JP7155900B2 - Composition for forming heat-storage layer, heat-storage layer using the composition, and heat-storage laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for forming a heat storage and heat release layer, a heat storage and heat release layer using the composition, and a heat storage and heat release laminate.

In recent years, for the purpose of more efficient heat utilization, there has been a demand for a technique for storing the generated thermal energy and generating heat according to the situation. Patent Document 1 describes a thermal energy storage material containing a heat storage material such as 2-amino-2-methyl-1,3-propanediol and a resin. However, by simply mixing the resin and the heat storage material, a uniform sheet state cannot be obtained because the average primary particle size of the heat storage material is large. In addition, the heat storage property is inferior, the amount of heat storage and heat release energy is small, and there are many cases where no heat is generated in repeated tests of heat storage and heat release, and stable repeated heat storage property cannot be obtained.
Further, Patent Literature 2 describes a heat storage sheet in which a heat storage material is dispersed in a resin matrix. However, since paraffin is microencapsulated with an outer shell made of resin as a heat storage material, it is possible to seep out during melting due to the phase change, which is a solid-liquid phase transition, and to change the volume. Not only is it difficult to maintain the shape, but the heat storage property is also inferior. Therefore, encapsulation is required, but with the encapsulation method, the content of the heat storage material must be set low in order to obtain a good sheet state, and the heat storage and heat storage properties are lowered. In addition, since the outer shell portion of the capsule does not have heat storage properties, the heat storage properties are further reduced. Furthermore, encapsulation also has the problems of complicated manufacturing processes and high costs.

JP-A-61-233904 WO2017/221727

An object of the present invention is to provide a composition for forming a heat storage and heat release layer, which has a high heat storage amount and heat generation amount, excellent resistance to repeated heat storage and heat release, and excellent adhesion to a substrate, and the composition. An object of the present invention is to provide a heat storage/radiation layer and a heat storage/radiation laminate.

The present invention relates to the following inventions [1] to [9].

[1] A composition for forming a heat-storage layer containing 2-amino-2-methyl-1,3-propanediol (A), a resin (B), and an organic solvent (C), wherein 2-amino-2 -Methyl-1,3-propanediol has an average primary particle size of 1 to 20 µm.

[2] The composition for forming a heat storage/radiation layer according to [1], wherein the solubility of the resin (B) in the organic solvent (C) at 25°C is 10% by mass or more.

[3] The composition for forming a heat storage/radiation layer according to [1] or [2], wherein the solubility of the resin (B) in water at 25°C is 5% by mass or less.

[4] The heat storage and release layer according to any one of [1] to [3], wherein the resin (B) is at least one resin selected from the group consisting of acrylic resins, epoxy resins, and polyester resins. Forming composition.

[5] [1] to [4], wherein the content of the 2-amino-2-methyl-1,3-propanediol (A) is 50 to 90% by mass relative to the total solid content in the composition; ] The composition for forming a heat storage/radiation layer according to any one of the items.

[6] A method for producing a composition for forming a heat storage/release layer containing 2-amino-2-methyl-1,3-propanediol (A), a resin (B), and an organic solvent (C),
For forming a heat storage and release layer, characterized in that a mixture of the 2-amino-2-methyl-1,3-propanediol (A), the resin (B), and the organic solvent (C) is dispersed by a media dispersing machine. A method of making the composition.

[7] A heat storage/release layer formed from the composition for forming a heat storage/release layer according to any one of [1] to [5], wherein 2-amino-2-methyl-1 in the heat storage/release layer , 3-propanediol having an average primary particle size of 1 to 20 μm.

[8] The heat storage/release layer according to [7], wherein the heat storage/release layer has a moisture content of 7.5% or less.

[9] A heat storage/radiation laminate comprising at least a substrate and the heat storage/radiation layer according to [7] or [8].

According to the present invention, a composition for forming a heat storage and heat release layer having a high heat storage amount and heat generation amount, excellent resistance to repeated heat storage and heat release, and excellent adhesion to a substrate, and a composition using the composition A heat storage layer and a heat storage laminate can be provided.

The composition for forming a heat storage and heat release layer of the present invention contains 2-amino-2-methyl-1,3-propanediol (A), a resin (B), and an organic solvent (C), and comprises 2-amino-2- The methyl-1,3-propanediol is characterized by having an average primary particle size of 1 to 20 μm. Since 2-amino-2-methyl-1,3-propanediol is fine particles with an average primary particle diameter of 1 to 20 μm, it can be uniformly dispersed in the resin, has little volume change, and has unevenness and unevenness. It is possible to form a heat storage and release layer in a good coating state with less As a result, excellent heat storage amount, heat generation amount, and resistance to repeated storage and release of heat are exhibited, and furthermore, excellent substrate adhesion is exhibited.
The present invention will be described in detail below.

<2-amino-2-methyl-1,3-propanediol (A)>
The composition for forming a heat storage layer of the present invention contains 2-amino-2-methyl-1,3-propanediol having an average primary particle size of 1 to 20 μm as a heat storage material. By including such fine particles of 2-amino-2-methyl-1,3-propanediol, when the heat storage layer is formed, 2-amino-2-methyl-1,3 - Propanediol has an average primary particle size of 1 to 20 µm, and can achieve excellent heat storage, heat generation, resistance to repeated storage and release of heat, and adhesion to substrates.
2-Amino-2-methyl-1,3-propanediol is a material that exhibits heat storage properties due to a phase change due to a solid-solid phase transition. It absorbs heat and maintains the endothermic state even if the temperature is lowered to around -50°C in the endothermic state. After that, heat is generated by heating from around -50°C to around 0°C to 70°C, physical stimulation, introduction of seed crystals, and the like. The content of 2-amino-2-methyl-1,3-propanediol (A) is 50 to 95% by mass, preferably 60% by mass, based on the total solid content in the composition, from the viewpoint of heat storage property. ~90% by mass.
The composition for forming a heat storage layer of the present invention can also use a heat storage material other than 2-amino-2-methyl-1,3-propanediol as a heat storage material. For example, paraffin wax, Inorganic oxides such as titanium oxide and vanadium oxide, polyhydric alcohols such as 2-methyl, 2-nitro, 1,3-propanediol, etc., can be mentioned. The proportion of 2-amino-2-methyl-1,3-propanediol is preferably 50% by mass or more.

<Resin (B)>
The composition for forming a heat storage and heat release layer of the present invention contains a resin (B). Conventionally known resins (B) can be used without limitation, and examples thereof include various resins such as thermoplastic resins, thermosetting resins, and UV-curable resins. The resin may be used alone or in combination of two or more.
Specific examples of the resin (B) include polyurethane resins, polyester resins, polyester urethane resins, urethane urea resins, alkyd resins, butyral resins, acetal resins, polyamide resins, acrylic resins, styrene-acrylic resins, styrene resins, and nitrocellulose. , benzyl cellulose, cellulose (tri) acetate, casein, shellac, gilsonite, styrene-maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene vinyl acetate resin , vinyl chloride/vinyl acetate copolymer resin, vinyl chloride/vinyl acetate/maleic acid copolymer resin, fluorine resin, silicon resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine Resin, ketone resin, petroleum resin, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, carboxymethyl Nitrocellulose, ethylene/vinyl alcohol resin, polyolefin resin, chlorinated polyolefin resin, modified chlorinated polyolefin resin, and chlorinated polyurethane resin, etc.

The resin (B) may be used in combination with a curing agent, if necessary. There are no restrictions on the curing agent that can be used, but examples include polyisocyanate and epoxy resin.

Further, as the resin (B), a component composed of oligomers and/or monomers and curable with electron beams or ultraviolet rays may be used.
Monofunctional monomers are not particularly limited, but examples include 2-(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, indecyl acrylate, isoctyl acrylate, tridecyl acrylate, caprolactone acrylate, 4-hydroxybutyl acrylate, ethoxylated nonyphenol acrylate, propoxylated nonylphenol acrylate, phenoxyethyl acrylate, phenoxydiethylene acrylate, ethylene oxide-modified nonylphenyl acrylate, methoxytriethylene glycol acrylate, ethylene oxide 2-ethylhexyl Acrylate, isobornyl acrylate, dipropylene glycol acrylate and the like, and methacrylate monomers thereof can be mentioned.

Bifunctional monomers include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated Neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, (hydrogenated) bisphenol A diacrylate, (hydrogenated) ethylene oxide-modified bisphenol A diacrylate, (hydrogenated) propylene glycol-modified bisphenol A diacrylate, 1, Examples include 6-hexanediol diacrylate, 2-ethyl, 2-butyl-propanediol diacrylate, 1,9-nonanediol diacrylate, and methacrylate monomers thereof.

Polyfunctional monomers include tris(2-hydroxyethyl) isocyanurate triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified glyceryl triacrylate, pentaerythritol triacrylate, and trimethylol. Propane acrylate, ethylene oxide-modified trimethylolpropane acrylate, propylene oxide-modified trimethylolpropane acrylate, tris(acryloxyethyl)isocyanurate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, ethoxylated pentaerythritol Examples include tetraacrylate, pentaacrylate ester, dipentaerythritol hexaacrylate, and methacrylate monomers thereof.

When a component composed of an oligomer and/or a monomer and curable by electron beams or ultraviolet rays is used as the resin (B), a photopolymerization initiator or a polymerization accelerator may be used in combination, if necessary.
The photopolymerization initiator is not particularly limited, and examples thereof include acetophenones, benzophenones, thioxanthones, aromatic diazonium salts, metallocenes and the like. Moreover, amines and phosphines are mentioned as a polymerization accelerator. When cross-linking is performed by electron beams, these may not be added.
In the case of cross-linking a cationic reactive component with ultraviolet rays, a cationic initiator may be used in combination as necessary. Examples of cationic initiators include diazonium salts of Lewis acids and iodonium salts of Lewis acids. Salts, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, borate initiators, and other photoacid generators. When cross-linking is performed by electron beams, these may not be added.

As the resin (B), at least one selected from the group consisting of acrylic resins, epoxy resins, and polyester resins is used from the viewpoint of uniformity of the sheet state, sheet strength, adhesion to the substrate, and heat storage properties. is preferred.

The solubility of the resin (B) in the organic solvent (C) at 25° C. described below is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the mass of (C). When the solubility is 30% by mass or more, the resin (B) is uniformly dissolved in the organic solvent (C), the 2-amino-2-methyl-1,3-propanediol is dispersed well, and the average primary Since the particle size is in the preferred range, particularly good heat storage and heat dissipation properties can be obtained.

Also, the solubility of the resin (B) in water at 25° C. is preferably less than 5% by mass, more preferably less than 1% by mass relative to the mass of water. When the solubility is less than 5% by mass, the particles can be in a dispersed state without dissolving the hydrophilic 2-amino-2-methyl-1,3-propanediol, so the sheet state can be obtained. uniformity, sheet strength, adhesion to the substrate, and good heat-storage properties can be obtained.

<Organic solvent (C)>
The composition for forming a heat storage layer of the present invention contains an organic solvent (C) for dispersing 2-amino-2-methyl-1,3-propanediol. The organic solvent (C) used is preferably a medium that is liquid at 25°C. Specifically, ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, propylene glycol 1-monomethyl ether 2-acetate, alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol. Aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, diisopropyl ketone and cyclohexanone; Available.

<Other ingredients>
The composition for forming a heat storage and heat release layer of the present invention can further contain a pigment dispersant, a pigment derivative, a surfactant, a flame retardant, a filler, and other various additives.
A pigment derivative is obtained by introducing a specific substituent into an organic pigment residue described in the Color Index. Examples of flame retardants include aluminum hydroxide, magnesium hydroxide, and phosphoric acid compounds. Additives include, for example, a coupling agent for enhancing adhesion to the substrate, an ion scavenger/antioxidant for enhancing reliability during moisture absorption and at high temperatures, and a leveling agent.

<Composition for forming heat storage layer>
The composition for forming a heat storage layer can be obtained by various methods, and may contain 2-amino-2-methyl-1,3-propanediol having an average primary particle size of 1 to 20 μm,
A composition containing 2-amino-2-methyl-1,3-propanediol having an average primary particle size of more than 20 μm may be subjected to refining treatment to adjust the average primary particle size to 1 to 20 μm.
Above all, it is preferable to perform dispersion treatment in order to adjust the average primary particle size of 2-amino-2-methyl-1,3-propanediol to 1 to 20 μm. For example, a mixture of a heat storage material containing 2-amino-2-methyl-1,3-propanediol and an organic solvent may be dispersed using a dispersing machine and then the resin component may be added. A mixture of 2-methyl-1,3-propanediol, a resin component and an organic solvent may be dispersed using a disperser.

There are no particular restrictions on the dispersing machine, and examples include kneaders, attritors, ball mills, sand mills using glass beads or zirconia beads, Scandex, Eiger mills, paint conditioners, media dispersing machines such as paint shakers, and colloid mills. can.

The average primary particle size of 2-amino-2-methyl-1,3-propanediol (A) in the composition for forming a heat storage/release layer of the present invention is There are no particular restrictions as long as the average primary particle size can be 1 to 20 μm. In addition, it is difficult to imagine that the average primary particle size will fluctuate in the process of forming the heat-storage/release layer from the composition, and the average primary particle size in the heat-storage/release layer is the same as the average particle size in the composition for forming the heat-storage/release layer. be.
The average primary particle size of 2-amino-2-methyl-1,3-propanediol is preferably 1 μm to 10 μm, more preferably 3 μm to 6 μm. When it is 1 μm or more, it has a particle shape different from a completely dissolved state, and when it is used as a heat storage and heat storage layer, heat storage and heat storage properties are expressed. It is presumed that the uniformity of the layer surface state is high, and the adhesion to the substrate and the heat storage property are improved. It is presumed that when the particle size is 20 μm or less, a uniform surface condition of the heat storage and release layer can be obtained, and the heat storage and release properties are improved due to an appropriate particle state.

Further, the mass ratio (A):(B) of 2-amino-2-methyl-1,3-propanediol (A) and resin (B) is 50:50 to 90:10, preferably 60: 40 to 90:10, more preferably 70:30 to 80:20. A ratio of 2-amino-2-methyl-1,3-propanediol (A) of 50% or more is preferable because good heat storage and heat dissipation properties are exhibited. When it is 60% or more, the heat storage and release amount is further improved, which is preferable. Further, when it is 90% or less, the strength of the heat storage/radiation layer is improved, which is preferable.

<Heat-storage layer, heat-storage sheet, heat-storage laminate>
The heat storage and release layer of the present invention is formed from the composition for forming a heat storage and release layer. is dispersed, and the average primary particle size of 2-amino-2-methyl-1,3-propanediol is 1 to 20 μm. As described above, when the average primary particle size of the 2-amino-2-methyl-1,3-propanediol is within a predetermined range, excellent heat storage properties, resistance to repeated heat storage, and excellent base Adhesion to the material can be achieved.

As for the amount of heat absorption and heat of the heat storage and heat storage layer of the present invention, it is preferable that the amount of heat absorption is 50 J/g or more and the amount of heat generation is 30 J/g or more. More specifically, it absorbs heat in the process of increasing the temperature from 25°C to 95°C, does not generate heat when the temperature is decreased from 95°C to -50°C, but maintains the endothermic state, and generates heat when the temperature is increased from this state to 70°C. Even if it is repeated, heat absorption and heat generation occur again. Specifically, from the state where heat is generated when the temperature is raised to 70° C., heat is absorbed again in the process of raising the temperature to 95° C., and when the temperature is lowered from 95° C. to −50° C., the endothermic state is maintained without generating heat. to 70°C.
This repeated heat storage resistance relates to the average primary particle size of 2-amino-2-methyl-1,3-propanediol (A), which is more preferably 1 to 10 μm, particularly preferably 3 to 6 μm. be. An average primary particle size of 1 to 10 μm is preferable because it exhibits excellent resistance to repeated heat and heat storage.

The heat storage and heat generation layer of the present invention has a high heat storage amount and heat generation amount, has excellent resistance to repeated heat storage and heat release, and further has excellent adhesion to the substrate. From the viewpoint of controlling the average primary particle size of 2-amino-2-methyl-1,3-propanediol to 1 to 20 μm, the moisture content of the heat storage and release layer is preferably low, preferably less than 10%, and more It is preferably less than 5%, more preferably less than 1.5%, and particularly preferably less than 0.5%.

The heat storage/radiation laminate of the present invention has at least a substrate and the heat storage/radiation layer described above.
The heat storage/radiation layered product can be produced by applying a heat storage layer-forming composition onto a base material and drying the composition.
Examples of the coating method include known methods such as gravure printing, flexographic printing, inkjet printing, coater coating, spray coating, and spin coater. More specifically, for example, the heat storage layer and the heat storage layer and the heat storage laminate of the present invention are prepared by coating a composition for forming a heat storage layer on one main surface of a base material by a roll coating method, a spin coating method, a dip coating method, a A coating film is formed by applying various coating methods such as spray coating, bar coating, slit coating, slit & spin coating, flow coating, and die coating, and the organic solvent is removed from the coating film. It can be easily obtained by forming a coating film and, if necessary, curing the coating film.

The substrate is not particularly limited, but for example, glass substrates, plastic substrates, metal substrates, paper substrates, wood substrates (wooden substrates), stone substrates, cloth substrates, leather A base material etc. can be mentioned. Moreover, the shape thereof includes a flat plate, a film, a sheet, a three-dimensional shape, and the like, and can be appropriately selected based on the intended use and conditions of use.
As the substrate, it is preferable to use films of synthetic resins such as polyester, polypropylene, polyethylene and nylon, composites of these films, and glass.

Moreover, the heat storage and heat storage layer of the present invention may be used alone, and can be used as, for example, a heat storage and heat storage sheet. When the heat storage and heat storage layer is obtained alone, for example, the heat storage and heat storage layer forming composition can be applied to a release substrate, dried, and then peeled off from the release substrate to obtain the heat storage and heat storage layer alone. Examples of the releasable substrate include resin films such as polyester films, polyethylene films, polypropylene films, and polyimide films that have undergone release treatment.
In addition, when used as a heat storage sheet, flexibility and tensile strength are required in order to suppress cracking during processing and transportation. In order to express such physical properties, a thermoplastic resin can be preferably used as the resin (B) because it is easy to form a coating film. Thermoplastic resins include vinyl chloride resins, acrylic resins, urethane resins, olefin resins, ethylene-vinyl acetate copolymer, styrene-butadiene resins, polystyrene resins, polybutadiene resins, polyester resins, and polyamide resins. , polyimide resins, polycarbonate resins, 1,2-polybutadiene resins, polycarbonate resins, polyimide resins, and the like. Among them, it is preferable to use a vinyl chloride resin because it is easy to obtain moldability at low temperatures and dispersibility of the heat storage material.

Further, when the heat storage sheet of the present invention is used by being attached to an object, the heat storage sheet may be provided with an adhesive layer containing an adhesive. The adhesive is not particularly limited as long as it is a material having adhesiveness after coating, but in order to avoid dissolution of 2-amino-2-methyl-1,3-propanediol, a water-insoluble adhesive is preferable. . Examples of adhesives include acrylic adhesives, urethane adhesives, silicon adhesives, rubber adhesives, and the like. The coating amount of the adhesive layer is not particularly limited and can be appropriately selected according to the adhesive used and the desired adhesive strength, but is generally about 3 to 50 g/m ² .

The film thickness of the heat storage and heat storage sheet of the present invention is preferably 20 μm or more, more preferably 80 μm or more, and particularly preferably 150 μm or more. When the film thickness is 20 μm or more, the content of 2-amino-2-methyl-1,3-propanediol in the coating film becomes a sufficient amount to exhibit good heat storage property, and the coating It is preferable because the uniformity of the coating film is improved at the time and the adhesion to the substrate is excellent.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Parts and % in the present invention represent parts by mass and % by mass unless otherwise specified.

<Adjustment of Resin (B)>
Resin B1: acrylic resin (solid content 100%)
(Product name: Dianal BR80, manufactured by Mitsubishi Chemical Corporation)
Resin B2: epoxy resin (solid content 100%)
(Product name: jER1007, manufactured by Mitsubishi Chemical Corporation)
Resin B3: polyester resin (solid content 100%)
(Product name: Byron 200, manufactured by Toyobo Co., Ltd.)
Resin B4: cycloolefin resin (solid content 100%)
(trade name ZEONEX480R, manufactured by Nippon Zeon Co., Ltd.)

(Resin solution B1-1)
30 parts of resin B1 and 70 parts of methyl ethyl ketone were stirred and mixed to obtain a resin solution (B1-1) having a solid concentration of 30% by mass.

(Resin solution B1-2)
30 parts of resin B1 and 70 parts of hexane were stirred and mixed to obtain a resin solution (B1-2) having a solid concentration of 30% by mass.

(Resin solution B2-1)
30 parts of resin B2 and 70 parts of methyl ethyl ketone were stirred and mixed to obtain a resin solution (B2-1) having a solid concentration of 30% by mass.

(Resin solution B2-2)
30 parts of resin B2 and 70 parts of propylene glycol 1-monomethyl ether 2-acetate were stirred and mixed to obtain a resin solution (B2-2) having a solid concentration of 30% by mass.

(Resin solution B3-1)
30 parts of resin B3 and 70 parts of methyl ethyl ketone were stirred and mixed to obtain a resin solution (B3-1) having a solid concentration of 30% by mass.

(Resin solution B4-1)
30 parts of resin B4 and 70 parts of methyl ethyl ketone were stirred and mixed to obtain a resin solution (B4-1) having a solid concentration of 30% by mass.

(Resin solution B5-1)
Resin B5 (manufactured by Mitsui Chemicals, Inc. "WS-5000" (aqueous urethane resin, solid content concentration 30% by mass)) was used as a resin solution (B5-1).

<Production of composition for forming heat storage layer>
[Example 1]
(Composition 1 for forming a heat storage layer)
7.5 parts of 2-amino-2-methyl-1,3-propanediol, 8.33 parts of resin solution (B1-1), 31.8 parts of methyl ethyl ketone, and 20 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed, and dispersed with a paint shaker for 1.5 hours to obtain a composition 1 for forming a heat storage/radiation layer.

[Examples 2 to 8]
(Compositions 2 to 8 for forming a heat storage layer)
Compositions 2 to 8 for forming a heat storage layer were obtained in the same manner as for Composition 1 for forming a heat storage layer, except that the resin solution, organic solvent, and dispersion time shown in Table 1 were changed.

[Example 9]
(Composition 9 for forming a heat storage layer)
7.5 parts of 2-amino-2-methyl-1,3-propanediol, 6.66 parts of resin solution (B1-1), 0.5 parts of dispersant BYK111 (manufactured by BYK Chemie Co., Ltd.), methyl ethyl ketone 31 8 parts and 20 parts of glass beads with a diameter of 3 mm were placed in a container, stirred and mixed, and dispersed with a paint shaker for 1.5 hours to obtain a composition 9 for forming a heat storage/radiation layer.

[Example 10]
(Composition 10 for forming a heat storage layer)
4.5 parts of 2-amino-2-methyl-1,3-propanediol, 18.3 parts of resin solution (B1-1), 45.7 parts of methyl ethyl ketone, and 28 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed, and dispersed with a paint shaker for 1.5 hours to obtain a composition 10 for forming a heat storage layer.

[Example 11]
(Composition 11 for forming a heat storage layer)
5.5 parts of 2-amino-2-methyl-1,3-propanediol, 15.0 parts of resin solution (B1-1), 41.0 parts of methyl ethyl ketone, and 26 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed and dispersed with a paint shaker for 1.5 hours to obtain a composition 11 for forming a heat storage layer.

[Example 12]
(Composition 12 for forming a heat storage layer)
8.5 parts of 2-amino-2-methyl-1,3-propanediol, 5.0 parts of resin solution (B1-1), 33.7 parts of methyl ethyl ketone, and 17 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed and dispersed with a paint shaker for 1.5 hours to obtain a composition 12 for forming a heat storage layer.

[Example 13]
(Composition 13 for forming a heat storage layer)
9.5 parts of 2-amino-2-methyl-1,3-propanediol, 1.7 parts of resin solution (B1-1), 33.5 parts of methyl ethyl ketone, and 14 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed, and dispersed with a paint shaker for 1.5 hours to obtain a composition 13 for forming a heat storage layer.

[Comparative Example 1]
(Composition 101 for forming a heat storage layer)
7.5 parts of 2-amino-2-methyl-1,3-propanediol, 8.33 parts of resin solution (B1-1), 31.8 parts of methyl ethyl ketone, and 20 parts of glass beads with a diameter of 3 mm were placed in a container, They were stirred and mixed to obtain a heat storage sheet composition 101 .

[Comparative Example 2]
(Composition 102 for forming a heat storage layer)
A composition 102 for forming a heat storage layer was obtained in the same manner as the composition 101 for forming a heat storage layer except that the resin solution (B2-1) was used.

[Comparative Example 3]
(Composition 103 for forming a heat storage layer)
10 parts of 2-amino-2-methyl-1,3-propanediol, 30 parts of methyl ethyl ketone, and 20 parts of glass beads with a diameter of 3 mm are placed in a container, stirred and mixed, and dispersed with a paint shaker for 1.5 hours to form a heat storage layer. A forming composition 13 was obtained.

[Comparative Example 4]
(Composition 104 for forming a heat storage layer)
7.5 parts of 2-amino-2-methyl-1,3-propanediol, 8.33 parts of resin solution (B5-1), 31.8 parts of water, and 20 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed to obtain a composition 104 for forming a heat storage layer.

[Comparative Example 5]
(Composition 105 for forming a heat storage layer)
A heat-storage sheet composition 105 was obtained in the same manner as the heat-storage sheet composition 104, except that the resin solution (B1-1) was used.

[Comparative Example 6]
(Composition 106 for forming a heat storage layer)
7.5 parts of 2-methyl-2-nitro-1,3-propanediol, 8.33 parts of resin solution (B1-1), 31.8 parts of methyl ethyl ketone, and 20 parts of glass beads with a diameter of 3 mm were placed in a container, The mixture was stirred and mixed and dispersed with a paint shaker for 1.5 hours to obtain a composition 106 for forming a heat storage layer.

The obtained composition for forming a heat storage layer is shown in Table 1 together with the solubility of the resin (B) in the organic solvent (C) at 25°C and the solubility of the resin (B) in water at 25°C.

Abbreviations in Table 1 are shown.
MEK: methyl ethyl ketone PGMAC: propylene glycol 1-monomethyl ether 2-acetate

<Production of heat storage layer (free film)>
[Example 14]
(Storage and heat release layer 1)
The composition 1 for forming a heat storage layer is applied to the release surface of a release sheet (a polyethylene terephthalate film with a thickness of 75 μm and a release treatment) using a blade coater, dried at 40° C. for 20 minutes, and then the release film is removed. It was peeled off to obtain a heat storage/radiation layer 1 having a film thickness of 200 μm.

[Examples 15-26, Comparative Examples 7-12]
(Storage and release layers 2 to 13, 101 to 106)
Heat storage and release layers 2 to 13 and 101 to 106 were obtained in the same manner as for heat storage and release layer 1, except that composition 1 for forming heat storage layer was changed to one shown in Table 2.

[Example 27]
(Storage and heat release layer 14)
A blade coater was used to apply the composition 1 for forming a heat storage layer to the release surface of a release sheet (75 μm-thick release-treated polyethylene terephthalate film), dried at 40° C. for 20 minutes, and dried at 25° C. with a humidity of 80. After standing for 5 minutes in an environment of % RH, the release film was peeled off to obtain a heat storage and release layer 14 having a thickness of 200 μm.

[Example 28]
(Storage and heat release layer 15)
A heat-storage layer 15 was obtained in the same manner as for the heat-storage layer 14 except that the standing time was changed to 20 minutes.

[Example 29]
(Storage and heat release layer 16)
A heat-storage layer 16 was obtained in the same manner as the heat-storage layer 14 except that the standing time was changed to 60 minutes.

<Evaluation of heat storage layer (free film)>
The following evaluations were carried out on the obtained heat storage/radiation layer. Table 2 shows the results.

[Average primary particle size]
Using a digital microscope VHX900 manufactured by Keyence Corporation, arbitrarily select 10 particles of the heat storage material observed in the field of view with a lens magnification of 1000 times, visually measure the primary particle diameter, and the average value is the average primary particle diameter.

[Water content]
The moisture content of the heat storage/radiation layer was obtained by the Karl Fischer titration method (moisture vaporization method) of JIS K0068:2001 (Method for measuring moisture content of chemical products). Specifically, a 50.0 mg sample was collected from the heat storage and heat release layer using an electronic balance, and set in a Karl Fischer moisture meter (coulometric method) MKC-610 manufactured by Kyoto Electronics Industry Co., Ltd. and a moisture vaporizer ADP-611. The amount of water was measured, and the water content was converted into a ratio per unit mass of the composition to obtain the water content of the heat storage/radiation layer.
The measurement was carried out using ChemAqua anolyte AKE and ChemAqua catholyte CGE manufactured by Kyoto Electronics Industry Co., Ltd. as the anolyte and catholyte, respectively, at a measurement temperature of 140° C., using nitrogen as the carrier gas, and at a flow rate of 200 mL/ I went as min.

[The heat absorption and heat absorption and the cycle resistance of the heat absorption and heat]
Using Mettler-Toledo's "DSC-1", about 5 mg of the heat storage and release layer was weighed into a standard aluminum container, and the heat absorption and heat generation were determined from the differential heat curve of the reversible component in the cycle test described below. .
1st cycle: The temperature was raised from 25° C. to 95° C. at a rate of 10° C./min, and the amount of heat absorbed during that time was calculated. After maintaining the temperature at 95° C. for 5 minutes, the temperature was lowered from 95° C. to −50° C. at a rate of 10° C./min, and the temperature was maintained at −50° C. for 5 minutes. Next, the temperature was raised from -50°C to 70°C at a rate of 10°C/min, and the amount of heat generated during that time was calculated.
For example, in the first cycle of Example 1, the endothermic amount was 141 J / g in the temperature rising process from 25 ° C. to 95 ° C. After the temperature was lowered to -50 ° C., the temperature was raised from -50 ° C. to 70 ° C. , the calorific value is 97 J/g. Therefore, the amount of heat absorbed in the first cycle is 141 J/g, and the amount of heat generated is 97 J/g.
Second cycle: After the end of the first cycle, the temperature was raised to 95°C at a rate of 10°C/min, and the amount of heat absorbed during that time was calculated. After maintaining the temperature at 95° C. for 5 minutes, the temperature was lowered from 95° C. to −50° C. at a rate of 10° C./min, and the temperature was maintained at −50° C. for 5 minutes. Next, the temperature was raised from -50°C to 70°C at a rate of 10°C/min, and the amount of heat generated during that time was calculated.
After the 3rd cycle: The temperature was raised, lowered, and raised in the same manner as in the 2nd cycle, and the amount of heat absorbed and the amount of heat generated were calculated.

[Fever due to external stimulation]
The heat storage/radiation layers 1 to 16 and the heat storage/radiation laminates 1 to 16 thus obtained were heated from 25° C. to 95° C. at a rate of 10° C./min in the same manner as in the cycle test described above to absorb heat. C. for 5 minutes, then the temperature was lowered from 95.degree. C. to -50.degree. C. at a rate of 10.degree. Subsequently, by poking the surface of the heat storage/radiation layer 1 once with the tip of a spatula, it was confirmed that heat was generated without going through the second heating step. On the other hand, it was confirmed that heat storage/radiation layers 101 to 106 and heat storage/radiation laminates 1 to 16 did not generate heat even when similar actions were performed.

<Manufacturing heat-storage laminate>
[Example 30]
(Storage and heat release laminate 1)
On a polyester film (Toyobo Co., Ltd., E5101, thickness 188 μm), which is a substrate, the composition 1 for forming a heat storage layer is coated using a blade coater, dried at 40 ° C. for 20 minutes, and a film is formed on the substrate. A heat-storage laminate 1 having a heat-storage layer with a thickness of 200 μm was obtained.

[Examples 31-42, Comparative Examples 13-18]
(Storage and heat release laminates 2 to 13, 101 to 106)
The same method as for the heat storage layer laminate 1 was performed except that the heat storage layer forming composition described in Table 2 was used instead of the heat storage layer forming composition 1, and the film thickness was adjusted by the number of the blade coater. to obtain heat storage/radiation laminates 2 to 13 and 101 to 106 having a heat storage/radiation layer having a film thickness of 200 μm on the substrate.

[Example 43]
(Storage and heat release laminate 14)
On a polyester film (Toyobo Co., Ltd., E5101, thickness 188 μm), which is a base material, the composition 1 for forming a heat storage layer is coated using a blade coater, dried at 40° C. for 20 minutes, and dried at 25° C. and a humidity of 80%. After standing for 60 minutes in a RH environment, a heat storage/radiation laminate 14 having a heat storage layer with a film thickness of 200 μm on the substrate was obtained.

[Example 44]
(Storage and heat release laminate 15)
A heat-storage laminate 15 was obtained in the same manner as the heat-storage laminate 14 except that the standing time was changed to 120 minutes.

[Example 45]
(Storage and heat release laminate 16)
A heat-storage laminate 16 was obtained in the same manner as the heat-storage laminate 14 except that the standing time was changed to 300 minutes.

<Evaluation of heat storage/radiation laminate>
The obtained heat storage/radiation laminate was evaluated as follows. Table 2 shows the results.

[exterior]
The surface state of the heat storage and heat storage layer was visually observed from the side of the heat storage and heat release layer, and evaluated according to the following criteria.
◎: There is no unevenness, it is in a uniform state (very good)
○: Very slightly uneven (good)
△: Slightly uneven (can be used)
×: Clear unevenness (cannot be used)

[Substrate Adhesion]
Cellophane tape (18 mm width, manufactured by Nichiban Co., Ltd.) was affixed to the surface of the heat storage and heat storage layer, and a peeling test was performed in the vertical direction. Evaluation criteria are as follows.
◯: Less ink peeling (less than 10%) (good)
△: Ink peeling (10% or more, less than 50%) (usable)
×; There is considerable peeling of ink (50% or more) (cannot be used)

Abbreviations in Table 2 are shown.
AMP: 2-amino-2-methyl-1,3-propanediol

Examples 1 to 5 (Examples 14 to 18 and 30 to 34) use a preferable resin from the viewpoint of solubility in the organic solvent (C) and water, and have undergone an appropriate dispersion process, 2-Amino-2-methyl-1,3-propanediol had a good average primary particle size, and had good heat storage capacity and repeated resistance.
In addition, the water content of the heat storage layer is important, and in Examples 14 to 16 (Examples 27 to 29, 43 to 45), the increase in the water content resulted in a decrease in the heat storage amount. It is presumed that this is because part of 2-amino-2-methyl-1,3-propanediol became dissolved.
Examples 10-13 (Examples 23-26, 39-42) vary the ratio of 2-amino-2-methyl-1,3-propanediol to resin, and 2-amino-2-methyl- When the concentration of 1,3-propanediol is low, the amount of heat and heat storage decreases, while when the concentration is high, the dispersibility decreases, the average primary particle size becomes relatively large, and the repeated resistance related to heat and heat storage performance decreases. did.

On the other hand, Comparative Examples 101 and 102 (Comparative Examples 7, 8, 13, and 14) are similar to Examples 1 to 5 in that they use preferable resins, but the average primary particle diameter was very large, and the repeated resistance related to the heat storage and heat dissipation performance was poor. Furthermore, the coating film was conspicuously rough, and the adhesion to the substrate was also deteriorated.
Comparative Example 103 (Comparative Examples 9 and 15) did not contain a resin, so a good dispersion state was not obtained, the average primary particle size was large, and the repeated resistance related to the heat storage and release performance was poor. Furthermore, the coating film was conspicuously rough, and the adhesion to the substrate was also deteriorated.
In Comparative Example 104 (Comparative Examples 10 and 16), the solubility of the resin in water is as high as 30% or more, and 2-amino-2-methyl-1,3-propanediol is in a dissolved state, so heat storage and heat generation are exhibited. A suitable crystal structure could not be obtained, and the heat storage property was not exhibited.
Comparative Example 105 (Comparative Examples 11 and 17) contains water, but the solubility of the resin in water is as low as less than 1%, so a good dispersion state cannot be obtained, and the average primary particle size is large. Repeated resistance related to heat dissipation performance was poor. Furthermore, the coating film was conspicuously rough, and the adhesion to the substrate was also deteriorated.
In Comparative Example 106 (Comparative Examples 12 and 18), 2-amino-2-methyl-1,3-propanediol was not used, so in the heating step during the special heating/cooling step like the present invention, Pyrogenicity could not be confirmed.

Claims (8)

A composition for forming a heat storage layer containing 2-amino-2-methyl-1,3-propanediol (A), a resin (B), and an organic solvent (C), wherein 2-amino-2-methyl- A composition for forming a heat-storage layer, wherein the average primary particle size of 1,3-propanediol is from 1 to 20 μm. The composition for forming a heat storage and heat release layer according to claim 1, wherein the solubility of the resin (B) in the organic solvent (C) at 25°C is 10% by mass or more. The composition for forming a heat storage/radiation layer according to claim 1 or 2, wherein the solubility of the resin (B) in water at 25°C is 5% by mass or less. The composition for forming a heat storage layer according to any one of claims 1 to 3, wherein the resin (B) is at least one resin selected from the group consisting of acrylic resins, epoxy resins, and polyester resins. Any one of claims 1 to 4, wherein the content of the 2-amino-2-methyl-1,3-propanediol (A) is 50 to 90% by mass relative to the total solid content in the composition. The composition for forming a heat storage and heat release layer according to 1. A heat storage/release layer formed from the composition for forming a heat storage/release layer according to any one of claims 1 to 5, wherein 2-amino-2-methyl-1,3-propanediol in the heat storage/release layer The average primary particle size of the heat storage and release layer is 1 to 20 μm. The heat storage/release layer according to claim 6 , wherein the heat storage/release layer has a moisture content of 7.5% or less. A heat storage/radiation laminate comprising at least a substrate and the heat storage/radiation layer according to claim 6 or 7 .