. In such a floor heating structure, sufficient heat storage performance cannot be exhibited, the power ON / OFF cycle is short, and the energy saving effect cannot be exhibited sufficiently.

(Comparative Example 2)
As shown in FIG. 3, Example 1 and Example 1 except that a sheet heating layer, a temperature sensor, a heat storage layer / heat-resistant layer, and a flooring layer were sequentially stacked on a plywood (300 × 180 mm, thickness 5 mm). By the same method, the test body was produced and floor heating performance evaluation was performed. The results are shown in FIG. In such a floor heating structure, the temperature rise from the rise on the floor surface becomes gradual and lacks immediate effect.

(Comparative Example 3)
A test specimen was prepared in the same manner as in Example 1 except that the heat storage layer / heat resistant layer shown below was used.
Heat storage layer / heat-resistant layer: 70 parts by weight of methyl stearate (phase change temperature 38 ° C., latent heat 240 kJ / kg), 11 parts by weight of organically treated layered clay mineral, polyether polyol (propylene oxide and ethylene starting from glycerol) Oxide polycondensate, hydroxyl value 55 mgKOH / g, molecular weight 3000, solid content 100%, number of OH groups: 11.8 parts by weight, polyoxyethylene sorbitan monolaurate (HLB = 16.7, hydroxyl value 100 mgKOH / g) OH group number: 3) 3.0 parts by weight, isocyanurate of hexamethylene diisocyanate (NCO% 16.0%, solid content 100%) 4.0 parts by weight, dibutyltin dilaurate 0.2 parts by weight at a temperature of 50 ° C. Mix evenly and stir well. After stirring, it is poured into a 300 × 180 × 5 mm mold with a heat-resistant layer (glass layer / aluminum layer, thickness 100 μm), cured at 50 ° C. for 60 minutes, demolded, and methyl stearate (heat storage material) ) Filled with a heat storage layer (thickness 5 mm) and a heat-resistant layer (heat storage layer / glass layer / aluminum layer). The NCO / OH ratio (mixing ratio of (c-1) and (c-2)) is 1.3, and the NCO / OH ratio (the total amount of (c-1) and (d) and (c-2) The mixing ratio) was 0.9.
The floor heating performance evaluation was not carried out due to leakage of heat storage materials.

Claims (5)

On the upper side of the heat storage layer is a floor heating structure in which a planar heating element and a flooring layer are laminated in order,
The heat storage layer is an organic latent heat storage material (a), an organically treated layered clay mineral (b), a polyol having 3 or more OH groups in one molecule and a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less. (C-1), containing an isocyanate compound (c-2), wherein the mixing ratio of (c-1) and (c-2) is 1.5 or more and 8.0 or less in terms of the NCO / OH ratio,
A floor heating structure in which a temperature sensor for temperature control is installed only below the heat storage layer.   The heat storage layer is an organic latent heat storage material (a), an organically treated layered clay mineral (b), a polyol having 3 or more OH groups in one molecule and a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less. (C-1), an isocyanate compound (c-2), and a nonionic surfactant (d), and the mixing ratio of (c-1) and (c-2) is 1.5 or more in NCO / OH ratio. It is 8.0 or less, The floor heating structure of Claim 1 characterized by the above-mentioned.   The nonionic surfactant (d) is a nonionic surfactant (d) having at least two or more OH groups in one molecule, and the total amount of (c-1) and (d) and (c The mixing ratio of -2) is an NCO / OH ratio of 1.0 or more and less than 1.5, and the floor heating structure according to claim 2.   The floor heating structure according to any one of claims 1 to 3, wherein a heat-resistant layer is laminated between the heat storage layer and the planar heating element.   The floor heating structure according to any one of claims 1 to 4, wherein the heat storage layer has a thickness of 1 mm or more and 20 mm or less.

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