JP4558529B2 - Thermoreversible discoloration structure - Google Patents

Description

  The present invention relates to a thermoreversible discoloration structure having thermochromic performance.

Conventionally, various coloring materials are used in various fields such as coating fields such as paints, inks, and printing, cosmetics fields, dyeing fields, and plastic fields.
Each coloring material has its own color development performance depending on the chemical and physical properties of the material, and various colors can be expressed by appropriately selecting and combining these coloring materials. Is possible.

  For example, common coloring materials in the coating field include organic pigments, inorganic pigments, metal powder pigments, dyes and the like. By mixing and dispersing one or more of these coloring materials in a binder, a coating material having uniform color development performance can be obtained.

  Examples of other coloring materials include thermoreversible color-changing materials whose hue changes with heat. This thermoreversible color-changing material is a material that exhibits the property of discoloring significantly (thermochromic performance) due to temperature changes. For example, by forming a film with a coating material containing a thermoreversible color-changing material, it is unique due to the color-changing effect. Can be expressed (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2000-221885

  As materials showing such thermochromic performance, organic materials, inorganic materials, liquid crystal materials, and the like are known. Among these materials, inorganic materials often contain harmful elements such as mercury and are not very practical because they may cause direct harm to the human body. On the other hand, since organic materials and liquid crystal materials have advantages such as high safety and the ability to freely select the color type and the color change temperature, practical use can be expected.

  However, organic materials and liquid crystal materials have a problem that they are vulnerable to heat. That is, the heat resistance temperature of organic materials and liquid crystal materials is relatively low, and when the temperature reaches a temperature equal to or higher than the heat resistance temperature, the original hue changes, the thermoreversibility is lost, and the color fading may occur. In particular, such a tendency tends to be seen in summer and places where it is greatly affected by sunlight.

  In order to solve the above-mentioned problems, the present inventor has intensively studied and as a result, a thermoreversible color changing layer (A) containing a thermoreversible color changing material and a heat storage layer containing a heat storage material having a melting point in a specific temperature region. The thermoreversible discoloration structure laminated with (B) has a property (thermochromic performance) that significantly changes color due to temperature change, suppresses fading due to the influence of heat, maintains thermoreversibility, and is a long-term thermostat. The inventors have found that chromic performance is exhibited and have completed the present invention.

（Ｒ^１は水素（−Ｈ）またはメチル基（−ＣＨ_３）、Ｘはエステル結合（−ＣＯＯ−）、エーテル結合（−Ｏ−）またはアミド結合（−ＣＯＮＨ−）、Ｒ^２は炭素数１２から３６の直鎖アルキル基）
４．蓄熱層が、蓄熱材（ｂ−１）を多孔体に充填したものであることを特徴とする１．に記載の熱可逆性変色構造体。
５．蓄熱層が、蓄熱材（ｂ−１）と、粘性調整剤及び／または熱伝導性物質を多孔体に充填したものであることを特徴とする１．に記載の熱可逆性変色構造体。
６．多孔体が、反応性官能基を含有する化合物（ｂ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｂ−３）との反応により形成されたものであることを特徴とする４．または５．に記載の熱可逆性変色構造体。
７．蓄熱層が、蓄熱材（ｂ−１）、反応性官能基を含有する化合物（ｂ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｂ−３）を均一に混合し、（ｂ−２）成分と（ｂ−３）成分を反応させて得られるものであることを特徴とする１．に記載の熱可逆性変色構造体。
８．蓄熱層が、蓄熱材（ｂ−１）と、粘性調整剤及び／または熱伝導性物質、反応性官能基を含有する化合物（ｂ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｂ−３）を均一に混合し、（ｂ−２）成分と（ｂ−３）成分を反応させて得られるものであることを特徴とする１．に記載の熱可逆性変色構造体。
９．蓄熱層が、蓄熱材（ｂ−１）、親水親油バランス（ＨＬＢ値）が１０以上の非イオン性界面活性剤、反応性官能基を含有する化合物（ｂ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｂ−３）を混合し、蓄熱材（ｂ−１）をコロイド状に分散させ、（ｂ−２）成分と（ｂ−３）成分を反応させて得られるものであることを特徴とする１．に記載の熱可逆性変色構造体。
１０．蓄熱層が、蓄熱材（ｂ−１）と、粘性調整剤及び／または熱伝導性物質、親水親油バランス（ＨＬＢ値）が１０以上の非イオン性界面活性剤、反応性官能基を含有する化合物（ｂ−２）と該反応性官能基と反応可能な反応性官能基を含有する化合物（ｂ−３）を混合し、蓄熱材（ｂ−１）をコロイド状に分散させ、（ｂ−２）成分と（ｂ−３）成分を反応させて得られるものであることを特徴とする１．に記載の熱可逆性変色構造体。
１１．蓄熱材（ｂ−１）が有機潜熱蓄熱材であることを特徴とする１．から１０．のいずれかに記載の熱可逆性変色構造体。 That is, the present invention has the following characteristics.
1. A thermoreversible color change layer (A) containing a thermoreversible color change material, and a heat storage material (b) having a melting point in a temperature range higher than the color change temperature of the thermoreversible color change material and lower than the heat resistance temperature of the thermoreversible color change material (b) A thermoreversible discoloration structure obtained by laminating a heat storage layer (B) containing -1).
2. The heat storage layer contains a heat storage capsule in which the heat storage material (b-1) is encapsulated. The thermoreversible discoloration structure described in 1.
3. In the heat storage capsule encapsulating the heat storage material (b-1), the capsule wall of the capsule is formed from a polymer obtained by polymerizing a monomer mainly composed of a crystalline vinyl monomer represented by the following chemical formula 1. 1. It is characterized by being The thermoreversible discoloration structure described in 1.
(Chemical formula 1)

(R ¹ is hydrogen (—H) or a methyl group (—CH ₃ ), X is an ester bond (—COO—), an ether bond (—O—) or an amide bond (—CONH—), and R ² is 12 carbon atoms. To 36 linear alkyl groups)
4). The heat storage layer is a porous material filled with a heat storage material (b-1). The thermoreversible discoloration structure described in 1.
5). 1. The heat storage layer is a porous material filled with a heat storage material (b-1), a viscosity adjusting agent and / or a heat conductive material. The thermoreversible discoloration structure described in 1.
6). The porous body is formed by a reaction between a compound (b-2) containing a reactive functional group and a compound (b-3) containing a reactive functional group capable of reacting with the reactive functional group. 4. It is characterized by this. Or 5. The thermoreversible discoloration structure described in 1.
7). The heat storage layer uniformly contains the heat storage material (b-1), the compound (b-2) containing a reactive functional group and the compound (b-3) containing a reactive functional group capable of reacting with the reactive functional group. 1 and obtained by reacting the component (b-2) and the component (b-3). The thermoreversible discoloration structure described in 1.
8). The thermal storage layer has a thermal storage material (b-1), a viscosity modifier and / or a thermally conductive substance, a compound (b-2) containing a reactive functional group, and a reactive functional group capable of reacting with the reactive functional group. 1. A compound (b-3) containing a group is uniformly mixed and obtained by reacting the component (b-2) and the component (b-3). The thermoreversible discoloration structure described in 1.
9. The heat storage layer is a heat storage material (b-1), a hydrophilic / lipophilic balance (HLB value) of 10 or more, a nonionic surfactant, a compound (b-2) containing a reactive functional group, and the reactive functional group The compound (b-3) containing a reactive functional group capable of reacting with is mixed, the heat storage material (b-1) is dispersed in a colloidal form, and the component (b-2) and the component (b-3) are reacted. It is what is obtained by making it 1. The thermoreversible discoloration structure described in 1.
10. The heat storage layer contains a heat storage material (b-1), a viscosity modifier and / or a heat conductive substance, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, and a reactive functional group. Compound (b-2) and compound (b-3) containing a reactive functional group capable of reacting with the reactive functional group are mixed, and heat storage material (b-1) is dispersed in a colloidal form (b- 2) It is obtained by reacting the component and the component (b-3). The thermoreversible discoloration structure described in 1.
11. 1. The heat storage material (b-1) is an organic latent heat storage material. To 10. The thermoreversible discoloration structure according to any one of the above.

  The thermoreversible discoloration structure of the present invention has the property of discoloring significantly (thermochromic performance) with temperature change, suppresses fading due to the influence of heat, maintains thermoreversibility, and has long-term thermochromic performance. Can show.

  Hereinafter, it explains in detail with the best form for carrying out the present invention.

  The thermoreversible color change structure of the present invention includes a thermoreversible color change layer containing a thermoreversible color change material (hereinafter also referred to as “(A) layer”), a temperature higher than the color change temperature of the thermoreversible color change material, A heat storage layer (hereinafter, also referred to as “(B) layer”) containing a heat storage material having a melting point in a temperature range lower than the heat resistance temperature of the reversible color-changing material is laminated.

  The color change temperature of the thermoreversible color change material is a temperature at which the thermoreversible color change material described later changes color. The heat-resistant temperature of the thermoreversible color changing material is a temperature at which the thermoreversible color changing material is decomposed at a temperature higher than that, causing discoloration and loss of thermoreversibility.

  The layer (B) of the present invention contains a heat storage material having a melting point in a temperature range higher than the discoloration temperature of the thermoreversible color change material and lower than the heat resistance temperature of the thermoreversible color change material.

  In the present invention, since the layer (B) contains a heat storage material, the temperature can be maintained in a temperature range that is higher than the color change temperature of the thermoreversible color change material and lower than the heat resistance temperature of the thermoreversible color change material. Therefore, it is possible to suppress the heat-resistant temperature of the thermoreversible color-changing material from becoming higher than the heat-resistant temperature, to prevent the thermoreversible color-changing material from fading, to maintain thermoreversibility, and to exhibit thermochromic performance over a long period of time. .

-Thermoreversible color changing layer ((A) layer)-
The (A) layer in the present invention is not particularly limited as long as it contains a thermoreversible color changing material (hereinafter referred to as “component (a-1)”).

The component (a-1) has thermochromic performance.
The component (a-1) is not particularly limited, but it is preferable to use an organic thermoreversible color-changing material because it has high color-change accuracy and can freely select a color type and a color-change temperature.
Specifically, as the organic thermoreversible color-changing material, (p) an electron-donating color-forming organic compound, an electron-accepting organic compound, a microcapsule containing a polar organic compound (hereinafter referred to as “(p) component”), Alternatively, (q) liquid crystal (hereinafter referred to as “(q) component”) can be preferably used.

  The component (p) is an electron-donating color-forming organic compound (color component), an electron-accepting organic compound (color-developing agent) that expresses another color by binding to it, and a color component with a certain temperature as a boundary. Three components of a polar organic compound (decoloring agent) having the ability to dissolve any of the components by cutting the bond between the colorant and the color former are encapsulated. That is, at a low temperature, a first color is displayed due to the combination of the color component and the color former, and at a high temperature, the bond between the color component and the color developer is broken due to the activity of the decoloring agent, and the second color is changed. It is expressed.

  Specifically, as the electron donating color-forming organic compound contained in the component (p), for example, diaryl phthalides, triaryl methane phthalides, leuco triaryl methanes, leuco xanthenes, leuco phenothiazines, Leucophenoxazines, leucooxazines, leucoin digoids, leucooramines, acyl auramines, aryl auramines, diaryl methanes, diaryl phthalides, polyaryl carbinols, indoline phthalides And azaphthalides, fluorans, thiofluorans, spiropyrans, rhodamine B lactams, chromenopyrazoles, methines, quinazolines, diazaxanthenes, bislactones, fluorenes and the like.

  Examples of the electron-accepting organic compound include 1,2,3-triazoles, phenols, thiourea derivatives, oxyaromatic carboxylic acids, and the like.

  Examples of the polar organic compound include alcohols, alcohol / acrylonitrile adducts, azomethines, and esters.

  In addition to the above-described components, the component (p) may contain a surfactant, a hydrophilic protective colloid substance, and the like as necessary.

  For forming the (p) component microcapsules, a thermoplastic resin is usually used. As such a thermoplastic resin, a conventionally well-known thing can be used widely. This thermoplastic resin film may contain an organic photochromic compound in a matrix state.

  On the other hand, as the component (q), for example, cholesteric liquid crystal, terphenyl liquid crystal, nematic liquid crystal, or the like can be used. Those encapsulated in microcapsules can also be used.

  The layer (A) in the present invention is not particularly limited as long as it contains the component (a-1). For example, the layer (A-1) and a binder (hereinafter also referred to as “component (a-2)”). ) To obtain a molded product.

For example, as the component (a-2), a synthetic resin binder and / or an inorganic binder can be used.
Synthetic resin binders include, for example, ethylene resins, vinyl acetate resins, polyester resins, alkyd resins, vinyl chloride resins, epoxy resins, acrylic resins, silicone resins, acrylic silicone resins, urethane resins, fluororesins, etc. Any resin such as a solvent-soluble resin, a non-water-dispersed resin, a water-soluble resin, a water-dispersed resin, and a solvent-free resin can be used. In particular, the use of one or more resins selected from acrylic resins, urethane resins, silicon resins, and fluororesins is preferred because durability can be increased.
By using a synthetic resin binder, the coating film containing the component (a-1) can have flexibility. Further, the degree of flexibility can be freely changed by adjusting the glass transition temperature of the synthetic resin.

  Examples of the inorganic binder include Portland cement, blast furnace cement, silica cement, fly ash cement, white cement, calcined gypsum, colloidal silica, water-soluble alkali metal silicate, and the like. Can be used.

  When a synthetic resin binder is included as the component (a-2), the synthetic resin binder is preferably a reactive functional group-containing synthetic resin binder. As the reactive functional group of the synthetic resin binder, those capable of reacting with the functional group of the crosslinking agent described later can be used. Examples of such functional group combinations include, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, and carbonyl group. A hydrazide group, an epoxy group, an amino group, etc. are mentioned.

  In the present invention, a carboxyl group is particularly preferably used as the reactive functional group of the synthetic resin binder. Examples of carboxyl group-containing synthetic resin binders include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid, and ammonium salts, organic amine salts, and alkali metals. It can be obtained by copolymerizing a carboxyl group-containing monomer such as a salt. These monomers can be used alone or in combination of two or more.

The weight ratio of the component (a-1) and the component (a-2) is such that the solid content of the component (a-1) is 0.1 to 200 parts by weight with respect to 100 parts by weight of the solid content of the component (a-2). (Preferably 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight).
When the ratio of the component (a-1) is more than 200 parts by weight, the adhesion with the layer (B) described later may be inferior, and when it is less than 0.1 parts by weight, the thermochromic performance is insufficient. There is a case.

  The layer (A) can further contain a metal oxide (hereinafter also referred to as “component (a-3)”). The component (a-3) is a component that can mainly suppress deterioration due to ultraviolet rays, and by containing the component (a-3), the deterioration of the component (a-1) and the like due to ultraviolet rays is suppressed. And fading of the component (a-1) can be further prevented over a long period of time.

  Examples of the component (a-3) include titanium oxide, zinc oxide, cerium oxide, and iron oxide. Moreover, what coat | covered the surface of these metal oxides with a silica, an alumina, a silicone, a stearate, a laurate, a hexametaphosphate etc. can be used. These can be used alone or in combination of two or more.

(A-3) The average primary particle diameter of a component becomes like this. Preferably it is 200 nm or less, More preferably, it is 100 nm or less, More preferably, it is 5-50 nm. When the average primary particle diameter is larger than this value, it may be difficult to sufficiently suppress the fading of the component (a-1).
In addition, the average primary particle diameter in this invention is a value calculated by observation using a transmission electron microscope.

The weight ratio of the component (a-3) is, when the component (a-2) is used, the component (a-3) is 0.1 to 100 weights per 100 parts by weight of the solid content of the component (a-2). Parts (preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight).
When the ratio of the component (a-3) is more than 100 parts by weight, the thermochromic performance of the component (a-1) may be reduced. When the ratio is less than 0.1 part by weight, the component (a-1) It is difficult to obtain the effect of suppressing such deterioration.

  In addition to the above-mentioned components, the (A) layer may contain pigments, aggregates, fibers, surfactants, catalysts, antifoaming agents, film-forming aids, leveling agents, plasticizers, antifreeze agents, pH It can also contain additives such as regulators, antiseptics, antifungal agents, anti-algae agents, antibacterial agents, light stabilizers, dispersants, crosslinking agents, thickeners, moisturizers, flame retardants, and fragrances.

-Thermal storage layer ((B) layer)-
The heat storage layer of the present invention has an excellent heat storage property, and has a melting point in a temperature range higher than the color change temperature of the thermoreversible color change material and lower than the heat resistant temperature of the thermoreversible color change material (hereinafter referred to as “( It is not particularly limited as long as it also includes “b-1) component”.

  In this invention, latent heat storage materials, such as an inorganic latent heat storage material and an organic latent heat storage material, are mentioned as (b-1) component.

  Examples of the inorganic latent heat storage material include hydrates such as sodium sulfate decahydrate, sodium carbonate decahydrate, sodium hydrogen phosphate dodecahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, etc. Examples include salts.

  Examples of the organic latent heat storage material include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, long chain fatty acid esters, fatty acid triglycerides, polyether compounds, and the like, and one or more of these heat storage materials are used. Can be used.

  In the present invention, an organic latent heat storage material can be particularly preferably used. Organic latent heat storage materials are preferred because they have a high boiling point and are less likely to volatilize, so there is almost no volume change (thinning) during the heat storage layer molding and the heat storage performance lasts for a long time. Furthermore, when an organic latent heat storage material is used, it is easy to set the phase change temperature according to the application. For example, by mixing two or more organic latent heat storage materials having different phase change temperatures, the phase change temperature can be easily set. Can be set.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used. Specifically, n-decane (melting point −30 ° C.), n-undecane (melting point −25 ° C.), n-dodecane (melting point -8 ° C), n-tridecane (melting point -5 ° C), n-tetradecane (melting point 8 ° C), pentadecane (melting point 10 ° C), n-hexadecane (melting point 17 ° C), n-heptadecane (melting point) 22 ° C), n-octadecane (melting point 28 ° C), n-nonadecane (melting point 32 ° C), icosane (melting point 36 ° C), docosan (melting point 44 ° C), and a mixture 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.), octadecanoic acid (melting point 70 ° C.), hexadecanoic acid (melting point 63 ° C.), and the like.

  As the long-chain fatty acid ester, for example, a long-chain fatty acid ester having 8 to 36 carbon atoms can be used. Specifically, methyl laurate (melting point 5 ° C.), methyl myristate (melting point 19 ° C.), palmitic acid Examples include methyl (melting point: 30 ° C.), methyl stearate (melting point: 38 ° C.), butyl stearate (melting point: 25 ° C.), and methyl arachidate (melting point: 45 ° C.).

  Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and medium-chain fatty acid triglycerides and long-chain fatty acid triglycerides that are refined processed products thereof.

  Examples of the polyether compound include diethylene glycol, triethylene glycol, tetraethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, polypropylene glycol, polyethylene glycol, polypropylene glycol diacrylate, and ethyl ethylene glycol.

  In the present invention, as the component (b-1), 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, an 8 to 36 carbon atoms, It is preferable to use a long chain fatty acid ester, and it is more preferable to use an aliphatic hydrocarbon having 8 to 36 carbon atoms and a long chain fatty acid ester having 8 to 36 carbon atoms. Among these, it is preferable to use a long-chain fatty acid ester having 15 to 22 carbon atoms and an aliphatic hydrocarbon having 15 to 22 carbon atoms. Such a heat storage material has a high latent heat amount and has a phase change temperature ( Since it has a melting point), it is easy to use for various purposes.

  Such heat storage materials may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to use an organic latent heat storage material in that the melting point can be freely designed. In particular, when a heat storage material is applied to the interior material, it is preferable to use a heat storage material having a melting point of 0 ° C. or more and less than 50 ° C.

When mixing and using 2 or more types of (b-1) component, it is preferable to use a compatibilizing agent. By using a compatibilizing agent, the compatibility between the components (b-1) (particularly, the organic latent heat storage material) can be improved.
Examples of the compatibilizing agent include fatty acid triglycerides, nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less), and one or two of these. The above can be mixed and used.

  As described above, the fatty acid triglyceride is a substance that is also used as an organic latent heat storage material. Such fatty acid triglycerides are particularly preferable because they can further improve the compatibility between the organic latent heat storage materials and have excellent heat storage properties. Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and fatty acid triglycerides such as caprylic acid triglyceride, palmitic acid triglyceride, and stearic acid triglyceride, which are refined processed products thereof. More than seeds can be used.

  Examples of the nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 (preferably 1 or more and 5 or less) include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, Sorbitan sesquioleate, sorbitan trioleate, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, glycerol monostearate, glycerol monostearate, glycerol monooleate, stearic acid Examples include glyceryl, glyceryl caprylate, sorbitan stearate, sorbitan oleate, sorbitan sesquioleate, and coconut fatty acid sorbitan.

  The mixing ratio of the compatibilizer and the component (b-1) is usually 0.1 to 20 parts by weight (preferably 0.5 to 10 parts by weight) with respect to 100 parts by weight of the component (b-1). Part by weight).

  Furthermore, a viscosity regulator, a heat conductive substance, etc. can be mixed and used for (b-1) component.

Examples of the viscosity modifier include clay minerals, and it is particularly preferable to use an organically treated layered clay mineral (hereinafter also referred to as “organically treated clay mineral”).
By mixing the component (b-1) and the organically treated clay mineral, the component (b-1) enters between the layers of the organically treated clay mineral, and the heat storage material is easily held between the layers of the organically treated clay mineral.
Furthermore, since the organically treated clay mineral is organically treated, the component (b-1) can easily enter between the layers of the organically treated clay mineral, and the component (b-1) is retained between the layers of the organically treated clay mineral. It has a structure that is easy to be done.

  By mixing such an organically treated clay mineral and the component (b-1), as a result, the viscosity of the component (b-1) is increased, and the component (b-1) is supported in the heat storage layer. It is stably supported and can be held. As will be described later, even when the component (b-1) is encapsulated or filled in a porous body, the component (b-1) can be more stably supported and held in the capsule or the porous body. .

  Furthermore, when the organic latent heat storage material is used as the component (b-1), the organically treated clay mineral hardly reacts with the organic latent heat storage material, and affects the melting point and other various physical properties of the organic latent heat storage material. Therefore, it is preferable because the performance as a heat storage material can be efficiently exhibited and the phase change temperature (melting point) can be easily set.

  The distance between the bottom surfaces of the organically treated clay mineral is preferably about 13.0 to 30.0 mm (preferably 15.0 to 26.0 mm). By being in such a range, the component (b-1) can easily enter between layers of the organically treated clay mineral. 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 (b-1) and the organically treated clay mineral 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 (b-1) component and organic processing clay mineral 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 a viscosity and TI value, the component (b-1) is easily carried in the heat storage layer, and the component (b-1) carried in the heat storage layer is easily held. Even when the component (b-1) is encapsulated or filled into a porous body, the component (b-1) can be stably supported and held in the capsule or the porous body. Therefore, it is possible to prevent the heat storage material from leaking to the outside of the heat storage layer, and to obtain a heat storage layer that is more excellent in heat storage property and more excellent in workability and workability.

  Examples of the organically treated 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 organically treated layered clay mineral and the component (b-1) is usually 0.5 to 50 parts by weight (preferably 1 to 30 parts by weight, based on 100 parts by weight of the component (b-1), More preferably, it may be about 3 to 15 parts by weight.

  Furthermore, a heat conductive substance can also be mixed with (b-1) component. By mixing the heat conductive substance, the movement of heat can be made smooth, the thermal efficiency of the heat storage material can be improved, and more excellent heat storage performance can be obtained.

  Examples of the thermally conductive material include metals such as copper, iron, zinc, beryllium, magnesium, cobalt, nickel, titanium, zirconium, molybdenum, tungsten, boron, aluminum, gallium, silicon, germanium, tin, and alloys thereof. Or metal oxides containing these metals, metal nitrides, metal carbides, metal phosphides and other metal compounds, and scaly graphite, massive graphite, earth graphite, fibrous graphite, etc. One kind or a mixture of two or more kinds can be used.

The thermal conductivity of the thermally conductive material is preferably 1 W / (m · K) or more, more preferably 3 W / (m · K) or more, and further preferably 5 W / (m · K) or more. By mixing a heat conductive material having such a heat conductivity, the heat efficiency of the heat storage material can be improved more efficiently.
Moreover, it is preferable to use a heat conductive substance as microparticles | fine-particles, and it is preferable that an average particle diameter is 1-100 micrometers, Furthermore, it is preferable that it is 5-50 micrometers.

  The mixing ratio of the thermally conductive substance and the component (b-1) is usually 5 to 200 parts by weight (preferably 10 to 80 parts by weight, more preferably 100 parts by weight of the component (b-1). 20 parts by weight to 60 parts by weight).

In the present invention, the component (b-1) can be encapsulated in a film as it is to form a heat storage layer, or the component (b-1) encapsulated or the component (b-1) What filled the porous body can also be used as a heat storage layer.
In the present invention, in particular, the component (b-1) encapsulated or the component (b-1) filled in the porous body can be suitably used as the heat storage layer. , (B-1) component leakage and penetration can be prevented.

As a method (laminating method) in which the component (b-1) is encapsulated in the film as it is, even if the component (b-1) is directly encapsulated in the laminate film, the component (b-1) is gelled with a gelling agent. You may enclose it. In the present invention, a gel-treated product can be suitably used from the viewpoint of shape stability.
In the present invention, the component (b-1) (preferably a latent heat storage material) laminated by such a lamination method can be used as a heat storage layer. Moreover, the thermal storage layer with a wide application temperature range can be obtained by installing two or more types of laminated thermal storage materials having different melting points on the component (b-1).

  The material and shape of the laminate film are not particularly limited. For example, organic materials such as polyethylene, polypropylene, nylon, polyester, polyethylene terephthalate, vinylidene chloride, ethylene / vinyl acetate copolymer, aluminum, gold, silver, copper, chromium , Zinc, titanium, nickel, cobalt, etc. or a metal such as an alloy thereof, silicon oxide, titanium oxide, indium oxide, metal oxides such as aluminum oxide, etc. Can be used.

  In the present invention, in particular, in terms of thermal efficiency, heat resistance, and film strength, 10.0 W / (m · K) or more (preferably 20.0 W / (m · K) or more, more preferably 100 W / (m · K). It is preferable to use a film containing a metal or metal oxide having a thermal conductivity of In the present invention, it is particularly preferable to use aluminum as a material having a thermal conductivity of 10.0 W / (m · K) or more.

(B-1) As a method of encapsulating the component, a chemical production method such as an interfacial polymerization method, an in-situ polymerization method, a double orifice method, a physicochemical production method such as a coacervation method, a submerged drying method, etc. Is available. The size and shape of the capsule of the heat storage capsule thus obtained are not particularly limited. From the viewpoint of handling and filling rate, dry spherical capsules are desirable.
In the present invention, the component (b-1) (preferably latent heat storage material) encapsulated by such an encapsulation method can be used as the heat storage layer.

  For example, as a method for encapsulating the component (b-1) by the interfacial polymerization method, it may be encapsulated by a known method, but the emulsion polymerization method is performed by mixing the component (b-1) and the monomer shown below. Then, by polymerizing the monomer by a known polymerization method such as a suspension polymerization method, the heat storage material can be enclosed in a capsule having the polymer of the monomer as a capsule wall.

Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate. , T-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate and the like containing a lower alkyl group (Meth) acrylic monomers;
Higher alkyl group-containing (meth) acrylic monomers such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate;

Carboxyl group-containing (meth) acrylic monomers such as (meth) acrylic acid;
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- Hydroxyl group-containing monomers such as 2-hydroxybutyl, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate;

Aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, N-tbutylamino Ethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Amine-containing (meth) acrylic monomers such as N, N-dimethylaminopropyl (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate;
(Meth) acrylamide, ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-cyclopropyl ( (Meth) acrylamide, N- (meth) acryloylpyrrolidine, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl Amide-containing (meth) acrylic monomers such as -N-n-propyl (meth) acrylamide;

Glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, (meth) acrylic acid-ε-caprolactone modified glycidyl, (meth) acrylic acid-β -Epoxy group-containing (meth) acrylic monomers such as methylglycidyl;
Nitrile group-containing (meth) acrylic monomers such as acrylonitrile and methacrylonitrile;
Diacetone (meth) acrylate, diacetone acrylamide, acrolein, vinyl methyl ketone, acetonyl acrylate, diacetone methacrylamide, vinyl ethyl ketone, vinyl isobutyl ketone, acryloxyalkylpropanals, methacryloxyalkylpropanals, 2-hydroxy Carbonyl group-containing monomers such as propyl acrylate acetyl acetate and butanediol acrylate acetyl acetate;

Isocyanate group-containing monomers such as methacryloyl isocyanate;
Hydrazino group-containing monomers such as propylene-1,3-dihydrazine and butylene-1,4-dihydrazine;
Oxazoline group-containing monomers such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline;
Di (meth) acrylate such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A type di (meth) acrylate, divinylbenzene, N, N′-methylenebisacrylamide (Meth) acrylic monomers;
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;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;

Aromatic hydrocarbon monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene;
Sulfonic acid-containing monomers such as styrene sulfonic acid and vinyl sulfonic acid;
Vinyl ester vinyl monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate;
Vinylidene halide monomers such as vinylidene fluoride;
Vinyl ether vinyl monomers such as lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether;
Non-vinyl monomers such as melamine are listed.

  When an organic latent heat storage material is used as the heat storage material, it is preferable to use a monomer mainly composed of a crystalline vinyl monomer represented by the following chemical formula 1 as the monomer.

（Ｒ^１は水素（−Ｈ）またはメチル基（−ＣＨ_３）、Ｘはエステル結合（−ＣＯＯ−）、エーテル結合（−Ｏ−）またはアミド結合（−ＣＯＮＨ−）、Ｒ^２は炭素数１２から３６（好ましくは炭素数が１２から３０、さらに好ましくは炭素数が１４から２２）の直鎖アルキル基） (Chemical formula 1)

(R ¹ is hydrogen (—H) or a methyl group (—CH ₃ ), X is an ester bond (—COO—), an ether bond (—O—) or an amide bond (—CONH—), and R ² is 12 carbon atoms. To 36 (preferably a linear alkyl group having 12 to 30 carbon atoms, more preferably 14 to 22 carbon atoms)

Examples of such crystalline vinyl monomers include higher alkyl groups (meth) such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. Acrylic monomers;
Vinyl ester vinyl monomers such as vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate;
Vinyl ether vinyl monomers such as lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether;
Etc.

  A heat storage capsule encapsulated with such a monomer can also prevent cracking and shape change of the heat storage layer due to volume shrinkage due to phase change of the heat storage material (particularly change from liquid to solid).

  When encapsulated using such a crystalline vinyl monomer, the capsule wall of the heat storage capsule is hardly plasticized by the organic latent heat storage material, and the capsules are not easily fused and aggregated. In addition, since a vinyl-based monomer is used, there is flexibility with respect to force, and when the capsule is kneaded and stirred, the organic latent heat storage material is less likely to leak without crushing the capsule wall, which is preferable.

Further, as the crystalline vinyl monomer, a crystalline vinyl monomer having a linear alkyl group having 12 to 36 carbon atoms (preferably having 12 to 30 carbon atoms, more preferably 15 to 22 carbon atoms) is used. Excellent compatibility with organic latent heat storage materials. Therefore, a high content of organic latent heat storage material can be included in the capsule, and excellent heat storage properties can be exhibited.
When a monomer having less than 12 carbon atoms is used as a main component, the capsule wall is easily plasticized and the capsules may be fused and aggregated. Further, when a non-vinyl monomer is used, for example, when melamine or the like is used, the capsule wall tends to be hard and brittle. Therefore, when the capsule is kneaded and stirred, the capsule wall is easily crushed and the organic latent heat storage material is likely to leak.

  The content of the crystalline vinyl monomer is not particularly limited as long as the effect of the present invention is not impaired, and is 50% by weight or more, further 70% by weight or more based on the total amount of monomers constituting the capsule wall. Is preferred.

  Furthermore, the crystallization temperature of the capsule wall obtained by polymerizing the above monomer containing a crystalline vinyl monomer may be appropriately set according to the intended use, but is usually 25 to 90 ° C, more preferably 30 to 70 ° C. Preferably there is. Such a crystallization temperature is preferable because the effects of the present invention can be obtained at a practical level. If the crystallization temperature is too low, the capsule may soften at room temperature and the capsules may be fused and aggregated.

  The crystallization temperature is a value measured with a differential scanning calorimeter (DSC220CU: manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min.

  In the present invention, the method of encapsulating the latent heat storage material includes, for example, mixing the latent heat storage material and the above monomer, emulsion polymerization, miniemulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, seed polymerization. By polymerizing the monomer by a method such as dispersion polymerization, feed polymerization, suspension polymerization, or the like, a heat storage capsule using a polymer of the monomer as the latent heat storage material as a capsule wall can be produced. In such an encapsulation method, in addition to the latent heat storage material and monomer, known initiators, emulsifiers, dispersants, solvents, polymerization inhibitors, polymerization inhibitors, buffering agents, cross-linking agents, pH adjusters, chain transfer agents Etc. can also be mixed.

As the emulsifier, anionic emulsifier, cationic emulsifier, nonionic emulsifier, amphoteric emulsifier, nonionic emulsifier and the like are not particularly limited and can be used.
For example, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate and sodium dodecyl sulfate, fatty acid salts, rosinates, alkyl sulfates, alkyl sulfosuccinates, α-olefin sulfonates, alkyl naphthalene sulfonates, polyoxyethylenes Anionic emulsifiers such as alkyl (aryl) sulfate esters,
Quaternary ammonium salts such as lauryl trialkyl ammonium salts, stearyl trialkyl ammonium salts, trialkyl benzyl ammonium salts, primary to tertiary amine salts, lauryl pyridinium salts, benzalkonium salts, benzethonium salts, or Cationic surfactants such as laurylamine acetate,
C1-C20 alkanol, phenol, naphthol, bisphenols, C1-C20 alkylphenol, C1-C20 alkyl naphthol, polyoxyethylene (propylene) glycol, ethylene oxide and / or propylene such as aliphatic amine Nonionic surfactants such as oxide adducts,
Examples include amphoteric surfactants such as carboxybetaine type, sulfobetaine type, aminocarboxylic acid type, and imidazoline derivative type.
In the present invention, it is particularly preferable to use a nonionic surfactant and / or an anionic emulsifier.

  Examples of the initiator include persulfate initiators such as ammonium persulfate, potassium persulfate, and sodium persulfate, 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis [2- (2-imidazoline) -2-yl) propane] dihydrochloride, azo initiators such as 2,2′-azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, dialkyl peroxides such as decanoyl peroxide, t-butyl Peroxyesters such as peroxybenzoate, organic peroxide initiators such as cumene hydroperoxide, paramentane hydroperoxide, hydroperoxide such as t-butyl hydroperoxide, hydrogen peroxide, redox initiator, photopolymerization An initiator, a reactive initiator, etc. can be used.

For example, when an organic latent heat storage material is used as the heat storage material, as a method of encapsulating the organic latent heat storage material, in particular,
(1) A step of mixing a monomer having a crystalline vinyl monomer represented by Chemical Formula 1 as a main component with an organic latent heat storage material or the like and performing emulsion polymerization at a temperature higher than the crystallization temperature of the polymer of the monomer. ,
(2) It is preferable to encapsulate after the polymerization by a step of cooling to a temperature lower than the crystallization temperature of the polymer.

In such a production method, a polymer obtained by polymerizing monomers forms the outermost wall of the capsule, and a heat storage capsule in which an organic latent heat storage material is included in the capsule can be easily obtained by a general emulsion polymerization method. It is characteristic that it can be manufactured. In particular, the crystalline vinyl monomer has excellent compatibility with the organic latent heat storage material, the crystalline vinyl monomer and the organic latent heat storage material can be uniformly mixed before the emulsion polymerization, and the capsule obtained after the emulsion polymerization has a high content. The organic latent heat storage material can be included, and a capsule having excellent heat storage properties can be manufactured.
In the emulsion polymerization, it is essential to carry out the emulsion polymerization at a temperature higher than the crystallization temperature of the polymer obtained by polymerizing the monomer. By emulsion polymerization at such a temperature, an amorphous polymer (capsule wall) is formed during the polymerization, and the organic latent heat storage material is easily encapsulated in the capsule. Furthermore, after the polymerization, the polymer is phase-changed by cooling to a temperature lower than the crystallization temperature of the polymer to form a capsule wall which is the outermost wall of the capsule, and the encapsulated organic latent heat A heat storage capsule can be obtained in which the heat storage material does not leak from the capsule.
With such a phase change mechanism, it is possible to obtain a heat storage capsule in which the organic latent heat storage material does not leak from the capsule even though the organic latent heat storage material with a high content is included in the capsule. Further, such a heat storage capsule is not particularly limited as long as the outermost wall is a polymer obtained by polymerizing monomers, and the capsule may be a core-shell shape in which the organic latent heat storage material is a core and the polymer is a shell. It may be a porous shape in which a large number of organic latent heat storage materials are dispersed, or a gel shape.

Specifically, in the first step, by using a crystalline vinyl monomer, the capsule wall is hardly plasticized by the organic latent heat storage material, and the capsules are not easily fused and aggregated. In addition, since a vinyl monomer is used, it is more flexible than melamine and the like, and when the capsule is kneaded and stirred, the capsule wall is not crushed and the organic latent heat storage material does not leak. Therefore, heat storage capsules are easy to handle when dispersed in a solvent such as water, and are easy to recover and easy to handle when used as a solid fine powder.
Moreover, since the crystalline vinyl monomer which has a C12-C36 linear alkyl group is used, it is excellent in compatibility with an organic latent heat storage material. Therefore, a high content of organic latent heat storage material can be included in the capsule, and excellent heat storage properties can be exhibited.

The second step (2) is characterized by cooling to a temperature lower than the crystallization temperature of the polymer. By cooling to such a temperature, the polymer that forms the capsule wall that is the outermost wall is phase-changed and crystallized, and the encapsulated organic latent heat storage material is obtained without leaking from the capsule. be able to.
The cooling method is not particularly limited, but a known cooling device or a cooling substance may be used, and depending on the crystallization temperature, if the crystallization temperature is higher than room temperature, natural cooling is performed at room temperature. You can also.

The heat storage capsule thus obtained can be used as a heat storage capsule dispersion, or the heat storage capsule can be taken out of the emulsion liquid and used as a solid fine powder.
When using a heat storage capsule as a solid fine powder, it is preferable to collect | recover at a temperature lower than the crystallization temperature of a polymer as a 3rd process. The recovery process in the present invention includes a separation process, a drying process, a classification process, and the like, and a solid fine powder capsule is obtained by such a recovery process. In the present invention, by collecting at a temperature lower than the crystallization temperature of the polymer, the polymer can be recovered while maintaining the crystallinity, the organic latent heat storage material does not leak from the capsule, and the capsule wall It is also possible to prevent the capsules from being fused and agglomerated without breaking. Therefore, it is easy to collect the capsule as a solid fine powder, and the solid fine powder can be obtained in a high yield. As the recovery step, a known method may be adopted as long as the temperature is lower than the crystallization temperature of the polymer.
Moreover, the obtained capsule solid fine powder can be used again by being dispersed in a solvent such as water.

The encapsulated heat storage capsule can contain the latent heat storage material at a high content. Specifically, it can be encapsulated in an amount of usually 30% by weight or more, further 50% by weight or more with respect to the total amount of the heat storage capsule. By being such content, the outstanding thermal storage property can also be shown. In addition, since the capsule wall of the heat storage capsule is crystalline, the capsule wall is hardly plasticized by the organic latent heat storage material included in the capsule, and fusion / aggregation of the capsules can be prevented.
Furthermore, the capsule wall itself formed from the crystalline vinyl monomer used in the present invention has a heat storage property. Therefore, more excellent heat storage property can be shown by the heat storage property of the organic latent heat storage material and the heat storage property of the capsule wall.

  When the encapsulated heat storage capsule is used as a heat storage layer, for example, the heat storage capsule can be encapsulated in the above-described film as it is, or a molded product of a slurry in which the heat storage capsule and the binder are kneaded is enclosed in the film. In addition, it can be manufactured by a method of impregnating various materials by a dipping method, a reduced pressure / pressure injection method, or a combination of these.

  For example, as a method of encapsulating the heat storage capsule as it is in the film, a film in which the heat storage capsule is dispersed in a solvent such as water or a solid fine powder of the heat storage capsule may be enclosed in the film.

Moreover, what is necessary is just to form using the well-known thing as a method of forming the slurry which knead | mixed the heat storage capsule and binder.
Examples of such binders include acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, vinyl acetate resin, acrylic / acetic acid Solvent soluble types such as vinyl resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / versaic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin Synthetic rubber such as resin, NAD type resin, water soluble resin, water dispersion type resin, solventless type resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber Organic binder such as
Examples include inorganic binders such as Portland cement, blast furnace cement, silica cement, fly ash cement, white cement, calcined gypsum, colloidal silica, and water-soluble alkali metal silicates. Use one or more of these. Can do.

  In the present invention, it is particularly preferable to use an organic binder. Among the organic binders, either a one-component type or a two-component type can be used, but a two-component type is more preferable. The use of the two-component type is preferable because the reaction proceeds quickly, a high-strength molded product is formed, and a molded product in which the heat storage capsules are uniformly dispersed is easily obtained.

  As the two-component type, for example, 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 and carbodiimide group, Examples include those utilizing a crosslinking reaction such as a carboxyl group and an oxazoline group, a carbonyl group and a hydrazide group, and a carboxyl group and an aziridine group. In particular, it is preferable to use a crosslinking reaction between a hydroxyl group and an isocyanate group because the reaction proceeds quickly and a molded product in which the heat storage capsules are more uniformly dispersed is easily obtained.

  In addition to the binder, the slurry includes a solvent, a pigment, an aggregate, a viscosity modifier, a buffer, a dispersant, an antifoaming agent, a plasticizer, an antiseptic, an antifungal agent, an antialgae, a flame retardant, Various additives such as a leveling agent, an anti-settling agent, an anti-sagging agent, and a dehydrating agent can be kneaded.

  In the formation of such a molded product, such a slurry may be formed into a sheet by a known method, or may be formed by enclosing the slurry in the aforementioned film. In the present invention, since a heat storage capsule having a specific capsule wall is used, the capsule wall can be efficiently dispersed in the slurry without being crushed and without being fused or agglomerated between the capsules during formation. Further, a molded product having excellent heat storage properties, and further a heat storage layer can be easily produced.

Further, in the method of impregnation by the dipping method, the reduced pressure / pressure injection method or the like, the material shown below may be impregnated with the heat storage capsule.
Examples of materials include inorganic materials such as concrete, gypsum board, mortar, and slate board,
Synthetic fibers such as glass fiber, pulp fiber, polyethylene fiber, polypropylene fiber, vinylon fiber, tetron fiber, polyester fiber, cellulose fiber, nylon fiber, natural fiber such as cotton, cotton, asbestos, hemp, palm, cork, kenaf, etc. Fiber material,
Acrylic resin, silicone resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, vinyl acetate resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / urethane resin Silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / versaic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methacryl Organic materials such as acid-methyl-butadiene rubber, synthetic rubber such as butadiene rubber,
Wood materials such as pine, lawan, beech, hinoki and plywood, and other papers, synthetic papers, ceramic papers and the like can be mentioned, and one or more of these can be used.

  In the present invention, in particular, when encapsulated using a crystalline vinyl monomer, the capsule wall is not crushed, and the capsules are not fused or aggregated, so that they are dispersed in a solvent such as water. Even when used as a solid fine powder or as a slurry, a heat storage layer having excellent heat storage properties can be easily produced.

  The content of the heat storage capsule in the heat storage layer is preferably 10% by weight or more, more preferably 20% by weight or more and 70% by weight or less with respect to the total amount of the heat storage layer. By being in such a range, it can have the outstanding heat storage property.

  The porous material filled with the heat storage material is not particularly limited as long as the heat storage material is supported and held on the porous material. In the case where the porous body is filled with such a heat storage material, since the heat storage material is subdivided in the pores of the porous body, the heat conduction between the heat storage material and the heat storage material is delayed, and the solid-liquid of the heat storage material This is preferable because the change is suppressed and the heat storage effect is sustained.

The shape of the porous body is not particularly limited as long as the heat storage material can be supported and held, and examples thereof include those having a shape such as a particle aggregation type porous body, a sponge type porous body, and a three-dimensional stitch structure type porous body. In the present invention, in particular, a three-dimensional stitch structure type porous body is preferable because the heat storage material is more easily supported and held.
Moreover, when the thermal conductivity of the porous body component is low (specifically, 0.15 W / (m · K) or less), it is preferable because the thermal conduction is further delayed and the heat storage effect is further sustained.

  As the porous body, an inorganic porous body, an organic porous body, and the like can be used without particular limitation, but an organic porous body is preferably used from the viewpoint that the heat storage material is more easily supported and held. Furthermore, the organic porous body can also prevent cracking and shape change of the heat storage layer due to volume shrinkage due to phase change of the heat storage material (particularly, change from liquid to solid).

  Examples of the resin component that forms such an organic porous material include acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, and acetic acid. Solvents such as vinyl resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / veova resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, etc. Soluble type, NAD type, water soluble type, water dispersion type, solventless type, etc., or synthetic rubber such as chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber Of these, among these Or more can be used species or two or.

  Further, in the present invention, among the resin components, either one liquid type or two liquid type can be used, but the two liquid type is more preferable. For example, a compound containing a reactive functional group (hereinafter referred to as “component (b-2)”) and a compound containing a reactive functional group capable of reacting with the reactive functional group (hereinafter referred to as “(b-3)”. 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, In addition, it can be suitably used because it forms a well-crosslinked structure, has good compatibility with the heat storage material, and easily suppresses leakage of the heat storage material from the porous 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, 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 methyl cellulose, ethyl cellulose, 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 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 heat storage material may be reduced, and the heat storage material 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 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 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 (b-2) and the component (b-3), 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-2) and the component (b-3) 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 porous body can be made strong, and a uniform and dense cross-linked structure with no leakage of the heat storage material can be obtained.
When the NCO / OH ratio is less than 0.1, the crosslinking rate is low, and sufficient physical properties such as curability, durability, and strength may not be ensured, and the heat storage material is likely to leak. When the NCO / OH ratio is larger than 1.8, unreacted isocyanate remains, adversely affects various physical properties of the porous body, the porous body is easily deformed, and the heat storage material is liable to leak.

Moreover, in reaction of (b-2) component and (b-3) 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 curability and strength of the porous body are insufficient, and the swelling tends to occur easily. When the amount is more than 10 parts by weight, the weather resistance, discoloration resistance and the like tend to decrease.

  In addition to the above components, as a component for forming a porous body, pigments, aggregates, plasticizers, antiseptics, antifungal agents, antialgae agents, antifoaming agents, foaming agents, leveling agents, pigment dispersants, antisettling agents Additives such as a sagging inhibitor, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer may be mixed.

  What is necessary is just to manufacture a porous body by a well-known method using the said component.

  As a method of filling the porous body with the heat storage material, a method of filling the porous body with the heat storage material by an immersion method, a reduced pressure / pressure injection method, or the like, or mixing the heat storage material in advance when manufacturing the porous body And the like.

  In this invention, the method of mixing and filling a heat storage material beforehand at the time of porous body manufacture is preferable, and such a method can prevent that a heat storage material leaks from a porous body more, and is preferable.

  Specifically, first, the heat storage material and the porous body forming component are mixed, and then the porous body forming component is cured to obtain a heat storage material in which the heat storage material is filled in the porous body.

For example,
(I) (b-1) component (viscosity adjusting agent, heat conductive substance if necessary), (b-2) component, (b-3) component are mixed uniformly, and (b-2) component (B-3) a method of reacting the components and filling the porous body with the heat storage material,
(Ii) component (b-1) (as necessary, a viscosity modifier, a heat conductive substance), and a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, (b-2) Mix the component and the component (b-3), disperse the component (b-1) in a colloidal form, react the component (b-2) and the component (b-3), and fill the porous body with the heat storage material And the like.

In the method (i), the (b-1) component, the (b-2) component, and the (b-2) component are uniformly mixed to obtain a compatible state. Next, the porous body filled with the component (b-1) is obtained by reacting the component (b-2) and the component (b-3).
In this process, microphase separation accompanying the change from the compatible state to the incompatible state occurs, and a densely packed three-dimensional stitch structure type porous body composed of the component (b-2) and the component (b-3) is formed. It seems to be done.
The three-dimensional stitch structure type porous body is filled with the component (b-1), and a porous body filled with the component (b-1) is formed.

In particular, when a viscosity modifier is mixed in addition to the component (b-1), the viscosity of the component (b-1) is adjusted, and the component (b-1) filled in the porous body leaks to the outside. Can be prevented. Therefore, it is preferable because a high heat storage material content can be achieved.
Furthermore, by appropriately setting the porous body forming component, the interaction with the porous body forming component works, and the component (b-1) can be further prevented from leaking to the outside.
Further, if the porous body is a three-dimensional stitch structure type porous body, the component (b-1) can be further prevented from leaking to the outside because of its dense structure.

In the production of such a three-dimensional stitch structure type porous body, it is preferable that the compatibilizer described above is further mixed and produced. The compatibilizer improves not only the compatibility between the components (b-1) but also the compatibility between the component (b-1) and the resin component (the component (b-2), the component (b-3), etc.). Therefore, it is possible to further prevent the (b-1) component from leaking from the porous body by forming a denser three-dimensional stitch structure type porous body.
Examples of the compatibilizing agent include fatty acid triglycerides and nonionic surfactants having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10, and the compatibility between the component (b-1) and the resin component. In particular, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB) of 1 or more and less than 10 is preferred.

  In the method (i), the reaction temperature is preferably equal to or higher than the melting point of the component (b-1). Although specific reaction temperature changes with kinds of (b-1) component, it is about 20 to 100 degreeC normally. (B-1) By making it react above the melting point of a component, it will be in a compatible state easily. Moreover, what is necessary is just to make reaction time into about 0.2 to 10 hours normally.

In the method (i), for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, but is 500 to 10,000. It is desirable that it is 1000-3000. With such a molecular weight, it can be easily melt-mixed with the component (b-1), 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 (b-1), a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, the component (b-2) and the component (b-3) Mix and disperse the component (b-1) in the form of a colloid in the component (b-2) and the component (b-3). Next, by reacting the component (b-2) and the component (b-3), a porous body filled with the component (b-1) can be obtained.

  In such a method, the component (b-1) is contained in the component (b-2) and / or the component (b-3) with a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more. It is possible to create a fine colloidal dispersion. By reacting the component (b-2) and the component (b-3) in such a state, a porous body filled with the component (b-1) can be obtained.

  Specific examples of the production method of the present invention include (b-1) component, a nonionic surfactant having a hydrophilic / lipophilic balance (HLB value) of 10 or more, (b-2) component, and (b-3). ) Component is mixed and (b-2) component and (b-3) component are reacted, or (b-1) component and hydrophilic / lipophilic balance (HLB value) of 10 or more nonionic surfactant The method of making it react by mixing an agent, (b-2) component (or (b-3) component), and adding (b-3) component (or (b-2) component) is mentioned.

In such a manufacturing method, although the content rate of (b-1) component can be enlarged and it has a high (b-1) component content rate, (b-1) ) No component leaks. Furthermore, even when the porous body filled with the component (b-1) is cut, the component (b-1) does not leak from the cut surface, and is excellent in workability. Since there is no leakage of components, it is excellent in installation workability.
Furthermore, since the component (b-1) is finely and uniformly dispersed, the shape change of the porous body itself due to the volume change accompanying the solid-liquid change of the component (b-1) can 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 (b-1) component, (b-2) component, and (b-3) 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 (b-1) (particularly, the organic latent heat storage material) is preferable because it is easy to disperse 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 (b-1), 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. When is used, it is preferable to have a long-chain alkyl group having 8 to 36 carbon atoms in the structure of the surfactant. In particular, the effects of the present invention can be further enhanced by selecting a 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 (b-1) is as follows: (b-1) component, (b-2) component, (b-3) component The amount of the surfactant 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 component (b-1). That's fine.
When the surfactant is less than 0.01 parts by weight, the component (b-1) and the component (b-2) and / or the component (b-3) are separated or easily cause a creaming phenomenon. The colloidal dispersion may not be performed efficiently, and the effects of the present invention may not be obtained. When the amount is more than 30 parts by weight, physical properties such as water resistance of the obtained heat storage layer may be adversely affected.

  In the above production method, the component (b-1) has 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) in the state before the reaction. It is characterized by being in a colloidally dispersed state. By reacting the component (b-2) and the component (b-3) from such a state, the component (b-1) can be finely dispersed (filled) in the porous body.

In the state before the reaction, the temperature in the system is preferably equal to or higher than the melting point of the component (a). Specifically, it is usually about 20 ° C. to 80 ° C., and at such a temperature, the component (a) is easily dispersed in a colloidal state, which is preferable.
The particle size is a value measured using an optical microscope (BHT-364M, manufactured by Olympus Optical Co., Ltd.).

  In such a production method, the specific reaction temperature varies depending on the type of component (b-1), but is usually about 20 ° C to 80 ° C. Above the melting point of the component (b-1), the component (b-1) tends to be in a colloidal state, which is preferable. Moreover, reaction time should just be normally about 0.2 to 5 hours.

In such production, for example, when using a compound containing a hydroxyl group and a compound containing an isocyanate group, the molecular weight of the compound containing a hydroxyl group is not particularly limited, and should be selected within a wide range. In general, it is preferably 500 to 10,000, more preferably 1000 to 3000. With such a molecular weight, the component (b-1) can be dispersed in a finer colloidal form, and the content of the component (b-1) can be further increased. Therefore, it is excellent in heat storage property, and it is possible to further reduce the shape change of the porous body itself due to the volume change accompanying the solid-liquid change of the component (b-1).
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 addition, in the method of mixing and filling the component (b-1) in advance during the production of the porous body, when using an isocyanate group, a carboxyl group, an imide group, or an aldehyde group as the reactive functional group, a long chain as a heat storage material The use of alcohol and polyether compounds 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 storage layer in the present invention, in addition to the above components, pigment, aggregate, plasticizer, preservative, antifungal agent, antialgae, antifoaming agent, foaming agent, leveling agent, pigment dispersant, anti-settling agent Additives such as an agent, an anti-sagging agent, a lubricant, a dehydrating agent, a matting agent, a flame retardant, an ultraviolet absorber, and a light stabilizer can also be contained.

-Lamination method-
The thermoreversible color change structure of the present invention is obtained by laminating the thermoreversible color change layer (A) and the heat storage layer (B), and the laminating method is not particularly limited. However, when there is a heat storage layer (B) on the thermoreversible color change layer (A), the heat storage layer (B) has transparency that does not hinder the color of the reversible color change layer (A). Preferably it is.
For example, a two-layer structure in which a thermoreversible color changing layer (A) and a heat storage layer (B) are stacked may be used, or a multilayer structure having three or more layers may be used. The thermoreversible color changing layer (A) may be a laminate of two or more thermoreversible color changing layers having different thermoreversible color changing materials.
Further, the thermoreversible discoloration structure may be laminated on a base material to be described later. In this case, the thermoreversible color-changing layer (A) and the heat storage layer (B) can be laminated in order on the substrate, or the heat storage layer (B) and the thermoreversible color-changing layer ( A) can also be laminated in order.

Specifically, in the lamination method, a heat storage layer (B) is prepared in advance by a known method, and a thermoreversible discoloration coating material composed of (a-1) component, (a-2) component, etc. is applied thereon. The thermoreversible color-changing layer (A) is formed from a thermoreversible color-changing coating material consisting of the (a-1) component, the (a-2) component, etc. in advance, A method of laminating with an adhesive / adhesive tape, a method of laminating by thermal fusion, a thermoreversible discoloration layer (A) is prepared in advance, and a heat storage layer (B) forming component ((b-1) component, (b -2) component, (b-3) component and the like) and the like.
In the method of applying the thermoreversible discoloration coating material and the heat storage layer (B) forming component, it may be applied using a coating device such as a brush, a trowel, a spray, a roller, a roll coater or a flow coater. Further, there are no particular limitations such as multiple coatings.

In the present invention, the present invention can be applied to a portion that expresses a unique color due to a color change effect, and in particular, furniture, toys, daily necessities, artificial flowers, beverage containers, vehicles, interior wall materials, exterior wall materials, ceiling materials, floor materials, etc. Can be applied. Furthermore, it can be applied to thermoelectric conversion systems, refrigeration / freezers, cooler boxes, heat insulation sheets, etc. by utilizing the heat storage effect.
Examples of the base material constituting such a part include concrete, inorganic molded plate, tile, plastic, metal, wood, paper, etc., and these base materials are those on which some kind of coating has already been formed. May be.
In this invention, what is necessary is just to laminate | stack on these base materials by the method similar to the above.

  Examples and Comparative Examples are shown below to clarify the features of the present invention.

Example 1
Using the raw materials shown in Table 1, the raw materials were mixed in the raw material composition shown in Table 2 to produce a thermoreversible color change coating material 1.
On the other hand, using the raw materials shown in Table 3, the heat storage material A, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A were uniformly mixed at a temperature of 40 ° C. in the blending amounts shown in Table 4, and the reaction accelerator A was added. Stir well. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 1 having a thickness of 5 mm. Leakage of the heat storage material from the heat storage layer 1 was hardly observed. The NCO / OH ratio was 1.0.
On the obtained heat storage layer 1, the thermoreversible color change coating material 1 was spray-coated so that the dry film thickness was 10 μm, and dried at room temperature for one week to obtain a test specimen.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.

(Heat resistance test)
In the heat resistance test, the obtained specimen was subjected to 5 cycles, with 1 cycle of “standing in a thermostat at 70 ° C. for 6 hours and standing at 25 ° C. for 18 hours” as one cycle.
For the specimens before and after the heat resistance test, the color difference (ΔE) at a temperature of 25 ° C. and a temperature of 15 ° C. was measured with a color difference meter (SPECTROTOPOMETER CM-3700d, manufactured by Minolta Co., Ltd.) and evaluated. Evaluation was performed by color difference, and four-step evaluation was performed: A: ΔE was 0.1, B: ΔE was 0.2, C: ΔE was 0.3, and D: ΔE was 0.4 or more. The results are shown in Table 5.

(Example 2)
A test body was obtained in the same manner as in Example 1 except that the thermoreversible color change coating material 1 was replaced with the thermoreversible color change coating material 2.
The obtained test body was green at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 3)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 2.
Heat storage layer 2: Using the raw materials shown in Table 3, the heat storage material B, the organically treated layered clay mineral A, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A are uniformly heated at a temperature of 40 in the blending amounts shown in Table 4. The mixture was mixed at 0 ° C., reaction accelerator A was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 2 having a thickness of 5 mm. Leakage of the heat storage material from the heat storage layer 2 was hardly observed. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

Example 4
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 3.
Heat storage layer 2: Heat storage material A, heat storage material B, compatibilizer, organically treated layered clay mineral B, hydroxyl group-containing compound B, isocyanate group using the raw materials shown in Table 3 in the blending amounts shown in Table 4 The contained compound B was uniformly mixed at a temperature of 40 ° C., the reaction accelerator A was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 3 having a thickness of 5 mm. Leakage of the heat storage material from the heat storage layer 3 was hardly observed. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 5)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 4.
Heat storage layer 4: Heat storage material A, organically treated layered clay mineral B, hydroxyl group-containing compound B, isocyanate group-containing compound B, thermal conductive material using the raw materials shown in Table 3 in the amounts shown in Table 4 Were uniformly mixed at a temperature of 40 ° C., the reaction accelerator A was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 4 having a thickness of 5 mm. Leakage of the heat storage material from the heat storage layer 4 was hardly observed. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 6)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 5.
Heat storage layer 5: Using the raw materials shown in Table 3, the heat storage material A, the surfactant, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A are mixed at a temperature of 40 ° C. in the blending amounts shown in Table 4, and the heat storage material A was dispersed in a colloidal form (average particle size 180 nm), reaction accelerator A was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 5 having a thickness of 5 mm. There was no leakage of the heat storage material from the heat storage layer 5. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 7)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 6.
Heat storage layer 6: Using the raw materials shown in Table 3, the heat storage material A, the surfactant, the organically treated layered clay mineral B, the hydroxyl group-containing compound A, and the isocyanate group-containing compound A are blended in the amounts shown in Table 4. The mixture was mixed at a temperature of 40 ° C. to disperse the heat storage material A in a colloidal form (average particle size: 420 nm), and the reaction accelerator A was added and sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame covered with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 6 having a thickness of 5 mm. There was no leakage of the heat storage material from the heat storage layer 6. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 8)
A test body was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 7.
Heat storage layer 7: Heat storage material A, heat storage material B, compatibilizing agent, surfactant, organically treated layered clay mineral B, hydroxyl group-containing compound using the raw materials shown in Table 3 in the amounts shown in Table 4 A and the isocyanate group-containing compound A were mixed at a temperature of 40 ° C., the heat storage materials A and B were dispersed in a colloidal form (average particle diameter 600 nm), the reaction accelerator A was added, and the mixture was sufficiently stirred. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 7 having a thickness of 5 mm. No leakage of the heat storage material from the heat storage layer 7 was observed. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

Example 9
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 8.
Heat storage layer 8: 60 parts by weight of n-octadecane, 40 parts by weight of stearyl acrylate and 3 parts by weight of polyethylene glycol dimethacrylate are uniformly mixed, and further 2 parts by weight of polyoxyethylene oleyl ether ammonium sulfate and 1 part by weight of polyoxyethylene stearyl ether Part, 1 part by weight of ammonium persulfate and 100 parts by weight of water were added and mixed in a polymerization tank to prepare a pre-emulsion solution. Next, the inside of a polymerization tank was deaerated and emulsion polymerization was performed at 80 ° C. for 3 hours in a nitrogen atmosphere. After the polymerization, the polymerization tank was cooled to room temperature (25 ° C.) to obtain a heat storage capsule (average particle size 1.7 μm).
This capsule was separated from the aqueous layer, pulverized and washed with a small pulverizer, dried in a dryer at 25 ° C. for 3 hours, and classified (100 mesh) to obtain a solid powder-like heat storage capsule. At this time, separation from the aqueous layer was simple, and the heat storage material did not leak from the capsule during pulverization, and the obtained capsule could be recovered with a size of approximately 100 mesh or less.
Next, 60 parts by weight of the obtained heat storage capsule, 33 parts by weight of the hydroxyl group-containing compound A shown in Table 1, and 9 parts by weight of the isocyanate group-containing compound A shown in Table 1 were mixed at a temperature of 40 ° C., and the reaction promotion shown in Table 1 was performed. 0.1 parts by weight of the agent was added and stirred sufficiently. After stirring, it was poured into a 300 × 180 × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 8 having a thickness of 5 mm. . At this time, in the heat storage capsule, the heat storage layer 8 could be easily manufactured without pulverizing the capsule wall.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Example 10)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 9.
Thermal storage layer 9: 60 parts by weight of methyl palmitate (phase change temperature 30.0 ° C., latent heat 200 kJ / kg), 40 parts by weight of stearyl acrylate and 3 parts by weight of polyethylene glycol dimethacrylate are uniformly mixed, and further dodecyl sulfate 3 parts by weight of sodium, 1 part by weight of ammonium persulfate and 100 parts by weight of water were added and mixed in a polymerization tank to prepare a pre-emulsion solution. Next, the inside of a polymerization tank was deaerated and emulsion polymerization was performed at 80 ° C. for 3 hours in a nitrogen atmosphere. After the polymerization, the polymerization tank was cooled to room temperature (25 ° C.) to obtain a heat storage capsule (average particle size 1.8 μm).
This capsule was separated from the aqueous layer, pulverized and washed with a small pulverizer, dried in a dryer at 25 ° C. for 3 hours, and classified (100 mesh) to obtain a solid powder-like heat storage capsule. At this time, separation from the aqueous layer was simple, and the heat storage material did not leak from the capsule during pulverization, and the obtained capsule could be recovered with a size of approximately 100 mesh or less.
Next, 60 parts by weight of the obtained heat storage capsule, 33 parts by weight of the hydroxyl group-containing compound A shown in Table 1, and 9 parts by weight of the isocyanate group-containing compound A shown in Table 1 were mixed at a temperature of 40 ° C., and the reaction promotion shown in Table 1 was performed. 0.1 parts by weight of the agent was added and stirred sufficiently. After stirring, the mixture was poured into a 300 × 180 × 5 mm mold with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 120 minutes, and demolded to obtain a heat storage layer 9 having a thickness of 5 mm. . At this time, in the heat storage capsule, the heat storage layer 9 could be easily manufactured without pulverizing the capsule wall.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
About this test body, the heat resistance test similar to Example 1 was done. The results are shown in Table 5.

(Comparative Example 1)
On the polyurethane foam (250 mm x 170 mm x 25 mm, thermal conductivity 0.03 W / (m · K), thickness 5 mm), the thermoreversible discoloration coating material 1 is spray-coated so that the dry film thickness is 10 μm. Then, it was dried at room temperature for 24 hours to obtain a test specimen.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
When the same heat resistance test as that of Example 1 was performed on this test body, the temperature on the thermoreversible color change layer side of the test body increased to about 70 ° C. and did not show any discoloration due to heat after the heat resistance test. .

(Comparative Example 2)
A specimen was obtained in the same manner as in Example 1 except that the heat storage layer 1 was replaced with the next heat storage layer 8.
Heat storage layer 8: Using the raw materials shown in Table 3, the heat storage material C, the organically treated layered clay mineral B, the hydroxyl group-containing compound B, and the isocyanate group-containing compound B were mixed at the temperature of 40 ° C. in the amounts shown in Table 4. Mix uniformly, add reaction accelerator A and stir well. After stirring, the mixture was poured into a 250 mm × 170 mm × 5 mm mold frame laid with a 50 μm polyethylene terephthalate film (PET film), cured at 50 ° C. for 180 minutes, and demolded to obtain a heat storage layer 8 having a thickness of 5 mm. The NCO / OH ratio was 1.0.
The obtained specimen was magenta at a temperature of 15 ° C., became white and transparent at a temperature of 25 ° C., and showed discoloration due to heat.
When the same heat resistance test as that of Example 1 was performed on this test body, the temperature on the thermoreversible color change layer side of the test body increased to about 70 ° C. and did not show any discoloration due to heat after the heat resistance test. .

Claims (4)

A thermoreversible color change layer (A) containing a thermoreversible color change material;
A heat storage layer (B) containing a heat storage material (b-1) having a melting point in a temperature range higher than the color change temperature of the thermoreversible color change material and lower than the heat resistant temperature of the thermoreversible color change material is laminated. A thermoreversible discoloration structure.   The thermoreversible discoloration structure according to claim 1, wherein the heat storage layer contains a heat storage capsule encapsulating the component (b-1).   The thermoreversible discoloration structure according to claim 1, wherein the heat storage layer is a porous body filled with the component (b-1). The thermoreversible discoloration structure according to any one of claims 1 to 3, wherein the heat storage material (b-1) is an organic latent heat storage material.