JP2006233176A - Method for producing heat storage form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a heat storage form having high heat-storing capacity, free from storage material leakage, and excellent in processability and workability. <P>SOLUTION: The method for producing the heat storage form comprises mixing together an organic latent-heat heat storage material(a), a nonionic surfactant(b) and a reactive functional group-containing compound(c-1) and a compound(c-2) containing a reactive functional group reactive to the above reactive functional group, colloidally dispersing the component(a) and then conducting a reaction between the components(c-1) and (c-2). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a heat storage body having high heat storage performance.

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, inorganic hydrate-based latent heat storage materials such as sodium sulfate decahydrate and organic latent heat storage materials such as paraffin are used. As these latent heat storage materials, those that undergo a phase change (solid-liquid change) in a temperature range of 15 ° C. to 50 ° C. are widely used. As the main usage, the latent heat storage materials are sealed in a liquid state. A method of sealing in a laminate sheet or a plastic case is common.

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

With respect to such a problem, Patent Document 1 describes a method (paragraph 0023) in which a microcapsule including an organic latent heat storage material is immobilized using a binder, which solves the problem.
In Non-Patent Document 1, n-paraffin (organic latent heat storage material) is impregnated in high-density polyethylene to produce a latent heat storage pellet, and this is mixed into a gypsum board to thereby prepare an organic latent heat storage material. The method of immobilization is described, and the problem is solved.

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 latent heat storage material itself is likely to be hindered, and the content rate of the latent heat storage material is also reduced, so that sufficient heat storage performance is obtained. There was a problem that it was difficult.

  On the other hand, in Patent Document 2, a latent heat storage material is supported on a porous body to solve the above problem and to obtain sufficient heat storage performance. However, if the latent heat storage material is simply supported on the porous body, the latent heat storage material may leak out in some cases.

JP-A-9-143461

  In order to solve the above problems, the present invention has been intensively studied. As a result, the organic latent heat storage material (a), the nonionic surfactant (b), the compound (c-1) containing a reactive functional group, The compound (c-2) containing a reactive functional group and a reactive functional group capable of reacting is mixed, the organic latent heat storage material (a) is dispersed in a colloidal form, and the component (c-1) and (c- 2) The heat storage body obtained by reacting the components was found to have excellent heat storage performance, no leakage of the heat storage material, excellent workability and workability, and the present invention was completed.

That is, the present invention has the following characteristics.
1. Organic latent heat storage material (a), nonionic surfactant (b), compound containing reactive functional group (c-1) and compound containing reactive functional group capable of reacting with the reactive functional group (C-2) is mixed, the organic latent heat storage material (a) is dispersed in a colloidal form, and the component (c-1) and the component (c-2) are reacted with each other.
2. 1. The hydrophilic / lipophilic balance (HLB value) of the nonionic surfactant (b) is 10 or more. The manufacturing method of the thermal storage body of description.
3. As a viscosity modifier, 0.5 to 50 parts by weight of the organically treated layered clay mineral (e) is mixed with 100 parts by weight of the organic latent heat storage material (a). Or 2. The manufacturing method of the thermal storage body of description.
4). The content of the organic latent heat storage material (a) is 40% by weight or more. To 3. The manufacturing method of the thermal storage body in any one of.

  The heat storage body obtained by the production method of the present invention has a high heat storage material content rate and excellent heat storage performance, and the heat storage material may leak over time despite having a high heat storage material content rate. Absent. Further, even if the heat storage body is cut, the latent heat storage material does not leak from the cut surface, and the workability is excellent, and the latent heat storage material does not leak even by 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 production method of the present invention comprises an organic latent heat storage material (hereinafter also referred to as “component (a)”), a nonionic surfactant (hereinafter also referred to as “component (b)”), and a reactive functional group. And a compound containing a reactive functional group capable of reacting with the reactive functional group (hereinafter also referred to as “component (c-2)”). And the component (c-1) and the component (c-2) are reacted.

In the production method of the present invention, the component (b) can create 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).
By reacting the component (c-1) and the component (c-2) in such a state, a molded product composed of the component (c-1) and the component (c-2) (hereinafter referred to as “component (c)”). (It is also called.) A heat storage body in which the component (a) is finely dispersed can be produced.

According to such a production method, since the content of the component (a) can be increased, the heat storage property is excellent, and the content of the component (a) is high over time despite having a high content of the component (a). (A) The heat storage body which does not leak a component can be manufactured.
In addition, even if the obtained heat storage body is cut, the (a) component does not leak from the cut surface and is excellent in workability, and the (a) component does not leak due to nailing or the like. Excellent in properties.
Furthermore, 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 body itself due to the volume change accompanying the solid-liquid change of the component (a) It is also possible to reduce the shape change.

  In the production of a heat storage body, the present invention dares to mix the component (b), and creates a state in which the component (a) is finely dispersed in a colloidal state (non-uniform state), and a molded product is obtained from such a state. Thus, the inventors have found that the above effects can be achieved.

  When (b) component is not included, when (a) component and (c-1) component and / or (c-2) component are not compatible, (a) component and (c-1) component and / or (C-2) It is difficult to form a heat storage body because the components are separated. Moreover, when (a) component and (c-1) component and / or (c-2) component are compatible (uniform state), although a heat storage body with high heat storage property can be formed, (a) Since there is a limit to selection (combination etc.) of the component and the component (c-1) and / or the component (c-2), it is difficult to use for a wide range of applications.

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

  In the present invention, particularly as component (b), 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, more preferably 12 or more and 18 or less, and most preferably 13 or more. 17 or less) nonionic surfactants can be preferably used. If it is such a range, since it is easy to disperse | distribute (a) component which is an organic latent heat storage material in colloidal form, it is preferable.

The mixing ratio of the component (b) 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). )
When the component (b) is less than 0.01 part by weight, the component (a) and the component (c-1) and / or the component (c-2) are easily separated or easily cause a creaming phenomenon, and efficiently. There is a high possibility that the component (a) and the component (c-1) and / or the component (c-2) are not compatible with each other, and the effects of the present invention may not be obtained. When the amount is more than 30 parts by weight, physical properties such as water resistance of the obtained heat storage may be adversely affected.

  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.

  Such a component (a) has a high boiling point and is excellent in compatibility with the component (c-1) and / or the component (c-2), and thus hardly volatilizes from the obtained heat accumulator. Therefore, there is almost no volume change (thinning) at the time of heat storage body formation, and since heat storage performance continues over a long period of time, it 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 ° C), 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 heat storage material, in particular, an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and a long chain fatty acid ester having 8 to 36 carbon atoms. It is preferable to use an aliphatic hydrocarbon having 8 to 36 carbon atoms and a long chain fatty acid ester having 8 to 36 carbon atoms. Among them, it is preferable to use a long-chain fatty acid ester having 8 to 36 carbon atoms, preferably a long-chain fatty acid ester having 15 to 22 carbon atoms. Such a long-chain fatty acid ester has a high latent heat and has a practical temperature range. Since it has a phase change temperature (melting point), it is easy to use for various applications.

  In the present invention, when a heat storage material having a long-chain alkyl group having 8 to 36 carbon atoms is used among the components (a), the long-chain alkyl group having 8 to 36 carbon atoms is included in the structure of the component (b). It is preferable to use a nonionic surfactant having 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 (b).

Moreover, when mixing and using 2 or more types of organic latent heat storage materials, it is preferable to use a compatibilizer (henceforth "(d) component"). By using the component (d), the compatibility between the organic latent heat storage materials can be improved.
Examples of the component (d) 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, which are refined processed products thereof. More than seeds can be used.

Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less) include:
Examples include sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, and sorbitan sesquioleate.

  The mixing ratio of the component (d) and the component (a) is usually 0.1 to 20 parts by weight (preferably 0.1 to 10 parts by weight) of the compatibilizer with respect to 100 parts by weight of the component (a). It should be about.

Further, in the present invention, the component (a) and an organically treated layered clay mineral (hereinafter also referred to as “component (e)”) can be mixed. Since the component (e) is organically treated, the component (a) is likely to enter between the layers of the component (e), and the component (a) is likely to be held between the layers of the component (e). Yes.
By mixing the component (e) and the component (a), the component (a) enters between the layers of the component (e). As a result, the viscosity of the component (a) is increased, and the component (c) The component (a) can be carried inside and kept further. Therefore, it is possible to prevent the component (a) from leaking to the outside of the heat storage body, and to obtain a heat storage body excellent in heat storage performance and excellent in workability and workability.
Furthermore, since the component (e) does not affect the phase change temperature of the organic latent heat storage material and other various physical properties, the performance as the heat storage material of the component (a) can be efficiently exhibited, This is preferable because the phase change temperature can be easily set.

  (E) It is preferable that the space | interval of the bottom face of a component is about 13.0-30.0cm (preferably 15.0-26.0cm). By being in such a range, the component (a) can easily enter between the layers of the component (e). 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 (e) 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. and a relative humidity of 50% RH.
Moreover, what is necessary is just to set the TI value at the time of (a) component and (e) component mixing to about 4.0-9.0. In addition, TI value is a value calculated | required by following formula 1 using a B-type rotational viscometer.
TI value = η1 / η2 (Formula 1)
(However, η1: Viscosity at 2 rpm (Pa · s: guide value for the second rotation), η2: Viscosity at 20 rpm (Pa · s: Guide value for the fourth rotation))

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

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

  The mixing ratio of the component (a) and the component (e) is usually 0.5 parts by weight to 50 parts by weight (preferably 1 part by weight to 30 parts by weight) with respect to 100 parts by weight of the component (a). More preferably, it may be about 3 to 20 parts by weight. When the amount is less than 0.5 parts by weight, the component (a) may easily leak from the component (c). When the amount is more than 50 parts by weight, the viscosity of the component (a) becomes too high, and the supporting / holding step on the component (c) may be difficult.

Further, in the present invention, a flame retardant (hereinafter also referred to as “component (f)”) can be mixed. By mixing the flame retardant, the heat storage body can be provided with flame retardancy.
Examples of the component (f) include phosphorus compounds, organic phosphorus compounds, metal compounds, and expandable graphite.
Examples of phosphorus compounds include phosphorus trichloride, phosphorus pentachloride, ammonium polyphosphate, amide-modified ammonium polyphosphate, melamine phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, ethylenediamine zinc phosphate salt, 1 And phosphoric acid amine salts such as 4-butanediamine phosphate, red phosphorus, and phosphoric acid esters.
Examples of organic phosphorus compounds include tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate. Fate, tri (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, di (polyoxyethylene) hydroxymethyl phosphonate, etc. Is mentioned.
Examples of the metal compound include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zinc hydroxystannate, zinc stannate, nickel oxide, cobalt oxide, iron oxide, copper oxide, molybdenum oxide, tin oxide, zinc oxide, and oxidation. Examples thereof include silicon, zeolite, zinc borate, sodium borate, zirconium oxide, antimony trioxide, and antimony pentoxide.
Examples of expansive graphite include those obtained by treating a powder such as natural flake graphite, pyrolytic graphite, and cache graphite with sulfuric acid, nitric acid, acetic acid, perchloric acid, perchlorate, permanganate, etc. Can be mentioned.

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. 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 component (a) and component (f) is usually about 5 to 100 parts by weight (preferably 10 to 50 parts by weight) of component (f) with respect to 100 parts by weight of component (a). do it. When the amount is less than 5 parts by weight, it is difficult to improve flame retardancy. When the amount is more than 100 parts by weight, the heat storage performance may be reduced.

  Furthermore, in this invention, a heat conductive substance can also be mixed. By mixing the heat conducting substance, the heat transfer in the heat storage body can be made smooth, and the thermal efficiency of the heat storage material can be improved.

  The component (c-1) and the component (c-2) used in the present invention are components that form a molded product (component (c)) by reaction, and support and hold the component (a).

  (C-1) Component, (c-2) As a combination of the reactive functional groups of component, hydroxyl group and isocyanate group, hydroxyl group and carboxyl group, hydroxyl group and imide group, hydroxyl group and aldehyde group, epoxy group and Examples thereof include amino groups, epoxy groups and carboxyl groups, carboxyl groups and carbodiimide groups, carboxyl groups and oxazoline groups, carbonyl groups and hydrazide groups, carboxyl groups and aziridine groups, and alkoxyl groups.

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

  In the present invention, in particular, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, cellulose and derivatives thereof are preferably used, and a dense cross-linked structure is formed by using such a compound containing a hydroxyl group. At the same time, it can be suitably used because it has good compatibility with the component (a) and can easily suppress leakage of the component (a) from the heat storage body.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The molecular weight of the polyol is not particularly limited, but is preferably 500 to 10,000, and more preferably 1000 to 3000. If it is such molecular weight, the bridge | crosslinking structure which can suppress the leakage of a thermal storage material can be obtained by the combination with the compound containing an isocyanate group, the compound containing a carboxyl group, etc. If the molecular weight is too small, the heat storage material may easily leak. If the molecular weight is too large, the heat storage material may not be sufficiently retained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Moreover, the mixing ratio of the component (c-1) and the component (c-2) is not particularly limited, and may be set as appropriate according to the application.
For example, when a compound containing a hydroxyl group and a compound containing an isocyanate group are used, the NCO / OH ratio is usually set within a range of 0.5 to 1.8, preferably 0.7 to 1.5. That's fine.
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 0.5, the crosslinking rate is low, and sufficient physical properties such as curability, durability, and strength may not be ensured, and the heat storage material is likely to leak. When the NCO / OH ratio is larger than 1.8, unreacted isocyanate remains, adversely affects various physical properties of the heat storage body, the heat storage body is easily deformed, and the heat storage material is likely to leak.

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

  The reaction accelerator is usually mixed at a ratio of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the compound containing a hydroxyl group. 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.

The method for producing a heat storage body of the present invention comprises (a) component (if necessary, (d) component, (e) component), (b) component, (c-1) component, and (c-2) component, And (c-1) component and (c-2) component are reacted.
In this case, the component (b) is used in order to create a state in which the component (a) is dispersed in a fine colloidal form in the component (c-1) and / or the component (c-2). Is.

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

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

  Furthermore, in the state before the reaction, the temperature in the system is preferably the phase change temperature of the component (a). Specifically, the temperature is usually about 20 ° C. to 80 ° C., and such a temperature is preferable because the component (a) is easily dispersed in a colloidal form.

In particular, the reaction temperature is preferably equal to or higher than the phase change temperature of component (a). Although specific reaction temperature changes with kinds of (a) component, it is about 20 to 80 degreeC normally. Above the phase change temperature of the component (a), the component (a) tends to be in a colloidal state, so that an excellent heat storage body is formed. Moreover, reaction time should just be normally about 0.2 to 5 hours.
At this time, in order to promote the reaction, the reaction accelerator and energy such as heat and light can be applied.

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

  In the production of the heat storage element of the present invention, in addition to the above components, pigments, aggregates, viscosity modifiers, plasticizers, film-forming aids, buffers, dispersants, crosslinking agents, pH adjusters, antiseptics, antifungal agents , Antibacterial agents, algaeproofing agents, wetting agents, antifoaming agents, foaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, anti-freezing agents, lubricants, dehydrating agents, matting agents, UV absorbers, It can also contain additives such as antioxidants, light stabilizers, fibers, fragrances, chemical adsorbents, photocatalysts, hygroscopic particles.

The shape of the heat storage body obtained by the production method of the present invention 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, the 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. A heat storage body can also be obtained by previously laminating materials. In this case, the method of forming the heat storage body is not particularly limited, and is applied by a known method such as extrusion molding, mold molding, or spray coating, roller coating, brush coating, trowel coating, pouring, etc. on various substrates. Can be formed.

  Moreover, the thickness of the sheet-shaped heat storage body is not particularly limited, but may be usually about 1 to 100 mm.

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

  The heat storage body of the present invention can be suitably used mainly as a material for interior / exterior materials such as wall materials, ceiling materials, floor materials, etc. of buildings such as houses. Furthermore, the heat storage body of the present invention includes floor heating systems, interior materials for vehicles, industrial products such as machinery and equipment, thermoelectric conversion systems, heat transfer media, refrigeration / freezers, bathtubs / bathrooms, cooler boxes, heat insulation sheets, electric It can also be applied as a material used for products, OA equipment, plants, tanks, clothes, curtains, carpets, bedding, daily necessities and the like.

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

For example, by laminating the heat storage body and the heat insulator of the present invention, the wall material, ceiling material, flooring, etc. of buildings, refrigerators / freezers, bathtubs / bathrooms, cooler boxes, etc. By applying to the above, the temperature in the space can be kept at an optimum temperature with respect to a change in the external temperature, and energy saving can be achieved.
Examples of such a heat insulator include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, etc., or a composite thereof. Etc. Moreover, you may use a commercially available heat insulator.
The thermal conductivity of the heat insulator is less than 0.1 W / (m · K) (more preferably 0.08 W / (m · K) or less, and even more preferably 0.05 W / (m · K) or less). Is preferred.

Further, a heat conductor having a thermal conductivity of 0.1 W / (m · K) or more can be stacked. Examples of the heat conductor include a resin board and a resin sheet such as a glass plate, acrylic resin, and vinyl resin, a metal plate such as copper, aluminum, iron, brass, zinc, magnesium, and nickel, or a resin board containing a metal material. Or a resin sheet, a slate board, a gypsum board, an ALC board, a wood wool cement board, a plywood etc. are mentioned.
Such a heat conductor may cause dew condensation at night or in winter, but by laminating the heat storage body of the present invention, the temperature change of the heat conductor can be mitigated and condensation can be prevented. it can. For example, the effect of preventing condensation can be obtained by laminating the heat storage body of the present invention on glass or a metal plate.

Moreover, by laminating the heat storage material of the present invention and a fireproofing material such as a flame retardant, a semi-incombustible material and a non-combustible material, in addition to excellent heat storage properties, fireproofing can be imparted and fireproofing is required It can apply also to the site | parts (for example, interior material etc. of a building).
Examples of such fireproof materials include concrete plates, glass plates, metal plates, wooden wool cement plates, plaster boards, flat plates such as calcium silicate plates, metal film, film molded products such as glass fibers, and foamable fireproof materials. And flame retardant-containing materials.

Moreover, by laminating the heat storage body and the heating element of the present invention, the present invention can be applied to a floor heating system, snow melting / sliding roof material, bath tub / bathroom, heat insulation sheet and the like.
When applied as a floor heating system, for example, a planar heating element, piping using hot water, or the like can be used as a heating element, and these heating elements can be combined with the heat storage element and flooring of the present invention. it can. Such a floor heating system can be stacked and installed by a known method. For example, a floor heating system in which a heating element, a planar heating element, and a floor material are stacked can suppress the thickness, and Even if the thickness is suppressed, an excellent floor heating effect and an energy saving effect can be exhibited, and particularly, it can be suitably used for reforming and the like.

Moreover, since the thermal storage body of this invention can continue maintaining the optimal temperature, it can obtain a comfortable environment by combining with the raw material used for clothing, a curtain, a carpet, bedding, etc. Furthermore, since it is possible to suppress the influence of external temperature even in extremely cold areas such as Antarctica and Siberia, and in high-temperature environments such as a fire place, it is also effective for cold clothes and fire clothes.
Such materials include natural fibers such as cotton, hemp, wool, silk, organic fibers such as nylon, tetron, acrylic, polyester, polyurethane, vinylon, rayon, aramid, azole, inorganic fibers such as glass and asbestos, or Examples of the fibers include flame retardant treatment and water repellent treatment. Moreover, a metal, a resin sheet, rubber | gum, etc. may be sufficient and it can use combining 1 type (s) or 2 or more types among these.

  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 organic latent heat storage material A, the nonionic surfactant A, the hydroxyl group-containing compound A, and the reaction accelerator at the blending amounts shown in Table 2 are 1000 rpm with a stirring blade at a temperature of 35 ° C. The organic latent heat storage material A was dispersed in a colloidal form (average particle size 180 μm). Further, after adding polyisocyanate A and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded to obtain a test specimen.

  The following test was performed using the obtained specimen.

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

(Workability test)
Under the atmosphere of temperature 30 ° C. and relative humidity 50% RH, 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 organic latent heat storage material A, the nonionic surfactant A, the organically treated layered clay mineral, the hydroxyl group-containing compound A, and the reaction accelerator in the blending amounts shown in Table 2. The mixture was stirred and mixed at 1000 rpm with a stirring blade at a temperature of 35 ° C. to disperse the organic latent heat storage material A in a colloidal form (average particle size 420 μm). Further, after adding polyisocyanate A and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded 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.

(Example 3)
Using the raw materials shown in Table 1, the organic latent heat storage material B, the nonionic surfactant B, the organically treated layered clay mineral, the hydroxyl group-containing compound B, the reaction accelerator in the blending amounts shown in Table 2, The mixture was stirred and mixed at 1000 rpm with a stirring blade at a temperature of 23 ° C. to disperse the organic latent heat storage material B in a colloidal form (average particle diameter of 500 μm). Further, after adding polyisocyanate B and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded 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.

Example 4
Using the raw materials shown in Table 1, the organic latent heat storage material A, the organic latent heat storage material B, the nonionic surfactant A, the organically treated layered clay mineral, and the hydroxyl group-containing compound A in the blending amounts shown in Table 2 The reaction accelerator was stirred and mixed at 1000 rpm with a stirring blade at a temperature of 35 ° C., and the organic latent heat storage materials A and B were dispersed in a colloidal form (average particle diameter of 480 μm). Further, after adding polyisocyanate A and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded 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.

(Example 5)
Using the raw materials shown in Table 1, the organic latent heat storage material A, the organic latent heat storage material B, the nonionic surfactant A, the compatibilizing agent, the organically treated layered clay mineral, hydroxyl in the blending amounts shown in Table 2 The group-containing compound A and the reaction accelerator were stirred and mixed at 1000 rpm with a stirring blade at a temperature of 35 ° C. to disperse the organic latent heat storage materials A and B in a colloidal form (average particle diameter 600 μm). Further, after adding polyisocyanate A and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded 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.

(Example 6)
Using the raw materials shown in Table 1, the organic latent heat storage material A, nonionic surfactant A, organically treated layered clay mineral, hydroxyl group-containing compound A, flame retardant, reaction acceleration in the blending amounts shown in Table 2 The agent was stirred and mixed at 1000 rpm with a stirring blade at a temperature of 35 ° C., and the organic latent heat storage material A was dispersed in a colloidal form (average particle size: 420 μm). Further, after adding polyisocyanate A and stirring, it was poured into a 250 mm × 170 mm × 5 mm mold, cured at 50 ° C. for 30 minutes, and demolded 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.
Moreover, the following flame retardance test was done about the obtained test body.
(Flame retardancy test)
The surface of the test specimen was evaluated for the presence or absence of ignition of the test specimen when a direct fire with a gas burner was applied for 1 minute. As a result, no ignition was observed.

(Comparative Example 1)
A paste was prepared by impregnating 7 parts by weight of silica powder (oil absorption amount 350 g / 100 g) with 20 parts by weight of the organic latent heat storage material A shown in Table 1. 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, dried at 50 ° C. for 12 hours, demolded and tested. Got. 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 organic latent 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, baking A slurry mixed with 40 parts by weight of gypsum was poured into a 250 mm × 170 mm × 5 mm mold, dried at 50 ° C. for 12 hours, and demolded to obtain a test specimen. About the obtained test body, the test similar to Example 1 was done. The results are shown in Table 3.
Moreover, the following flame retardance test was done about the obtained test body.
(Flame retardancy test)
The surface of the test specimen was evaluated for the presence or absence of ignition of the test specimen when a direct fire with a gas burner was applied for 1 minute. As a result, ignition was observed.

(Comparative Example 3)
The organic latent heat storage material A shown in Table 1 was laminated with an aluminum-deposited polyethylene terephthalate sheet (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)
An organic latent 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 an interior / exterior material bonded to an inner wall material, an outer wall material, a ceiling material, a floor material of a building such as a house, which is molded and processed into a sheet shape, and an interior material such as a vehicle. Is preferably used. 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 (4)

  Organic latent heat storage material (a), nonionic surfactant (b), compound containing reactive functional group (c-1) and compound containing reactive functional group capable of reacting with the reactive functional group (C-2) is mixed, the organic latent heat storage material (a) is dispersed in a colloidal form, and the component (c-1) and the component (c-2) are reacted with each other.   The method for producing a heat storage body according to claim 1, wherein the hydrophilic / lipophilic balance (HLB value) of the nonionic surfactant (b) is 10 or more.   The organic layered clay mineral (e) is mixed in an amount of 0.5 to 50 parts by weight as a viscosity modifier, with 100 parts by weight of the organic latent heat storage material (a). The manufacturing method of the thermal storage body of description. The method for producing a heat storage body according to any one of claims 1 to 3, wherein the content of the organic latent heat storage material (a) is 40% by weight or more.