JP5232355B2 - Thermal storage method of heat insulation material - Google Patents

Description

  The present invention relates to a heat insulating material capable of maintaining a target temperature for a long time and a heat storage method thereof.

Since ancient times, warmers and hot water bottles have been widely used as winter heating tools, and have become established as heat insulation materials.
Cairo uses heat generated by the oxidation reaction of iron powder and is widely used as a portable heat insulating material.
Hot water bottles use sensible heat of water and have been used for a long time as reusable heat insulation materials.

  However, the warmer has a problem that temperature control is difficult and it cannot be reused. In addition, hot water bottles can be reused, but there are problems such as that it takes time to boil hot water for reuse, and if it takes more time, sufficient heat retention cannot be obtained.

  In order to solve such a problem, a heat insulating material containing a heat storage material has been studied. Such a heat insulating material is expected to be temperature-controllable and reusable depending on the type of heat storage material.

Examples of the heat insulating material containing the heat storage material include a heat insulating material in which an inorganic hydrate containing crystal water is used as the heat storage material, the inorganic hydrate is gelled and injected into a container or a film.
Such a heat insulating material irradiates microwaves in a microwave oven, so that a hydrate in the heat storage material, that is, water molecules vibrate and generate heat, and the heat storage material stores heat, so that a sufficient heat retention effect is obtained. Is what you get. Therefore, heat can be easily stored at a desired temperature using a microwave oven or the like.
However, since such a heat insulating material contains a hydrate (water) in the heat storage material, there is a risk that, when irradiated with microwaves from a microwave oven, water may volatilize and the container or film may burst. Is expensive. In addition, when water volatilization occurs, the physical properties of the heat storage material itself change, making it difficult to reuse in the long term.

In order to solve such a problem, a heat insulating material in which a thermally and chemically stable organic latent heat storage material containing no hydrate (water) is injected into a container has been proposed.
As such an organic latent heat storage material, paraffin, olefin, and the like are often used. However, since these do not generate heat by microwaves in a microwave oven, it is necessary to immerse them in hot water or use another heat source. There was a problem that considerable energy and time were required to store heat.

With respect to such a problem, Patent Document 1 discloses a high-temperature heat storage body that includes a hydrate containing crystal water in a molten mixture of an ethylene-olefin copolymer and a crystalline organic compound (paraffin). It is disclosed.
However, in order to store this heat storage body with high frequency, a hydrate containing a large amount of crystal water is required. If the amount of hydrate containing a large amount of crystallization water is increased, the content of the crystalline organic compound (paraffin) is relatively reduced, and the heat retention and heat storage properties are inferior. In addition, water volatilization or the like is likely to occur, the heat storage body may burst, or the physical properties of the heat storage material itself may change, making it difficult to reuse in the long term.

Japanese Patent No. 2548850

  In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, the heat retaining material obtained by fixing the organic latent heat storage material (a) with a binder containing a segment that vibrates and heats by microwaves is obtained by using microwaves. Heat can be stored easily, for example, it can be stored in a microwave oven in a general household, heat insulation can be secured for a long time by microwave irradiation, and further, the heat insulating material itself accompanying microwave irradiation can be secured. It has been found that cracks and deterioration due to volume expansion can be suppressed, and the present invention has been completed.

That is, the present invention has the following characteristics.
1. It is a heat storage method of a heat insulating material characterized by irradiating the heat insulating material with microwaves,
The heat insulating material is
The organic latent heat storage material (a) is fixed with a binder (b) containing a segment that vibrates and generates heat by microwaves,
The organic latent heat storage material (a) is 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. One or more organic latent heat storage materials selected from
The binder (b) containing a segment that vibrates and generates heat by microwaves is obtained by reacting a polyether polyol (b-1) with an isocyanate group-containing compound (b-2). A heat storage method for a heat insulating material characterized by the above .
2. It is obtained by mixing an organic latent heat storage material (a), a polyether polyol (b-1), a compound (b-2) having an isocyanate group, and reacting (b-1) and (b-2). Features 1 The heat storage method of the heat insulating material as described in 2.
3. Organic latent heat storage material (a), non-ionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, polyether polyol (b-1), compound having an isocyanate group (b-2), 1. Obtained by reacting (b-1) and (b-2) The heat storage method of the heat insulating material as described in 2.
4). The content of the organic latent heat storage material (a) is 40% by weight or more. To 3. A heat storage method for a heat insulating material according to any one of the above.

  The heat insulating material of the present invention can be easily stored with microwaves, and can be stored with heat easily, for example, in a microwave oven in a general household. In addition, it is possible to ensure heat retention for a long time by microwave irradiation, and because it can suppress cracks and deterioration due to volume expansion of the heat insulating material itself accompanying microwave irradiation, it has excellent durability. It can be reused for a long time.

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

The heat insulating material of the present invention is an organic latent heat storage material (hereinafter also referred to as “component (a)”) and a binder (hereinafter referred to as “component (b)”) containing segments that vibrate and generate heat by microwaves. )).
Since the heat insulating material of the present invention does not contain water or a water-containing compound (hydrate), there is no risk of the heat insulating material bursting by microwaves, and it can be reused as a heat insulating material for a long time. Is possible. Furthermore, even if microwaves are excessively irradiated, the heat insulating material can be prevented from bursting.
In addition, the heat insulating material of the present invention can contain a large amount of component (a) in the heat insulating material because the binding material itself forming the heat insulating material vibrates and generates heat by microwaves. Therefore, it is excellent in heat storage and heat retention, and can maintain the heat retention function for a long time.

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

  Such a component (a) is preferable because it has a high boiling point, hardly volatilizes, has almost no volume change (thinning) during the formation of the heat insulating material, and has long-term heat storage performance. Furthermore, it is easy to set the phase change temperature according to the application of the organic latent heat storage material. For example, the phase change temperature can be easily set by mixing two or more types of organic latent heat storage materials having different phase change temperatures. It becomes possible.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used. Specifically, 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), icosane (melting point 36 ° C), docosan (melting point 44 ° C), and mixtures thereof N-paraffin, paraffin wax, etc. comprised by these.

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

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

Moreover, when mixing and using 2 or more types of organic latent heat storage materials, it is preferable to use a compatibilizer (henceforth "(c) component"). By using the component (c), the compatibility between the organic latent heat storage materials can be improved.
Examples of the component (c) 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 triglycerides include vegetable oils such as coconut oil and palm kernel oil, and fatty acid triglycerides such as caprylic acid triglyceride, palmitic acid triglyceride, and stearic acid triglyceride that are refined processed products thereof. More than seeds can be used.

Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less) include:
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 (c) 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.

Furthermore, in the present invention, the component (a) and an organically treated layered clay mineral (hereinafter also referred to as “component (d)”) can be mixed. By mixing the component (d) and the component (a), the component (a) enters between the layers of the component (d). Since the component (d) is organically treated, the (a) component easily enters the (d) component layer, and the (a) component is easily held between the (d) component layers. Yes.
By mixing the component (d) and the component (a), as a result, the viscosity of the component (a) can be increased, and the component (a) can be supported and kept further in the heat insulating material. . Therefore, it is possible to prevent the component (a) from leaking out of the heat insulating material, and to obtain a heat insulating material excellent in heat storage, excellent in workability and workability.
Furthermore, since the component (d) hardly reacts with the organic latent heat storage material and does not affect the melting point and other physical properties of the organic latent heat storage material, the performance as the heat storage material can be efficiently exhibited. Since the phase change temperature (melting point) can be easily set, it is preferable.

  (D) 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 (d). 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 (d) 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 let the TI value at the time of (a) component and (d) component mixing be about 4.0-9.0. In addition, TI value is a value calculated | required by following formula 1 using a B-type rotational viscometer.
TI value = η1 / η2 (Formula 1)
(However, η1: Viscosity at 2 rpm (Pa · s: guide value for the second rotation), η2: Viscosity at 20 rpm (Pa · s: Guide value for the fourth rotation))

  By setting such a viscosity and TI value, the component (a) is easily stably supported in the heat insulating material at the time of manufacturing the heat insulating material, and (a) in the heat insulating material after the heat insulating material is manufactured. ) The component is easily retained for a long time. Therefore, it is possible to prevent the component (a) from leaking to the outside of the heat insulating material, and to obtain a heat insulating material that is more excellent in heat storage properties and more excellent in workability and workability.

The component (d) is not particularly limited as long as it is an organically treated layered clay mineral.
Examples of the layered clay mineral include smectite, vermiculite, kaolinite, allophane, mica, talc, halloysite, and sepiolite. In addition, swellable fluorine mica, swellable synthetic mica, and the like can be used.
Examples of the organic treatment include ion exchange (intercalation) of a cation existing between layers of a layered clay mineral with a long-chain alkylammonium ion or the like.
In the present invention, smectite and vermiculite are particularly preferably used because they are easily organically treated. Furthermore, among the smectites, montmorillonite is particularly preferably used, and in the present invention, organically treated montmorillonite can be particularly preferably used.

Specifically, as an organically treated montmorillonite,
Hosung's Esben, Esven C, Esben E, Esben W, Esben P, Esben WX, Esven NX, Esven NZ, Esven N-400, Organite, Organite D, Organite T (trade name)
TIXOGEL MP, TIXOGEL VP, TIXOGEL VP, TIXOGEL MP, TIXOGEL EZ 100, MP 100, TIXOGEL UN, TIXOGEL DS, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A, TIXOGEL VP-A )
BENTONE 34, 38, 52, 500, 1000, 128, 27, SD-1, SD-3 (trade names) manufactured by Elementis Japan
Etc.

  The mixing ratio of the component (a) and the component (d) is usually 0.5 to 50 parts by weight (preferably 1 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 part by weight, the component (a) may easily leak from the heat insulating material. When the amount is more than 50 parts by weight, the viscosity of the component (a) becomes too high, and the step of supporting / holding the heat insulating material may be difficult.

  Further, in the present invention, the component (a) is also referred to as “component (e)” below the heat conductive substance. ) Can also be mixed. By mixing the component (e), heat can be transferred smoothly, the thermal efficiency of the heat insulating material can be improved, and more excellent heat storage performance can be obtained.

  Examples of the component (e) include copper, iron, zinc, beryllium, magnesium, cobalt, nickel, titanium, zirconium, molybdenum, tungsten, boron, aluminum, gallium, silicon, germanium, tin, and alloys thereof, 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. However, it is preferable to suppress the use of hydrates of the above substances as component (e).

The thermal conductivity of the component (e) 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 component (e) having such thermal conductivity, the thermal efficiency of the heat storage material can be improved more efficiently.
The component (e) is preferably used as fine particles, and the average particle size is preferably 1 to 100 μm, more preferably 5 to 50 μm.

  The mixing ratio of the component (e) and the component (a) is normally 5 to 200 parts by weight (preferably 10 to 80 parts by weight, more preferably 100 parts by weight of the component (a). May be about 20 to 60 parts by weight).

The component (b) used in the present invention is characterized by containing a segment that absorbs and heats microwaves.
In the present invention, by using a binder containing a segment that absorbs and heats microwaves, for example, heat can be stored easily with microwaves such as a microwave oven. Examples of the microwave include a microwave (2450 MHz) in a microwave oven, and may be in a range of usually 300 MHz to 300 GHz.

Examples of the segment that absorbs microwaves and heats include an ether bond, an ester bond, an amide bond, a urethane bond, and the like that are present in the skeleton, such as a carboxyl group, a hydroxyl group, an amino group, and a carbonyl group.
In particular, in the present invention, those having an ether bond or the like in the skeleton are preferable.

  In the present invention, any binder that includes a segment that absorbs and heats such microwaves can be used without any particular limitation.

  For example, polyether resin, polyester resin, vinyl acetate resin, alkyd resin, epoxy resin, acrylic resin, silicone resin, acrylic silicone resin, urethane resin, phenol resin, melamine resin, polycarbonate resin, fluorine resin, acrylic / vinyl acetate resin, Acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate resin, etc., or composites of these may be mentioned. These solvent-soluble resins, non-water-dispersed resins, water-soluble Mold resin, solventless resin, and the like, and one or more of these can be used.

Moreover, in this invention, although 1 liquid type and 2 liquid type can be used among binders, 2 liquid type is more preferable. Use of the two-component type is preferable because the reaction proceeds quickly, a high-strength heat insulating material is formed, and a heat insulating material in which the component (a) is uniformly dispersed is easily obtained.
For example, a compound containing a reactive functional group (hereinafter referred to as “component (b-1)”) and a compound containing a reactive functional group capable of reacting with the reactive functional group (hereinafter referred to as “(b-2)”. A two-component type consisting of “component”) is preferably used.

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

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

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

  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, 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. it can.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Cellulose and / or derivatives thereof have a hydroxyl group, but a portion of the hydroxyl group is preferably substituted with an alkoxyl group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). .
Specifically, the substitution degree is preferably 1.8 to 2.8, more preferably 2.2 to 2.6. The degree of substitution means a ratio in which three hydroxyl groups present in the glycolose unit constituting cellulose are substituted with alkoxyl groups and the like, and the degree of substitution is 3 when 100% substitution is performed.
By controlling the degree of substitution in such a range, the interaction with the heat storage material can be improved, and the heat storage material can be held in the heat insulating material for a long period of time.
When the degree of substitution is smaller than 1.8, the interaction with the heat storage material may decrease, and the heat storage material may not be sufficiently retained in the heat insulating material. 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 heat storage material 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 heat insulating material obtained 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 (b-1) and the component (b-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 (b-1) and the component (b-2) is not particularly limited, and may be set as appropriate according to the application.
For example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the NCO / OH ratio is usually 0.1 to 1.8, preferably 0.2 to 1.5, more preferably 0.3. What is necessary is just to set in the range used as -1.3.
By being within such a range of the NCO / OH ratio, the strength of the heat insulating material can be strengthened, and a uniform and dense cross-linked structure with no leakage of the heat storage material can be obtained.

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

  The reaction accelerator is usually mixed at a ratio of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the compound containing a hydroxyl group. When the reaction accelerator is less than 0.01 parts by weight, the heat-retaining material has insufficient curability and strength and tends to be swollen. When the amount is more than 10 parts by weight, the weather resistance, discoloration resistance and the like tend to decrease.

  What is necessary is just to manufacture the heat insulating material of this invention by a well-known method using the said component.

For example, in the present invention,
(I) The component (a) (if necessary, the component (c), the component (d), the component (e), etc.), the component (b-1), the component (b-2) are uniformly mixed, and (b -1) A method of immobilizing the heat storage material by reacting the component and the component (b-2),
(Ii) (a) component (as required, (c) component, (d) component, (e) component, etc.) and a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, ( The component (b-1) and the component (b-2) are mixed, the component (a) is dispersed in a colloidal state, the component (b-1) and the component (b-2) are reacted, and the heat storage material is fixed. Method, etc.

In the method (i), the component (a), the component (b-1), and the component (b-2) are uniformly mixed to obtain a compatible state. Next, by reacting the component (b-1) and the component (b-2), a heat insulating material having the component (a) immobilized thereon is obtained.
In this process, microphase separation occurs due to the change from the compatible state to the incompatible state, and a dense and intricate three-dimensional cross-linking structure composed of the components (b-1) and (b-2) is formed. I think that the. In this three-dimensional cross-linked structure, the component (a) is fixed, and a heat insulating material in which the component (a) is fixed is formed.

In particular, when the component (d) is mixed with the component (a), the viscosity of the component (a) is adjusted, and the component (a) fixed to the heat insulating material is prevented from leaking outside. Can do. Therefore, it is preferable because a high heat storage material content can be achieved.
Furthermore, by appropriately setting the heat insulating material forming component, the interaction with the heat insulating material forming component works to further prevent the component (a) from leaking to the outside.
Moreover, if it is a three-dimensional bridge | crosslinking structure as a heat insulating material, it can prevent more that (a) component leaks outside because of the precise | minute structure.

In the production of the heat insulating material having such a three-dimensional cross-linking structure, it is preferable that the above-described component (c) is further mixed and produced. The component (c) improves not only the compatibility between the components (a) but also the compatibility between the component (a) and the resin component (component (b-1), component (b-2), etc.). Therefore, the heat insulating material having a denser three-dimensional cross-linking structure is formed, and the leakage of the component (a) from the heat insulating material can be further prevented.
Examples of the component (c) include the above-described fatty acid triglycerides and nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10, but the compatibility between the component (a) and the resin component is included. Is particularly preferably a nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10.

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

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

  In the method (ii), the component (a) is mixed with a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, the component (b-1) and the component (b-2). The component (a) is dispersed in a colloidal form in the components (b-1) and (b-2). Next, by reacting the component (b-1) and the component (b-2), a heat insulating material in which the component (a) is immobilized can be obtained.

  In such a method, the non-ionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more allows the component (b-1) and / or the component (b-2) to have a fine component (a). A colloidally dispersed state can be created. By reacting the component (b-1) and the component (b-2) in such a state, a heat insulating material in which the component (a) is immobilized can be obtained.

  Specific examples of the production method of the present invention include, for example, component (a), a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, component (b-1) and component (b-2). Or (b) component and (b-2) component are reacted, or (a) component, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, (b The method of making it react by mixing (-1) component (or (b-2) component) and adding (b-2) component (or (b-1) component) etc. are mentioned.

In such a production method, the content of the component (a) can be increased, and the component (a) may leak over time despite having a high content of the component (a). Absent. Furthermore, even if the heat insulating material with the component (a) fixed is cut, the component (a) does not leak from the cut surface, and the processability is excellent, and the component (a) is not leaked by nailing or the like. Excellent installation workability.
Furthermore, since the component (a) is finely and uniformly dispersed, the shape change of the heat insulating material itself due to the volume change accompanying the solid-liquid change of the component (a) can also be reduced.

  What is necessary is just to select suitably as a nonionic surfactant whose hydrophilic lipophilic balance (HLB value) is 10 or more by (a) component, (b-1) component, and (b-2) component. Further, 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, most preferably 13 or more and 17 or less). In particular, the component (a) is preferable because it can be easily dispersed in a colloidal form.

Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene. Polyoxyethylene sorbitan fatty acid esters such as sorbitan monooleate,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether,
Polyoxyethylene sorbitol fatty acid esters such as tetraoleic acid polyoxyethylene sorbit,
Polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate,
Examples include polyoxyethylene hydrogenated castor oil and polyoxyethylene coconut oil fatty acid sorbitan.

  In particular, as the component (a), an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and a long chain fatty acid ester having 8 to 36 carbon atoms are used. If present, it is preferable that the surfactant has a long-chain alkyl group having 8 to 36 carbon atoms in the structure. In particular, the effect of the present invention can be further enhanced by selecting the component (b-1) that is similar to the carbon number of the long-chain alkyl group of the surfactant, or a similar one.

The mixing ratio of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more and the component (a) is appropriately set depending on the components (a), (b-1), and (b-2). Usually, the surfactant may be about 0.01 to 30 parts by weight (preferably 0.1 to 20 parts by weight) with respect to 100 parts by weight of component (a).
When the amount of the surfactant is less than 0.01 parts by weight, the component (a) and the component (b-1) and / or the component (b-2) are separated or easily cause a creaming phenomenon. The colloidal dispersion may not occur and the effects of the present invention may not be obtained. When the amount is more than 30 parts by weight, physical properties such as water resistance of the heat insulating material to be obtained may be adversely affected.

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

In the state before the reaction, the temperature in the system is preferably equal to or higher than the melting point of the component (a). Specifically, 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.
The particle diameter is a value measured using an optical microscope (BHT-364M, manufactured by Olympus Optical Co., Ltd.).

  In such a production method, the specific reaction temperature varies depending on the type of component (a), but is usually about 20 ° C to 80 ° C. Above the melting point of component (a), component (a) is likely to be in a colloidal state, which is preferable. Moreover, reaction time should just be normally about 0.2 to 5 hours.

Further, in such production, for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, and can be selected within a wide range. Although it is possible, it is usually desirable that it is 500 to 10,000, and more desirably 1000 to 3000. With such a molecular weight, the component (a) can be dispersed in a finer colloidal form, and the content of the component (a) can be further increased. Therefore, it is excellent in heat storage property, and it is possible to further reduce the shape change of the heat insulating material itself due to the volume change accompanying the solid-liquid change of the component (a).
Furthermore, the mixing ratio of the compound containing a hydroxyl group and the compound containing an isocyanate group is not particularly limited and may be set as appropriate, but the NCO / OH ratio is 0.1 to 1.8, preferably 0.8. The effect can be further enhanced by being 2 to 1.7, more preferably 0.3 to 1.6, and more preferably 0.5 to 1.5.

  In the methods (i) and (ii), when an isocyanate group, a carboxyl group, an imide group, or an aldehyde group is used as a reactive functional group, the use of a long chain alcohol as a heat storage material is excluded. In addition, when a hydroxyl group, an epoxy group, a carbodiimide group, an oxazoline group, or an aziridine group is used as a reactive functional group, the use of a long chain fatty acid as a heat storage material is excluded.

  In the production of the heat insulating material in the present invention, in addition to the above components, pigments, aggregates, plasticizers, antiseptics, antifungal agents, algaeproofing agents, antifoaming agents, foaming agents, leveling agents, pigment dispersants, anti-settling agents Additives such as an agent, an anti-sagging agent, a lubricant, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer can also be contained.

  The manufacturing method of the heat insulating material in this invention is not specifically limited, For example, it can manufacture by well-known methods, such as extrusion molding and mold forming, using the said component. The heat insulating material can be laminated with a nonwoven fabric, a woven fabric, paper, synthetic paper, a plastic film (PET film or the like), and the like.

The heat insulating material obtained by the production method of the present invention is not particularly limited in sheet shape, rod shape, needle shape, spherical shape, square shape, powder shape, etc. A sheet-like material is preferable.
Further, the thickness of the sheet-shaped heat insulating material is not particularly limited, but it may be generally about 1 to 30 mm (preferably 2 to 20 mm).

  The heat storage material content of the heat insulating 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 insulating material can be easily heated by using a microwave oven or the like in a general household, and can be stored and kept warm.
For example, when using a microwave oven in a general household, heat is easily stored at a target temperature by irradiating with microwaves (frequency: 2450 MHz) for about 1 to 5 minutes, preferably about 2 to 4 minutes. Is possible.
Since the heat insulating material of the present invention can be stored and heated easily using such a microwave oven, it can be applied to a heat insulating material for winter heating, etc., and also a container for home delivery pizza and a lunch box It can also be used for a heat insulating material used for a food heat insulating application such as a heat insulating material used for a health device. Moreover, a heat retention effect can also be heightened by combining with a heat insulating material etc.

  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.

(Experimental example 1)
Using the raw materials shown in Table 1, the heat storage material, surfactant, hydroxyl group-containing compound, and isocyanate group-containing compound were mixed at a temperature of 50 ° C. in the blending amounts shown in Table 2, and the heat storage material was colloidal (average particle size 20 μm), a reaction accelerator was added, and the mixture was sufficiently stirred to obtain a heat storage slurry. The obtained heat storage slurry was poured into a mold (100 mm × 100 mm × 5 mm), cured at 80 ° C. for 30 minutes, demolded from the mold, and a heat insulating material having a thickness of 5 mm was obtained. Two sheets of this heat insulating material were produced.

  The following test was performed using the obtained heat insulating material.

(Heat retention test)
The obtained heat insulating material (2 sheets) was irradiated with microwaves (2450 MHz) in a microwave oven for 2 minutes, taken out from the microwave oven, and stacked with the two heat insulating materials sandwiching a thermocouple, thereby obtaining a test specimen. . This test body was left still in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and the temperature change over time was measured. In the heat retention test, the temperature was evaluated immediately after microwave irradiation (after 0 hour), after 2 hours, and after 4 hours.
Furthermore, this operation was regarded as one cycle, and a total of 100 cycles were performed. The first, 50th and 100th temperatures were evaluated, and the reusability was also evaluated.
The results are shown in Table 3.

(Experimental example 2)
Using the raw materials shown in Table 1, the heat storage material, the organically treated layered clay mineral, the hydroxyl group-containing compound, and the isocyanate group-containing compound are uniformly mixed at a temperature of 50 ° C. in the blending amounts shown in Table 2, and the reaction accelerator Was added and the mixture was sufficiently stirred to obtain a heat storage slurry, and a heat insulating material was obtained in the same manner as in Example 1. About the obtained heat insulating material, the test similar to Example 1 was done. The results are shown in Table 3.

(Experimental example 3)
Using the raw materials shown in Table 1, heat storage materials, surfactants, organically treated layered clay minerals, hydroxyl group-containing compounds, and isocyanate group-containing compounds are mixed at a temperature of 50 ° C. in the blending amounts shown in Table 2 to store heat. A heat insulating material was obtained in the same manner as in Example 1 except that the material was dispersed in colloidal form (average particle size 42 μm), a reaction accelerator was added, and the mixture was sufficiently stirred to obtain a heat storage slurry. About the obtained heat insulating material, the test similar to Example 1 was done. The results are shown in Table 3.

Claims (4)

It is a heat storage method of a heat insulating material characterized by irradiating the heat insulating material with microwaves,
The heat insulating material is
The organic latent heat storage material (a) is fixed with a binder (b) containing a segment that vibrates and generates heat by microwaves,
The organic latent heat storage material (a) is 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. One or more organic latent heat storage materials selected from
The binder (b) containing a segment that vibrates and generates heat by microwaves is obtained by reacting a polyether polyol (b-1) with an isocyanate group-containing compound (b-2). A heat storage method for a heat insulating material characterized by the above . It is obtained by mixing an organic latent heat storage material (a), a polyether polyol (b-1), a compound (b-2) having an isocyanate group, and reacting (b-1) and (b-2). The heat storage method of the heat insulating material according to claim 1, wherein Organic latent heat storage material (a), non-ionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, polyether polyol (b-1), compound having an isocyanate group (b-2), It is obtained by making (b-1) and (b-2) react , The heat storage method of the heat insulating material of Claim 1 characterized by the above-mentioned. The content of the organic latent heat storage material (a) is 40% by weight or more, and the heat storage method for a heat insulating material according to any one of claims 1 to 3.