JP5048916B2 - Thermal storage - Google Patents

Description

  The present invention relates to a heat storage body having high heat storage properties.

In recent years, a technique for storing thermal energy, that is, a thermal storage technique, has attracted attention as one of the techniques for solving the recent energy problems.
Thermal storage technology is a technology that makes effective use of natural energy, such as solar heat and geothermal heat, and residual heat from air-conditioning equipment.For example, in homes, heat is stored using inexpensive nighttime power and used as a multipurpose heat source. It is used as a technology to reduce power consumption during the day.

  Examples of the heat storage material used in such a heat storage technology include a sensible heat storage material and a latent heat storage material, and in particular, a lot of latent heat storage materials using latent heat due to phase change of substances are employed.

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

However, the laminate sheet and the plastic case are limited to a standard 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. Furthermore, when a laminate sheet or a plastic case is fixed vertically, there is a problem that the heat storage material is biased toward the bottom and the heat storage material cannot be used effectively.
Therefore, when using a heat storage material, it is the actual condition that it is used only for the flat use represented by the heat storage material for heat storage type floor heating.

With respect to such a problem, Patent Document 1 allows a latent heat storage capsule to be carried on a coating film or sheet, thereby enabling processing such as cutting or construction such as nailing, and further biasing the bottom of the heat storage material. Suppressed heat storage bodies have been proposed.
Non-Patent Document 1 solves this problem by mixing a material such as gypsum board encapsulating a latent heat storage material and fixing it with an inorganic binder or resin.

JP-A-10-311893 (Claims) Architectural Institute of Japan Planning Papers No. 540, 23-29, February 2001

  However, in Patent Document 1 and Non-Patent Document 1, effective heat conduction to the heat storage material itself is likely to be hindered, and the content rate of the heat storage material is reduced, so that it is difficult to obtain sufficient heat storage performance. There was a problem.

  In order to solve the above problems, the present invention has been intensively studied. As a result, a three-dimensional crosslinked structure (i) obtained by reacting a polyol (a) and a compound (b) having a functional group capable of reacting with a hydroxyl group of the polyol is obtained. ), The heat storage body on which the heat storage material (ii) is carried has excellent heat storage properties, and there is no leakage of the heat storage material, and it is excellent in workability and workability. It came.

That is, the present invention includes the following features.
1. A heat storage material (ii) selected from a polyester polyol (a), a compound (b) having an isocyanate group, and a long-chain fatty acid ester having 8 to 30 carbon atoms is mixed uniformly, and the component (a) and (b ) A sheet-like heat storage body obtained by reacting components.
2. Heat storage material (ii), viscosity modifier (iii) and / or heat conductive substance (iv) selected from polyester polyol (a), compound (b) having an isocyanate group, long chain fatty acid ester having 8 to 30 carbon atoms Is a sheet-like heat storage body obtained by mixing (a) component and (b) component.
3. The component (a) is a solventless polyester polyol, and the component (b) is a compound having a solventless isocyanate group. Or 2. The heat storage body as described in 4.
4). The hydroxyl value of the component (a) is 20 to 150 KOHmg / g. To 3. The thermal storage body in any one of.
5. The molecular weight of the component (a) is 500 to 10,000. To 4. The thermal storage body in any one of.
6). The content of the heat storage material (ii) is 40% by weight or more. To 5. The thermal storage body in any one of.

  The heat storage material of the present invention has a high heat storage material content rate, is excellent in heat storage properties, and does not leak over time despite having a high heat storage material content rate. Furthermore, even if the heat storage body is cut, the heat storage material does not leak from the cut surface, and the workability is excellent. In addition, the heat storage material does not leak due to nailing or the like, so that the installation 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 is obtained by reacting a polyol (hereinafter also referred to as “component (a)”) with a compound having a functional group capable of reacting with a hydroxyl group of the polyol (hereinafter also referred to as “component (b)”). A heat storage body in which a heat storage material (hereinafter also referred to as “(ii) component”) is supported on a three-dimensional cross-linked structure (hereinafter also referred to as “(i) component”).

  The component (a) is a polyol containing a hydroxyl group, and is a component that reacts with the component (b) described later to form a three-dimensional crosslinked structure.

  Examples of the component (a) include polyester polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, polyether polyol, polycaprolactone polyol, polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, and epoxy. Examples include polyols, alkyd polyols, fluorine-containing polyols, silicon-containing polyols, and the like, and one or more of these can be used.

In the present invention, it is particularly preferable to use a polyester polyol, an acrylic polyol, a polyether polyol, or a polyolefin polyol, and it is more preferable to use a polyester polyol or a polyether polyol.
Polyester polyol is preferably used because it forms a dense cross-linked structure, has good compatibility with the component (ii) described later, and easily suppresses leakage of the component (ii) from the heat storage body. it can.

  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, 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 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 one or more hydroxyl groups in one molecule, or by copolymerizing another copolymerizable monomer.

As an acrylic monomer having one or more hydroxyl groups in one molecule, for example,
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid- (Meth) acrylic acid esters such as 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.

Further, as other copolymerizable monomers, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-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, Cyclohexyl (meth) acrylate, Octyl (meth) acrylate, Lauryl (meth) acrylate, Stearyl (meth) acrylate, Glycidyl (meth) acrylate, Trifluoroethyl (meth) acrylate, (Meth) acrylic acid n One amyl, isoamyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, ( T) Dodecyl acrylate, dodecenyl (meth) acrylate, otatadecyl (meth) acrylate, cyclohexyl (meth) acrylate, -4-tert-butylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, (meth) (Meth) acrylic acid such as isobornyl acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 4-methoxybutyl (meth) acrylate Esters;
Unsaturated carboxylic acids 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, saturated amino acids with and 4-vinylpyridine;

  (Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-monoalkyl (meth) acrylamide, N-isobutoxymethylacrylamide, N, N-dialkyl (meth) acrylamide, 2- (dimethylamino) ) Unsaturated amides such as ethyl (methacrylate), N- [3- (dimethylamino) propyl] (meth) acrylamide, 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, γ- (meth) acrylopropyltrimethoxysilane;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Vinylidene halides such as vinylidene fluoride;
Examples include styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, vinyl acetate, vinylanisole, vinylnaphthalene, divinylbenzene, ethylene, propylene, isoprene, butadiene, vinyl ether, vinyl ketone, silicone macromer, etc. The seeds or two or more kinds can be obtained by copolymerizing with the above-described monomer having one or more hydroxyl groups in one molecule.

  The polymerization method is not particularly limited, and known bulk polymerization, solution polymerization, dispersion polymerization, redox polymerization, etc. may be used, and if necessary, an initiator, a chain transfer agent, or other additives are added. Also good. 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.

  As the polyether polyol, for example, as a monomer component 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.

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

  Although the molecular weight of a polyol is not specifically limited, It is desirable that it is 500-10000, Furthermore, it is desirable that it is 1000-3000. 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.

The component (b) is not particularly limited as long as it is a compound containing a functional group capable of reacting with the hydroxyl group of the polyol. Examples of the functional group capable of reacting include an isocyanate group, a carboxyl group, an imide group, and an aldehyde group. Is mentioned.
In the present invention, it is particularly preferable to use a compound containing an isocyanate group. The isocyanate group is excellent in reactivity with the hydroxyl group, the reaction proceeds rapidly, and a dense cross-linked structure can be formed.

  Examples of the isocyanate group-containing compound include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa. Methylene 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 Caproate 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 di Isocyanate, 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 Ane - DOO, dianisidine diisocyanate - DOO, 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) Aromatic aliphatic diisocyanates such as -1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene;
Isocyanate group-containing compounds such as these, and those isocyanate group-containing compounds derivatized by allophanation, biuretization, dimerization (uretidione), trimerization (isocyanurate), adduct formation, carbodiimide reaction, and the like, and mixtures thereof Etc.

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

The mixing ratio of the component (a) and the component (b) is not particularly limited, and may be set as appropriate according to the application.
When a compound containing an isocyanate group is used as the component (b), the NCO / OH ratio is usually 0.1 to 1.8, preferably 0.2 to 1.5, and more preferably 0.3 to 1. It may be set within the range of 3.
By being within such a range of the NCO / OH ratio, the strength of the heat storage body can be strengthened, and a uniform and dense cross-linked structure with no leakage of the heat storage material can be obtained.
When the NCO / OH ratio is less than 0.1, the crosslinking rate is low, and sufficient physical properties such as curability, durability, and strength may not be ensured, and the heat storage material is likely to leak. When the NCO / OH ratio is larger than 1.8, unreacted isocyanate remains, adversely affects various physical properties of the heat storage body, the heat storage body is easily deformed, and the heat storage material is likely to leak.

Although it will not specifically limit as a component (ii) if it is a heat storage material, Preferably an inorganic latent heat storage material, 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, polyether compounds, fatty acid triglycerides, etc., 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. The organic latent heat storage material is preferable because it has a high boiling point and is less likely to volatilize, so that there is almost no skin thinning during the formation of the heat storage body 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 30 carbon atoms can be used. Specifically, tetradecane, pentadecane (melting point 6 ° C.), hexadecane (melting point 18 ° C.), heptadecane (melting point 22). ° C), octadecane (melting point 28 ° C), nonadecane (melting point 32 ° C), icosane (melting point 36 ° C), docosan (melting point 44 ° C), paraffin wax and the like.

  As the long chain alcohol, for example, a long chain alcohol having 8 to 30 carbon atoms can be used, and specific examples include lauryl alcohol, stearyl alcohol, myristyl alcohol and the like.

  As the long-chain fatty acid, for example, a long-chain fatty acid having 8 to 30 carbon atoms can be used, and specific examples include fatty acids such as octanoic acid, decanoic acid, lauric acid, and stearic acid.

  As the long-chain fatty acid ester, for example, a long-chain fatty acid ester having 8 to 30 carbon atoms can be used, and specific examples include methyl myristate, methyl palmitate, stearyl stearate, distearyl phthalate, and the like. .

  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, it is particularly preferable to use an aliphatic hydrocarbon or a long-chain fatty acid ester as the heat storage material, and it is more preferable to use a long-chain fatty acid ester. Among the long-chain fatty acid esters, it is particularly preferable to use a long-chain fatty acid ester having 15 to 22 carbon atoms. Such a long-chain fatty acid ester has a high latent heat amount and has a phase change temperature (melting point) in a practical temperature range. Therefore, it is easy to use for various purposes.

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 further improved.
Examples of the compatibilizer include fatty acid triglycerides, nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 to 10, and one or more of these 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 medium-chain fatty acid triglycerides and long-chain fatty acid triglycerides that are refined processed products thereof.

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

  The mixing ratio of the compatibilizer and the component (a) is usually about 0.1 to 30 parts by weight (preferably 0.5 to 20 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, a viscosity modifier (hereinafter also referred to as “component (iii)”) and / or a thermally conductive substance (hereinafter also referred to as “component (iv)”) may be mixed with component (ii). preferable. Particularly in the present invention, it is preferable to mix a viscosity modifier (hereinafter also referred to as “component (iii)”) and a heat conductive substance (hereinafter also referred to as “component (iv)”) together with component (ii). .

The component (iii) mainly adjusts the viscosity of the component (ii), mainly increases the viscosity of the component (ii), supports the component (ii) in the component (i) and holds it more. There is an effect to continue.
Therefore, despite having a high heat storage material content rate, the heat storage material does not leak over time. Furthermore, even if the heat storage body is cut, the heat storage material does not leak from the cut surface, and the workability is excellent, and the heat storage material does not leak due to nailing or the like, and the workability is excellent.

  Examples of the component (iii) include organic bentonite, amide wax, hydrophobic cellulose such as ethyl cellulose and cellulose nitrate, and polyolefin such as polyethylene and polypropylene, and one or more of these can be used. In the present invention, organic bentonite is particularly preferable.

  The mixing ratio of the component (ii) and the component (iii) is usually 0.5 to 50 parts by weight (preferably 1 to 30 parts by weight) of the component (iii) with respect to 100 parts by weight of the component (ii) 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 (ii) may easily leak from the component (i). When the amount is more than 50 parts by weight, the viscosity of the component (ii) becomes too high, and the supporting / holding step on the component (i) may be difficult.

The component (iv) can improve the thermal efficiency of the heat storage material and can obtain more excellent heat storage performance.
As the component (iv), for example, metals such as copper, iron, zinc, beryllium, magnesium, cobalt, nickel, titanium, zirconium, molybdenum, tungsten, boron, aluminum, gallium, silicon, germanium, tin, and alloys thereof, Or metal oxides containing these metals, metal nitrides, metal carbides, metal phosphides and other metal compounds, and scaly graphite, massive graphite, earth graphite, fibrous graphite, etc. One kind or a mixture of two or more kinds can be used.

The thermal conductivity of the thermally conductive material is preferably 1 W / (m · K) or more, more preferably 3 W / (m · K) or more, and further preferably 5 W / (m · K) or more. By mixing the heat conductive material having such a heat conductivity, the heat transfer in the heat storage body can be made smooth, and 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 component (ii) and component (iv) is usually 5 to 200 parts by weight (preferably 10 to 80 parts by weight, more preferably 100 parts by weight of component (ii) 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 increases, and it may be difficult to efficiently carry the component (i).

The production of the heat storage body of the present invention is not particularly limited and can be produced by a known method. In the present invention, in particular, the component (a), the component (b), the component (ii), the component (iii) and / or the component (iv) are mixed in advance, and the component (a) and the component (b) are mixed. A method of reacting to obtain a heat storage body is preferable.
Specifically, first, the component (a), the component (b), the component (ii), and the component (iii) and / or the component (iv) are mixed uniformly as needed, that is, the component (a), (b ) Component, (ii) component (and (iii) component, (iv) component) are made compatible. Next, by reacting the component (a) and the component (b), a dense and intricate three-dimensional crosslinked structure composed of the component (a) and the component (b) is formed. In this process, it is considered that microphase separation occurs due to the change from the compatible state to the incompatible state.
The (ii) component (and (iii) component, (iv) component) is supported on this three-dimensional crosslinked structure, and a heat storage body is formed.

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. Since the compatibilizer can improve not only the compatibility between the components (ii) but also the compatibility between the components (ii), (a) and (b), a more precise three-dimensional stitch structure A mold porous body is formed, and the leakage of the component (ii) (and the component (iii) and the component (iv)) from the porous body can be further prevented.
Examples of the compatibilizer include the fatty acid triglycerides described above and nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 to 10, and the like (ii) component, (a) component, and (b) component. In particular, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 to 10 is preferable.

  At this time, it is preferable that reaction temperature is more than melting | fusing point of (ii) component. Although specific reaction temperature changes with kinds of (ii) component, it is about 20 to 100 degreeC normally. (Ii) By reacting at a temperature equal to or higher than the melting point of the component, a compatible state is easily obtained, and an excellent heat storage body is formed. Moreover, reaction time should just be normally about 0.5 to 10 hours.

In such production, the molecular weight of the component (a) is not particularly limited, but is preferably 500 to 10,000, and more preferably 1000 to 3000. With such a molecular weight, it can be easily melt-mixed with the component (ii), and a compatible state can be easily produced. Therefore, a more excellent three-dimensional crosslinked structure can be obtained, and an excellent heat storage body can be obtained.
Furthermore, the mixing ratio of the component (a) and the component (b) is not particularly limited and may be appropriately set. However, when a compound containing an isocyanate group is used as the component (b), the NCO / OH ratio is 0.1 to 1.8, preferably 0.2 to 1.5, more preferably 0.3 to 1.3, whereby a more excellent three-dimensional crosslinked structure can be obtained and excellent heat storage You can get a body.

Moreover, in reaction of (a) component and (b) component, a hardening reaction can also be advanced rapidly using a reaction accelerator.
Examples of the reaction accelerator include amines such as triethylamine, triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylaminoethanol, dimer diamine, and 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.

  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 component (a). If the reaction accelerator is less than 0.01 parts by weight, curability and strength may be insufficient. When the amount is more than 10 parts by weight, durability, discoloration resistance and the like tend to decrease.

  Moreover, it is also possible to mix | blend various additives in the range which does not inhibit the effect of this invention other than the above-mentioned component. Examples of such additives include plasticizers, antiseptics, antifungal agents, algaeproofing agents, antifoaming agents, leveling agents, pigment dispersants, antisettling agents, antisagging agents, curing accelerators, dehydrating agents, Matting agents, flame retardants, ultraviolet absorbers, light stabilizers, and the like.

The heat storage body of the present invention can be manufactured by the above-described manufacturing method, and the shape thereof is not particularly limited, such as a sheet shape, a rod shape, a needle shape, a spherical shape, a square shape, and a powder shape.
In the present invention, a sheet form is preferable. For example, a sheet-like heat storage body can be laminated with various base materials on one side or both sides of the heat storage body according to the intended use. It can also be laminated in advance to form a heat storage body. At this time, the method for forming the heat storage body is not particularly limited, and is applied by a known method such as extrusion forming, mold forming, or spray coating, roller coating, brush coating, trowel coating, or pouring on various substrates. Can be formed.
Non-woven fabric, woven fabric, paper, synthetic paper, wood, particle board, ceramic paper, metal plate, metal foil, synthetic resin plate, plastic film (PET film, etc.), gypsum board, calcium silicate plate, cement type A board, a rigid foam board, a glass cloth, a mesh, etc. are mentioned.
Moreover, the thickness of the sheet-like heat storage body is not particularly limited, but it may be generally about 1 to 30 mm (preferably 2 to 20 mm).

The heat storage element of the present invention has a structure in which the three-dimensional cross-linking structure composed of the component (a) and the component (b) is closely packed, so that a large amount of the component (ii) can be supported. Specifically, the heat storage material content 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. Such a high heat storage material content ratio includes the components (a), (b), (ii) (and (iii) in addition to the dense three-dimensional crosslinked structure of the components (a) and (b). , (Iv) component).
Therefore, since it has a high heat storage material content rate, the heat storage material does not leak over time despite having excellent heat storage properties and a high heat storage material content rate. Furthermore, even if the heat storage body is cut, the heat storage material is not leaked from the cut surface and is excellent in workability, and since there is no leakage of the heat storage material due to nailing or the like, the workability is excellent.

  Furthermore, by controlling the types and mixing ratios of the components (a) and (b), the strength, flexibility, etc. of the formed body can be controlled, and the content of component (ii) can be controlled. Therefore, it can be applied to various uses.

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

Example 1
Using the raw materials shown in Table 1, the polyol A, polyisocyanate A, and heat storage material A were mixed uniformly at 50 ° C. in the blending amounts shown in Table 2, the reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. The following test was done about the obtained test body. The results are shown in Table 3.

(Heat storage material leakage evaluation test)
The obtained test specimens were allowed to stand for 72 hours in an atmosphere of 10 ° C. or 50 ° C., respectively, and then transferred to an environment of a temperature of 23 ° C. and a humidity of 50% (hereinafter also referred to as “standard state”). The leakage of the 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 property test)
Using DSC220CU (manufactured by Seiko Instruments Inc.), the phase change temperature (° C.) and the latent heat (kJ / kg) of the obtained specimen were measured by differential scanning calorimetry (DSC measurement). As measurement conditions, aluminum was used as a reference, and the temperature was measured in a temperature range of 10 ° C./min and −20 to 60 ° C. The results are shown in Table 3.

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

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

(Example 2)
Using the raw materials shown in Table 1, the polyol B, polyisocyanate B, and heat storage material B were mixed uniformly at 50 ° C. in the blending amounts shown in Table 2, and the reaction accelerator was added and sufficiently stirred. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Example 3)
Using the raw materials shown in Table 1, the polyol A, polyisocyanate A, heat storage material A, and viscosity modifier were mixed uniformly at 50 ° C. in the blending amounts shown in Table 2, the reaction accelerator was added, and the mixture was sufficiently stirred. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

Example 4
Using the raw materials shown in Table 1, the polyol C, polyisocyanate B, heat storage material A, and viscosity modifier were mixed uniformly at 50 ° C. in the blending amounts shown in Table 2, and the reaction accelerator was added and sufficiently stirred. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Example 5)
Using the raw materials shown in Table 1, with the blending amounts shown in Table 2, polyol C, polyisocyanate B, heat storage material A, viscosity modifier, and heat conduction material are uniformly mixed at 50 ° C., a reaction accelerator is added, Stir well. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Example 6)
Using the raw materials shown in Table 1, polyol C, polyisocyanate B, heat storage material A, and heat conductive material were uniformly mixed at 50 ° C. in the blending amounts shown in Table 2, and a reaction accelerator was added and stirred sufficiently. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Example 7)
Using the raw materials shown in Table 1, the polyol C, polyisocyanate B, heat storage material A, heat storage material B, viscosity modifier are uniformly mixed at 50 ° C. in the blending amounts shown in Table 2, and a reaction accelerator is added. Stir well. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Example 8)
Using the raw materials shown in Table 1, with the compounding amounts shown in Table 2, polyol C, polyisocyanate B, heat storage material A, heat storage material B, compatibilizer A, and viscosity modifier are mixed uniformly at 50 ° C. and reacted. An accelerator was added and stirred well. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

Example 9
Using the raw materials shown in Table 1, with the blending amounts shown in Table 2, the polyol C, polyisocyanate B, heat storage material A, heat storage material B, compatibilizer B, viscosity modifier, and heat conduction material are uniformly distributed at 50 ° C. Mix, add reaction accelerator and stir well. After stirring, it was poured into a 250 mm × 170 mm × 5 mm mold and cured at 80 ° C. for 30 minutes to obtain a test specimen. The NCO / OH ratio was 1.0. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

(Comparative Example 1)
A paste was prepared by impregnating 7 parts by weight of silica powder shown in Table 1 with 20 parts by weight of heat storage material A. Thereafter, a slurry in which 27 parts by weight of the prepared paste, 35 parts by weight of water, and 40 parts by weight of calcined gypsum were mixed was poured into a 250 mm × 170 mm × 5 mm mold and dried at 50 ° C. overnight to obtain a test specimen. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.

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

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

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

  The heat storage body of the present invention is mainly molded and processed into a sheet shape, such as an interior / exterior material bonded to the inner wall material, outer wall material, ceiling material, floor material of a building such as a house, a vehicle, etc. It can be suitably used as an interior material. Furthermore, the heat storage body of the present invention can be applied to a thermoelectric conversion system, a refrigerator / freezer, a cooler box, a heat insulating sheet, and the like.

Claims (6)

A heat storage material (ii) selected from a polyester polyol (a), a compound (b) having an isocyanate group, and a long-chain fatty acid ester having 8 to 30 carbon atoms is mixed uniformly, and the component (a) and (b ) A sheet-like heat storage body obtained by reacting components. Heat storage material (ii), viscosity modifier (iii) and / or heat conductive substance (iv) selected from polyester polyol (a), compound (b) having an isocyanate group, long chain fatty acid ester having 8 to 30 carbon atoms Is a sheet-like heat storage body obtained by mixing (a) component and (b) component.   The heat storage body according to claim 1 or 2, wherein the component (a) is a solventless polyester polyol, and the component (b) is a compound having a solventless isocyanate group.   The hydroxyl value of (a) component is 20-150 KOHmg / g, The heat storage body in any one of Claims 1-3 characterized by the above-mentioned.   The molecular weight of (a) component is 500-10000, The thermal storage body in any one of Claims 1-4 characterized by the above-mentioned. The content rate of heat storage material (ii) is 40 weight% or more, The heat storage body in any one of Claims 1-5 characterized by the above-mentioned.