WO2021241167A1 - Corps de stockage de chaleur et procédé de fabrication de corps de stockage de chaleur - Google Patents

Corps de stockage de chaleur et procédé de fabrication de corps de stockage de chaleur Download PDF

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Publication number
WO2021241167A1
WO2021241167A1 PCT/JP2021/017520 JP2021017520W WO2021241167A1 WO 2021241167 A1 WO2021241167 A1 WO 2021241167A1 JP 2021017520 W JP2021017520 W JP 2021017520W WO 2021241167 A1 WO2021241167 A1 WO 2021241167A1
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WIPO (PCT)
Prior art keywords
heat storage
storage body
microcapsules
resin
preferable
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PCT/JP2021/017520
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English (en)
Japanese (ja)
Inventor
哲朗 三ツ井
優樹 中川
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富士フイルム株式会社
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Publication of WO2021241167A1 publication Critical patent/WO2021241167A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to a heat storage body and a method for manufacturing the heat storage body.
  • Patent Document 1 discloses a heat storage sheet-shaped molded body obtained by molding and curing a heat storage acrylic resin composition containing a predetermined amount of microcapsules containing a heat storage material into a sheet shape.
  • the present inventors increased the amount of microcapsules containing a heat storage material as described in Patent Document 1, and when handling the obtained heat storage material (particularly when the heat storage material was pulled). , It was found that defects (for example, cracks and cracks) are likely to occur in the heat storage body. In particular, when the heat storage body is thick, defects are likely to occur in the heat storage body.
  • Another object of the present invention is to provide a heat storage body in which the occurrence of defects during handling is suppressed. Another object of the present invention is to provide a method for producing a heat storage body.
  • a heat storage body containing a microcapsule containing a heat storage material and a resin The content of the heat storage material with respect to the total mass of the heat storage body is 65% by mass or more. A heat storage body having a porosity of less than 10% by volume.
  • the heat storage body according to any one of (1) to (4), wherein the elongation at break of the resin is 300% or more.
  • the heat storage body according to any one of (1) to (5), wherein the ratio of the thickness of the capsule wall of the microcapsule to the volume-based median diameter of the microcapsule is 0.0075 or less.
  • the heat storage body according to any one of (1) to (6), wherein the thickness of the capsule wall of the microcapsule is 0.20 ⁇ m or less.
  • the heat storage body according to any one of (1) to (7), wherein the deformation rate of the microcapsules is 35% or more.
  • the heat storage body according to any one of (1) to (8), wherein the capsule wall of the microcapsule and the resin have the same functional group.
  • a method for producing a heat storage body which comprises producing a heat storage body using a composition for forming a heat storage body containing microcapsules, a resin, and water.
  • the present invention it is possible to provide a heat storage body in which the occurrence of defects during handling is suppressed. Further, according to the present invention, it is also possible to provide a method for producing a heat storage body.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • the various components described later may be used alone or in combination of two or more.
  • the polyisocyanate described later may be used alone or in combination of two or more.
  • the heat storage body of the present invention contains a predetermined amount of heat storage material and has a porosity of less than 10% by volume. According to the heat storage body of the present invention, the occurrence of defects during handling can be suppressed. This is presumed to be due to the following reasons. As the amount of microcapsules containing the heat storage material increases, defects are likely to occur in the heat storage material. It is considered that by lowering the porosity of such a heat storage material, the contact area between the microcapsules in the heat storage body is widened, and the strength of the heat storage body is improved. As a result, it is presumed that the brittleness of the heat storage body is increased and the occurrence of defects (for example, cracks and cracks) during handling of the heat storage body can be suppressed.
  • defects for example, cracks and cracks
  • the heat storage material of the present invention contains microcapsules containing the heat storage material and a resin, and the content ratio of the heat storage material to the total mass of the heat storage material is 65% by mass or more, and the void ratio is less than 10% by volume.
  • the materials contained in the heat storage body will be described in detail first, and then the characteristics of the heat storage body will be described in detail.
  • the microcapsule has a core portion and a capsule wall for encapsulating a core material (encapsulated material (also referred to as an encapsulating component)) forming the core portion.
  • encapsulated material also referred to as an encapsulating component
  • the microcapsule contains a heat storage material as a core material (inclusion component). Since the heat storage material is encapsulated in microcapsules, the heat storage material can stably exist in a phase state depending on the temperature.
  • the type of heat storage material is not particularly limited, and a material that changes phase in response to a temperature change can be used, and the phase change between the solid phase and the liquid phase that accompanies the state change of melting and solidification in response to the temperature change is repeated. Materials that can be used are preferred.
  • the phase change of the heat storage material is preferably based on the phase change temperature of the heat storage material itself, and in the case of the phase change between the solid phase and the liquid phase, it is preferably based on the melting point.
  • the heat storage material for example, a material that can store heat generated outside the heat storage body as sensible heat and a material that can store heat generated outside the heat storage body as latent heat (hereinafter, also referred to as "latent heat storage material”. ), A material that causes a phase change due to a reversible chemical change, or the like.
  • the heat storage material is preferably one that can release the stored heat.
  • the latent heat storage material is preferable as the heat storage material in terms of ease of control of the amount of heat that can be transferred and received and the size of the amount of heat.
  • the latent heat storage material is a material that stores heat generated outside the heat storage body as latent heat.
  • a phase change between a solid phase and a liquid phase it refers to a material capable of transferring heat by latent heat by repeating a change between melting and solidification with the melting point determined by the material as the phase change temperature.
  • the latent heat storage material utilizes the heat of fusion at the melting point and the heat of solidification at the freezing point, and can store heat and dissipate heat with the phase change between the solid and the liquid.
  • the type of the latent heat storage material is not particularly limited, and can be selected from compounds having a melting point and capable of a phase change.
  • Examples of the latent heat storage material include ice (water); inorganic salts; aliphatic hydrocarbons such as paraffin (for example, isoparaffin and normal paraffin); tri (capryl capric acid) glyceryl, methyl myristate (melting point 16-19 ° C.).
  • Fatty acid ester compounds such as isopropyl myristate (melting point 167 ° C.) and dibutyl phthalate (melting point ⁇ 35 ° C.); alkylnaphthalene compounds such as diisopropylnaphthalene (melting point 67-70 ° C.), 1-phenyl-1. -Diarylalkane compounds such as xylylethane (melting point less than -50 ° C), alkylbiphenyl compounds such as 4-isopropylbiphenyl (melting point 11 ° C), triarylmethane compounds, alkylbenzene compounds, benzylnaphthalene compounds, diarylalkylene compounds.
  • Fatty acid ester compounds such as isopropyl myristate (melting point 167 ° C.) and dibutyl phthalate (melting point ⁇ 35 ° C.); alkylnaphthalene compounds such as diisopropylnaphthalen
  • Aromatic hydrocarbons such as compounds and arylindan compounds; natural animal and vegetable oils such as camellia oil, soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, palm oil, castor oil, and fish oil; mineral oil; diethyl ethers. ; Fat group diols; sugars; sugar alcohols and the like.
  • the phase change temperature of the heat storage material is not particularly limited, and may be appropriately selected depending on the type of the heating element that generates heat, the heating element temperature of the heating element, the temperature or holding temperature after cooling, the cooling method, and the like.
  • the heat storage material it is preferable to select a material having a phase change temperature (preferably melting point) in a target temperature range (for example, the operating temperature of the heating element; hereinafter also referred to as “heat control region”).
  • the phase change temperature of the heat storage material varies depending on the heat control region, but is preferably 0 to 80 ° C, more preferably 10 to 70 ° C.
  • the heat storage material having the following melting points is preferable.
  • a heat storage material having a melting point of 0 to 80 ° C. is preferable.
  • the material having a melting point of less than 0 ° C. or more than 80 ° C. is not included in the heat storage material.
  • the material having a melting point of less than 0 ° C. or more than 80 ° C. the material in a liquid state may be used in combination with the heat storage material as a solvent.
  • a heat storage material having a melting point of 10 to 70 ° C. is preferable.
  • the material having a melting point of less than 10 ° C. or more than 70 ° C. is not included in the heat storage material.
  • the materials having a melting point of less than 10 ° C. or more than 70 ° C. the material in a liquid state may be used in combination with the heat storage material as a solvent.
  • a heat storage material having a melting point of 15 to 50 ° C. is preferable. When a heat storage material having a melting point of 15 to 50 ° C.
  • the material having a melting point of less than 15 ° C. or more than 50 ° C. is not included in the heat storage material.
  • the material having a melting point of less than 15 ° C. or more than 50 ° C. the material in a liquid state may be used in combination with the heat storage material as a solvent.
  • a heat storage material having a melting point of 20 to 62 ° C. is also preferable.
  • heating elements of thin or portable electronic devices such as notebook computers, tablets, and smartphones often have an operating temperature of 20 to 65 ° C, and it is suitable to use a heat storage material having a melting point of 20 to 62 ° C. ing.
  • the material having a melting point of less than 20 ° C. or more than 62 ° C. is not included in the heat storage material.
  • the material in a liquid state may be used in combination with a heat storage material as a solvent, but the fact that the material does not contain a solvent produces a large amount of heat generated by the heating element. It is preferable in that it absorbs heat.
  • an aliphatic hydrocarbon is preferable as the latent heat storage material, and paraffin is more preferable, in that the heat storage property of the heat storage body is more excellent and the void ratio of the microcapsules can be reduced.
  • the melting point of the aliphatic hydrocarbon is not particularly limited, but is preferably 0 ° C. or higher, more preferably 15 ° C. or higher, still more preferably 20 ° C. or higher in terms of application of the heat storage member to various uses.
  • the upper limit is not particularly limited, but is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, further preferably 60 ° C. or lower, and particularly preferably 50 ° C. or lower.
  • a linear aliphatic hydrocarbon is preferable in that the heat storage property of the heat storage member is more excellent.
  • the number of carbon atoms of the linear aliphatic hydrocarbon is not particularly limited, but 14 or more is preferable, 16 or more is more preferable, and 17 or more is further preferable.
  • the upper limit is not particularly limited, but is preferably 26 or less.
  • a linear aliphatic hydrocarbon having a melting point of 0 ° C. or higher is preferable, and a linear aliphatic hydrocarbon having a melting point of 0 ° C. or higher and having 14 or more carbon atoms is more preferable. preferable.
  • linear aliphatic hydrocarbon having a melting point of 0 ° C. or higher
  • linear aliphatic hydrocarbon melting point paraffin
  • melting point 6 ° C. melting point 6 ° C.
  • n-pentadecane melting point 10 ° C.
  • n-hexadecane melting point 18 ° C.
  • n-heptadecan (melting point 22 °C), n-octadecane (melting point 28 °C), n-nonadecan (melting point 32 °C), n-eicosan (melting point 37 °C), n-henikosan (melting point 40 °C), n- Docosan (melting point 44 ° C), n-tricosan (melting point 48-50 ° C), n-tetracosan (melting point 52 ° C), n-pentacosan (melting point 53-56 ° C), n-hexakosan (melting point 57 ° C), n-heptacosan (Melting point 60 ° C.), n-octacosane (melting point 62 ° C.), n-nonakosan (melting point 63-66 ° C.), and n-triacontane (melting
  • n-heptadecan (melting point 22 ° C.), n-octadecane (melting point 28 ° C.), n-nonadecan (melting point 32 ° C.), n-eicosan (melting point 37 ° C.), n-henikosan (melting point 40 ° C.), n- Docosan (melting point 44 ° C), n-tricosan (melting point 48-50 ° C), n-tetracosan (melting point 52 ° C), n-pentacosan (melting point 53-56 ° C), n-hexakosan (melting point 60 ° C), n-heptacosan (Melting point 60 ° C.) or n-octacosane (melting point 62 ° C.) is preferable.
  • the content of the linear aliphatic hydrocarbon is preferably 80% by mass or more, preferably 90% by mass or more, based on the content of the heat storage material. Is more preferable, 95% by mass or more is further preferable, and 98% by mass or more is particularly preferable.
  • the upper limit is 100% by mass.
  • an inorganic hydrate is preferable, and for example, an alkali metal chloride hydrate (eg, sodium chloride dihydrate, etc.) and an alkali metal acetate hydrate (eg, sodium acetate water) are preferable.
  • alkali metal sulfate hydrate eg, sodium sulfate hydrate, etc.
  • alkali metal thiosulfate hydrate eg, thiosulfate sodium hydrate, etc.
  • alkaline earth metal examples thereof include sulfate hydrate (eg, calcium sulfate hydrate, etc.) and alkaline earth metal chloride hydrate (eg, calcium chloride hydrate, etc.).
  • Examples of the aliphatic diol include 1,6-hexanediol and 1,8-octanediol.
  • sugars and sugar alcohols include xylitol, erythritol, galactitol, and dihydroxyacetone.
  • the heat storage material one type may be used alone, or two or more types may be mixed and used.
  • the temperature range in which heat storage property is exhibited and the amount of heat storage can be adjusted according to the application.
  • the temperature range in which heat can be stored can be expanded by mixing the heat storage material having a melting point before and after the heat storage material having a melting point at the center temperature at which the heat storage effect of the heat storage material is desired to be obtained.
  • paraffin a having a melting point at the center temperature at which the heat storage effect of the heat storage material is desired is used as the core material, and the number of carbon atoms before and after the paraffin a and the paraffin a is set.
  • the heat storage body can be designed to have a wide temperature region (heat control region).
  • the content of paraffin having a melting point at the center temperature at which the heat storage action is desired is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more with respect to the total mass of the heat storage material. Is more preferable, and 98% by mass or more is particularly preferable.
  • the upper limit is 100% by mass.
  • paraffin When paraffin is used as the heat storage material, one type of paraffin may be used alone, or two or more types may be mixed and used. When a plurality of types of paraffin having different melting points are used, the temperature range in which heat storage property is exhibited can be widened. When a plurality of paraffins having different melting points are used, a mixture containing only linear paraffins without substantially containing branched chain paraffins is desirable in order not to reduce the endothermic property.
  • substantially free of branched-chain paraffin means that the content of branched-chain paraffin is 5% by mass or less with respect to the total mass of paraffin, and 2% by mass or less. Is preferable, and 1% by mass or less is more preferable.
  • substantially one type of paraffin As the heat storage material for application to electronic devices, it is also preferable that there is substantially one type of paraffin.
  • substantially one type of paraffin means that the content of the main paraffin is 95 to 100% by mass with respect to the total mass of paraffin, and is preferably 98 to 100% by mass.
  • the content of the main paraffin is not particularly limited in terms of the temperature range in which heat storage is exhibited and the amount of heat storage, but 80 to 100% by mass is preferable with respect to the total mass of paraffin. 90 to 100% by mass is more preferable, and 95 to 100% by mass is further preferable.
  • the "main paraffin” refers to the paraffin having the highest content among the plurality of paraffins contained.
  • the content of the main paraffin is preferably 50% by mass or more with respect to the total mass of paraffin.
  • the content of paraffin is not particularly limited, but is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total mass of the heat storage material (preferably latent heat storage material).
  • the paraffin is preferably linear paraffin, and preferably does not substantially contain branched chain paraffin. This is because the heat storage property is further improved by containing the linear paraffin and substantially not containing the branched paraffin. It is presumed that the reason for this is that the association between the molecules of linear paraffin can be suppressed from being inhibited by the branched-chain paraffin.
  • the content of the heat storage material in the heat storage body is 65% by mass or more with respect to the total mass of the heat storage body. Among them, 70% by mass or more is preferable, and 75% by mass or more is more preferable, because the effect of the present invention is more excellent.
  • the upper limit of the content of the heat storage material is not particularly limited, but in terms of the strength of the heat storage body, it is preferably 99.9% by mass or less, more preferably 99% by mass or less, and 98% by mass or less with respect to the total mass of the heat storage body. Is more preferable.
  • the core material of the microcapsules may contain components other than the above-mentioned heat storage material.
  • Other components that can be encapsulated in the microcapsules as the core material include, for example, a solvent and an additive such as a flame retardant.
  • the content of the heat storage material in the core material is not particularly limited, but 80 to 100% by mass is preferable, and 90 to 100% by mass is more preferable with respect to the total mass of the core material in that the heat storage property of the heat storage body is more excellent. ..
  • the microcapsules may contain a solvent as a core material.
  • the solvent in this case include the above-mentioned heat storage material whose melting point is outside the temperature range in which the heat storage body is used (heat control range; for example, the operating temperature of the heat storage body). That is, the solvent refers to a solvent that does not undergo a phase change in the liquid state in the heat control region, and is distinguished from a heat storage material that causes a phase transition in the heat control region and causes an endothermic reaction.
  • the content of the solvent in the core material is not particularly limited, but is preferably less than 30% by mass, more preferably less than 10% by mass, still more preferably 1% by mass or less, based on the total mass of the core material.
  • the lower limit is not particularly limited, but may be 0% by mass.
  • Examples of other components that can be included in the microcapsules as the core material include additives such as ultraviolet absorbers, light stabilizers, antioxidants, waxes, and odor suppressants.
  • the microcapsules have a capsule wall that encloses the core material.
  • the material for forming the capsule wall in the microcapsules is not particularly limited, and examples thereof include polymers, and specific examples thereof include polyurethane urea, polyurethane, polyurea, melamine resin, and acrylic resin.
  • the capsule wall preferably contains polyurethane, polyurea, polyurethane urea, or melamine resin, and more preferably contains polyurethane, polyurea, or polyurethane urea, in that the capsule wall can be made thinner and the heat storage property of the heat storage body is more excellent. preferable.
  • the polyurethane is a polymer having a plurality of urethane bonds, and a reaction product of a polyol and a polyisocyanate is preferable.
  • the polyurea is a polymer having a plurality of urea bonds, and a reaction product of a polyamine and a polyisocyanate is preferable.
  • the polyurethane urea is a polymer having a urethane bond and a urea bond, and a reaction product of a polyol, a polyamine, and a polyisocyanate is preferable.
  • the capsule wall of the microcapsules preferably has a urethane bond.
  • Capsule walls with urethane bonds are obtained, for example, using the polyurethane ureas or polyurethanes described above. Since the urethane bond is a highly motile bond, it can provide thermoplasticity to the capsule wall. In addition, it is easy to adjust the flexibility of the capsule wall. Therefore, for example, if the drying time during the production of the heat storage body is lengthened, the microcapsules are easily deformed and bonded to each other. As a result, the microcapsules can easily form a close-packed structure, so that the porosity of the heat storage body can be further reduced.
  • the microcapsules exist as deformable particles.
  • the microcapsules can be deformed without breaking, and the filling rate of the microcapsules in the heat storage body can be improved.
  • the fact that the microcapsules are deformed without breaking means that the microcapsules are deformed from the shape in a state where no external pressure is applied to each microcapsule, regardless of the degree of deformation.
  • Deformations that occur in microcapsules include deformations in which when microcapsules are pressed against each other in a heat storage body, spherical surfaces come into contact with each other to form a planar surface, or a contact surface in which one is convex and the other is concave. Is done.
  • Polyurethane urea, polyurethane, or polyurea is preferable, polyurethane urea or polyurethane is more preferable, and polyurethane urea is further preferable as the material for forming the capsule wall in that the microcapsules can be deformable particles.
  • polyurethane, polyurea, and polyurethane urea are preferably formed using polyisocyanate.
  • the polyisocyanate is a compound having two or more isocyanate groups, and examples thereof include aromatic polyisocyanates and aliphatic polyisocyanates.
  • aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, naphthalene-1,4-diisocyanate, and diphenylmethane-4,4'-.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, and cyclohexylene-1,3-diisocyanate.
  • Cyclohexylene-1,4-diisocyanate, dicyclohexammethane-4,4'-diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, isophorone diisocyanate, lysine diisocyanate, and Hexamethylene diisocyanate can be mentioned.
  • trifunctional or higher functional polyisocyanates may also be used as polyisocyanates.
  • the polyisocyanate includes a burette or isocyanurate which is a trimer of the above-mentioned bifunctional polyisocyanate, an adduct of a polyol such as trimethylolpropane and a bifunctional polyisocyanate, and benzene.
  • Examples thereof include formarin condensates of isocyanates, polyisocyanates having a polymerizable group such as methacryloyloxyethyl isocyanate, and lysine triisocyanates.
  • Polyisocyanates are described in the "Polyurethane Resin Handbook" (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).
  • the polyisocyanate a trifunctional or higher functional polyisocyanate is preferable.
  • the trifunctional or higher functional polyisocyanate include a trifunctional or higher functional aromatic polyisocyanate and a trifunctional or higher functional aliphatic polyisocyanate.
  • trifunctional or higher functional polyisocyanate an adduct form (addition) of a bifunctional polyisocyanate and a compound having three or more active hydrogen groups in the molecule (for example, a trifunctional or higher functional polyol, polyamine, polythiol, etc.)
  • a trifunctional or higher polyisocyanate (adduct type trifunctional or higher polyisocyanate) and a trimer of bifunctional polyisocyanate (biuret type or isocyanurate type) are also preferable.
  • Examples of the adduct-type trifunctional or higher-functional polyisocyanate include Takenate® D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, and D-. 140N, D-160N (all manufactured by Mitsui Chemicals, Inc.), Death Module (registered trademark) L75, UL57SP (manufactured by Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HL, HX, L (manufactured by Nippon Polyurethane Co., Ltd.) ), P301-75E (manufactured by Asahi Kasei Corporation), and Barnock (registered trademark) D-750 (manufactured by DIC Co., Ltd.).
  • adduct-type trifunctional or higher polyisocyanate Takenate (registered trademark) D-110N, D-120N, D-140N, D-160N manufactured by Mitsui Chemicals, Inc., or Barnock manufactured by DIC Corporation. (Registered trademark) D-750 is preferable.
  • isocyanurate-type trifunctional or higher functional isocyanate include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N, and D-204 (manufactured by Mitsui Chemicals, Inc.).
  • Biuret-type trifunctional or higher functional isocyanates include, for example, Takenate (registered trademark) D-165N, NP1100 (manufactured by Mitsui Chemicals, Inc.), Death Module (registered trademark) N3200 (Sumitomo Bayer Urethane), and Duranate (registered trademark). ) 24A-100 (manufactured by Asahi Kasei Corporation).
  • the polyol is a compound having two or more hydroxyl groups, and is, for example, a low molecular weight polyol (eg, aliphatic polyol, aromatic polyol), a polyether polyol, a polyester-based polyol, a polylactone-based polyol, a castor oil-based polyol. , Polyol-based polyols, and hydroxyl group-containing amine-based compounds.
  • the low molecular weight polyol means a polyol having a molecular weight of 300 or less, for example, bifunctional low molecular weight polyols such as ethylene glycol, diethylene glycol, and propylene glycol, as well as glycerin, trimethylolpropane, hexanetriol, and penta. Examples thereof include trifunctional or higher low molecular weight polyols such as erythritol and sorbitol. As the above-mentioned polyol, a small molecule polyol is preferable because the microcapsules are easily deformed.
  • Examples of the hydroxyl group-containing amine compound include amino alcohols as oxyalkylated derivatives of amino compounds.
  • the amino alcohol include N, N, N', N'-tetrakis [2-hydroxypropyl] ethylenediamine, which are propylene oxides or adducts of ethylene oxide of amino compounds such as ethylenediamine, and N, N, N'. , N'-Tetrakis [2-hydroxyethyl] ethylenediamine and the like.
  • a polyamine is a compound having two or more amino groups (primary amino group or secondary amino group), and is a fat such as diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, and hexamethylenediamine.
  • Group polyvalent amines Epoxy compound adducts of aliphatic polyvalent amines; Alicyclic polyvalent amines such as piperazine; and 3,9-bis-aminopropyl-2,4,8,10-tetraoxaspiro- ( 5,5) Examples thereof include heterocyclic diamines such as undecane.
  • the mass of the capsule wall in the microcapsule is not particularly limited, but is preferably 12% by mass or less, more preferably 10% by mass or less, based on the total mass of the heat storage material contained in the core portion.
  • the fact that the mass of the capsule wall is 12% by mass or less with respect to the heat storage material which is the inclusion component indicates that the capsule wall is a thin wall.
  • the lower limit of the mass of the capsule wall is not particularly limited, but 1% by mass or more is preferable, 2% by mass or more is more preferable, and 3% by mass is more preferable with respect to the total mass of the heat storage material in terms of maintaining the pressure resistance of the microcapsules. The above is more preferable.
  • the particle size of the microcapsules is not particularly limited, but the volume-based median diameter (Dm) is preferably 1 to 80 ⁇ m, more preferably 10 to 70 ⁇ m, and even more preferably 15 to 50 ⁇ m.
  • Dm volume-based median diameter
  • the particle size of the microcapsules is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less in terms of volume-based median diameter (Dm).
  • the volume-based median diameter of the microcapsules can be controlled by changing the dispersion conditions in the emulsification step of the method described below for the method of producing microcapsules.
  • the volume-based median diameter of microcapsules is a grain in which the total volume of particles on the large diameter side and the small diameter side is equal when the entire microcapsule is divided into two with the particle size as a threshold. Refers to the diameter.
  • the volume-based median diameter of the microcapsules is measured by a laser diffraction / scattering method using a Microtrack MT3300EXII (manufactured by Nikkiso Co., Ltd.).
  • the isolated microcapsules can be obtained by immersing the heat storage body in water for 24 hours or more and centrifuging the obtained aqueous dispersion.
  • the particle size distribution of the microcapsules is not particularly limited, but the CV (Coefficient of Variation) value (correlation coefficient) of the median diameter based on the volume of the microcapsules calculated by the following formula may be 10 to 100%. preferable.
  • CV value standard deviation ⁇ / median diameter x 100
  • the standard deviation ⁇ is calculated based on the volume-based particle size of the microcapsules measured according to the above-mentioned method for measuring the median diameter.
  • the thickness (wall thickness) of the capsule wall of the microcapsules is not particularly limited, but the thinner the capsule wall, the easier it is to deform, reduce the number of voids, and / or increase the contact area between the microcapsules. Therefore, it is possible to further suppress the occurrence of defects during handling. Specifically, 10 ⁇ m or less is preferable, 0.20 ⁇ m or less is more preferable, 0.15 ⁇ m or less is further preferable, and 0.11 ⁇ m or less is particularly preferable, in that the effect of the present invention is more excellent. On the other hand, since the strength of the capsule wall can be maintained by having a certain thickness, the wall thickness is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more.
  • the wall thickness is an average value obtained by determining the individual wall thickness ( ⁇ m) of any 20 microcapsules with a scanning electron microscope (SEM) and averaging them. Specifically, a cross-sectional section of the heat storage body is prepared, the cross section is observed using SEM, and 20 microcapsules are formed for the microcapsules having a size of ⁇ 10% of the median diameter calculated by the above-mentioned measurement method. select. The wall thickness of the microcapsules is determined by observing the cross section of each of the selected microcapsules, measuring the wall thickness, and calculating the average value of the wall thicknesses of the 20 microcapsules.
  • SEM scanning electron microscope
  • the volume-based median diameter of the above-mentioned microcapsules is Dm [unit: ⁇ m] and the thickness of the capsule wall of the above-mentioned microcapsules is ⁇ [unit: ⁇ m], the microcapsules with respect to the volume-based median diameter of the microcapsules.
  • the ratio of the thickness of the capsule wall ( ⁇ / Dm) is preferably 0.02 or less, more preferably 0.0075 or less, further preferably 0.006 or less, and particularly preferably 0.005 or less.
  • ⁇ / Dm When ⁇ / Dm is 0.0075 or less, the microcapsules are easily deformed during the production of the heat storage body, so that the porosity of the heat storage body can be particularly low and / or the adjacency ratio of the microcapsules described later is particularly high. can.
  • the lower limit of ⁇ / Dm is preferably 0.001 or more, more preferably 0.0015 or more, still more preferably 0.0025 or more, from the viewpoint of maintaining the strength of the microcapsules.
  • the deformation rate of the microcapsules is not particularly limited, but a larger deformation rate is preferable in that the porosity of the capsule can be reduced and the capsule adjacency ratio can be increased.
  • the deformation rate of the microcapsules means a value measured by the following method. By directly removing the microcapsules from the heat storage body forming composition or eluting the microcapsules from the heat storage body with a solvent, 15 microcapsules having a particle size within ⁇ 10% of the average value are taken out. The microcapsules are heated on a hot plate set to a temperature of + 5 ° C. at which the inclusion component melts to melt the inclusion component.
  • an HM2000 type micro hardness tester manufactured by Fisher Instruments Co., Ltd. can be used as the indentation hardness tester.
  • As the deformation rate of the microcapsules 30% or more is preferable, 35% or more is more preferable, 40% or more is further preferable, and 50% or more is particularly preferable, because the effect of the present invention is more excellent. In particular, when the deformation rate is 35% or more, the effect is more excellent.
  • the upper limit is not particularly limited, but is, for example, 100% or less, preferably 60% or less from the viewpoint of ease of handling during manufacturing and the like.
  • the deformation rate of the microcapsules depends on, for example, the thickness of the capsule wall of the microcapsules, the ratio of the thickness of the capsule wall of the microcapsules to the median diameter based on the volume of the microcapsules ( ⁇ / Dm), and the material forming the capsule wall. , Can be adjusted.
  • the content of the microcapsules in the heat storage body is not particularly limited, but 80% by mass or more is preferable, and 85 to 99% by mass is more preferable with respect to the total mass of the heat storage body, in that the heat storage property of the heat storage body is more excellent. 90 to 99% by mass is more preferable.
  • the method for producing microcapsules is not particularly limited, and known methods can be adopted.
  • the capsule wall contains polyurethane urea, polyurethane, or polyurea
  • a step of dispersing an oil phase containing a heat storage material and a capsule wall material in an aqueous phase containing an emulsifier to prepare an emulsion emulsification step.
  • An interface polymerization method including a step of forming a capsule wall by polymerizing a capsule wall material at an interface between an oil phase and an aqueous phase to form a microcapsule containing a heat storage material (encapsulation step) can be mentioned.
  • the capsule wall contains melamine resin
  • the oil phase containing the heat storage material is dispersed in the aqueous phase containing the emulsifier to prepare an emulsified solution (emulsification step)
  • the capsule wall material is added to the aqueous phase to emulsify.
  • a core selvation method including a step of forming a polymer layer of a capsule wall material on the surface of a droplet to form a microcapsule containing a heat storage material (encapsulation step) can be mentioned.
  • the capsule wall material means a material that can form a capsule wall. In the following, each step of the interfacial polymerization method will be described in detail.
  • an oil phase containing a heat storage material and a capsule wall material is dispersed in an aqueous phase containing an emulsifier to prepare an emulsion.
  • the capsule wall material contains at least a polyisocyanate and at least one selected compound consisting of a polyol and a polyamine.
  • the emulsion is formed by dispersing an oil phase containing a heat storage material and a capsule wall material in an aqueous phase containing an emulsifier.
  • the oil phase contains at least a heat storage material and a capsule wall material, and may further contain other components such as a solvent and / or an additive, if necessary.
  • a water-insoluble organic solvent is preferable, and ethyl acetate, methyl ethyl ketone, or toluene is more preferable, because the dispersion stability is excellent.
  • the aqueous phase can include at least an aqueous medium and an emulsifier.
  • the aqueous medium include water and a mixed solvent of water and a water-soluble organic solvent, and water is preferable.
  • Water-soluble means that the amount of the target substance dissolved in 100% by mass of water at 25 ° C. is 5% by mass or more.
  • the content of the aqueous medium is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the emulsion which is a mixture of the oil phase and the aqueous phase. % Is more preferable.
  • the emulsifier examples include a dispersant, a surfactant and a combination thereof.
  • the dispersant a known dispersant can be used, and polyvinyl alcohol is preferable.
  • the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the emulsifier is preferably more than 0% by mass and 20% by mass or less, more preferably 0.005 to 10% by mass, and 0.01 to 10 with respect to the total mass of the emulsion which is a mixture of the oil phase and the aqueous phase.
  • the mass% is more preferable, and 1 to 5% by mass is particularly preferable.
  • the aqueous phase may contain other components such as UV absorbers, antioxidants, and preservatives, if desired.
  • Dispersion refers to dispersing the oil phase as oil droplets in the aqueous phase (emulsification). Dispersion can be carried out using means commonly used for dispersion between the oil phase and the aqueous phase (eg, homogenizers, manton gorries, ultrasonic dispersers, dissolvers, keddy mills, and other known dispersers).
  • means commonly used for dispersion between the oil phase and the aqueous phase eg, homogenizers, manton gorries, ultrasonic dispersers, dissolvers, keddy mills, and other known dispersers.
  • the mixing ratio of the oil phase to the aqueous phase is preferably 0.1 to 1.5, more preferably 0.2 to 1.2, and even more preferably 0.4 to 1.0. ..
  • the capsule wall material is polymerized at the interface between the oil phase and the aqueous phase to form a capsule wall, and microcapsules containing a heat storage material are formed.
  • Polymerization is preferably carried out under heating.
  • the reaction temperature in the polymerization is preferably 40 to 100 ° C, more preferably 50 to 80 ° C.
  • the reaction time of the polymerization is preferably about 0.5 to 10 hours, more preferably about 1 to 5 hours.
  • aqueous solution for example, water, an acetic acid aqueous solution, etc.
  • a dispersant for preventing aggregation may be added to the reaction system during the polymerization.
  • a charge regulator such as niglocin or any other auxiliary agent may be added to the reaction system during the polymerization.
  • the heat storage body contains a resin.
  • the resin is located between the above-mentioned microcapsules and functions as a binder for ensuring the adhesion between the microcapsules.
  • the type of resin is not particularly limited, and examples thereof include known resins.
  • the resin include polyurethane, polyurea, polyurethane urea, and poly (meth) acrylate.
  • the resin preferably contains at least one resin selected from the group consisting of polyurethane, polyurea, and polyurethane urea, because the effect of the present invention is more excellent.
  • the capsule wall and the resin of the microcapsules have the same functional group in that the effect of the present invention is more excellent.
  • the capsule wall and the resin of the microcapsules have the same polar functional group.
  • the polar functional group include a hydroxyl group, a carboxyl group, an amide group, a urethane group, and a urea group.
  • both the capsule wall and the resin of the microcapsules contain at least one selected from the group consisting of polyurethane, polyurea, and polyurethane urea, and the polyurethane urea is used. It is more preferable to include it.
  • the glass transition temperature of the resin is not particularly limited, but is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 20 ° C. or lower, in that the effect of the present invention is more excellent.
  • the lower limit is not particularly limited, but from the viewpoint of handleability, ⁇ 100 ° C. or higher is preferable, ⁇ 60 ° C. or higher is more preferable, and ⁇ 40 ° C. or higher is further preferable.
  • the method for measuring the glass transition temperature of the resin is as follows.
  • the glass transition temperature of the resin is measured from 25 ° C to (heat) at a temperature rise rate of 5 ° C / min using a differential scanning calorimeter DSC (device name: DSC-60A Plus, Shimadzu Corporation) and a closed pan. Measure in the range of decomposition temperature (° C) -5 ° C).
  • DSC differential scanning calorimeter
  • the value at the time of raising the temperature in the second cycle is used.
  • the glass transition temperature is described as the catalog value of the commercially available product, that value may be used as the glass transition temperature of the resin.
  • the elastic modulus (tensile elastic modulus) of the resin is not particularly limited, but is preferably 100 MPa or less, more preferably 15 MPa or less, in that the effect of the present invention is more excellent.
  • the lower limit is not particularly limited, but from the viewpoint of handleability, 0.1 MPa or more is preferable, 1 MPa or more is more preferable, and 6 MPa or more is further preferable.
  • the method for measuring the elastic modulus (tensile elastic modulus) of the resin is to measure the tensile elastic modulus (Young's modulus) at a temperature of 25 ° C. and a humidity of 40% using a static extensometer according to JIS7161. When a commercially available product is used as the resin, if the elastic modulus is described as the catalog value of the commercially available product, that value may be used as the elastic modulus of the resin.
  • the elongation at break of the resin is not particularly limited, but 300% or more is preferable, and 500% or more is more preferable, because the effect of the present invention is more excellent.
  • the upper limit is not particularly limited, but from the viewpoint of handleability, 5000% or less is preferable, and 2000% or less is more preferable.
  • the method for measuring the breaking elongation of the resin is measured according to JIS-C-2151. Specifically, it is calculated from the elongation when the sample is cut (broken) by tensioning at a speed of 200 mm / min using a tensile tester.
  • Fracture elongation (%) 100 ⁇ (L-Lo) / Lo Lo: Sample length before test, L: Sample length at break When using a commercially available resin, if the catalog value of the commercially available product describes the elongation at break, that value. May be used as the breaking elongation of the resin.
  • the resin may be used as a dispersion liquid in which the resin is dispersed in a solvent.
  • the solvent include water and a mixed solution of water and an organic solvent.
  • the resin When the resin is dispersed in the dispersion liquid, the resin may be in the form of particles. That is, the resin may be used as a latex in which particulate resin is dispersed in water.
  • the diameter of the particulate resin (resin particles) in the dispersion is not particularly limited, but 0.001 to 10 ⁇ m is preferable, and 0.01 to 1 ⁇ m is more preferable, because the effect of the present invention is more excellent.
  • the content of the resin in the heat storage body is not particularly limited, but 20% by mass or less is preferable and 1 to 15% by mass is more preferable with respect to the total mass of the heat storage body in that the heat storage property of the heat storage body is more excellent. Up to 15% by mass is more preferable.
  • the heat storage body may contain water, but when the water contained in the heat storage body evaporates, the portion where the water has evaporated may become a void in the heat storage body. Therefore, the water content in the heat storage body is preferably small from the viewpoint of suppressing the generation of voids. Specifically, the water content in the heat storage body is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the heat storage body, from the viewpoint of further suppressing the generation of voids in the heat storage body. 1% by mass or less is more preferable. The lower limit of the water content in the heat storage body is not particularly limited, but may be 0% by mass.
  • the method for measuring the water content in the heat storage body is as follows.
  • the heat storage body is stored in a constant temperature and humidity chamber at 25% RH and 40 ° C. for 24 hours to obtain the heat storage body A.
  • the heat storage body A taken out from the constant temperature and humidity chamber is dried at 100 ° C. for 3 hours to obtain a heat storage body B.
  • the masses of the heat storage body A and the heat storage body B thus obtained are measured, and the value obtained according to the following formula is used as the water content in the heat storage body.
  • Water content in the heat storage body (mass%) 100 ⁇ ⁇ (mass of heat storage body A)-(mass of heat storage body B) ⁇ / (mass of heat storage body A)
  • the heat storage body may contain other components other than the microcapsules and the resin.
  • Other components include thermally conductive materials, flame retardants, UV absorbers, antioxidants, and preservatives.
  • the content of the other components is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the heat storage body.
  • the lower limit is not particularly limited, but may be 0% by mass.
  • the "thermal conductivity" of the thermally conductive material a material having a thermal conductivity of 10 Wm -1 K -1 or more is preferable.
  • the thermal conductivity of the heat conductive material 50 Wm -1 K -1 or more is more preferable in terms of improving the heat dissipation of the heat storage body.
  • the thermal conductivity (unit: Wm -1 K -1 ) is a value measured by a flash method at a temperature of 25 ° C. by a method compliant with Japanese Industrial Standards (JIS) R1611.
  • the shape of the heat storage body is not particularly limited, and it can take any form (three-dimensional shape) such as a cylindrical shape, a spherical shape, and a lump shape as well as a sheet shape, a film shape, and a plate shape.
  • the effect of the present invention becomes remarkable when the heat storage body is thick, and the thickness of the heat storage body is preferably 0.5 mm or more, more preferably 1 mm or more, and further preferably 2 mm or more. It is preferably 3 mm or more, and particularly preferably 3 mm or more.
  • the upper limit is not particularly limited, but is preferably 1000 mm or less, and more preferably 100 mm or less.
  • the thickness means the shortest distance when the heat storage body is sandwiched between two parallel planes. However, when the heat storage body is plate-shaped, sheet-shaped, or film-shaped, the thickness of the heat storage body is determined by observing the cut surface of the heat storage body cut in parallel with the thickness direction with SEM and observing 5 arbitrary points. Measure and use the average value of the thicknesses of the five points.
  • the latent heat capacity of the heat storage body is not particularly limited, but 115J / cc or more is preferable, 120J / cc or more is more preferable, and 130J or more is preferable in that the heat storage property of the heat storage body is high and it is suitable for temperature control of the heat generating body that generates heat. / Cc or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 300 J / cc or less.
  • the latent heat capacity is a value calculated from the result of differential scanning calorimetry (DSC) and the density of the heat storage body (g / cm 3). The density is measured from the mass and volume of the sample. The mass of the sample is measured with an electronic balance.
  • the volume of the sample is calculated by measuring the area and thickness with a caliper, a contact type thickness measuring machine, etc. when the sample is in the form of a sheet, and when the sample is in the form of a lump, a solvent that does not dissolve or swell. Obtained from the increased volume by immersing in (water, alcohol, etc.). Considering that a high amount of heat storage is exhibited in a limited space, it is considered appropriate to grasp the amount of heat storage as "J / cc", but when considering the use of electronic devices, etc., The weight of the electronic device is also important. Therefore, if we consider that high heat storage is exhibited within a limited mass, it may be appropriate to consider it as "J / g (heat storage amount per unit mass)".
  • the latent heat capacity is preferably 150 J / g or more, more preferably 160 J / g or more.
  • the upper limit is not particularly limited, but is preferably 300 J / g or less.
  • the volume ratio of the microcapsules in the heat storage body is not particularly limited, but is preferably 60% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, based on the total volume of the heat storage body.
  • the upper limit is not particularly limited, but 100% by volume or less can be mentioned.
  • the porosity of the heat storage body means the volume fraction of the voids in the heat storage body.
  • the void means a region inside the heat storage body in which the material (solid and liquid) constituting the heat storage body does not exist and is surrounded by the material constituting the heat storage body, and is usually a gas (mainly). Is filled with air).
  • the void ratio of the heat storage body is less than 10% by volume with respect to the total volume of the heat storage body, and is preferably 6% by volume or less, preferably 5% by volume or less, from the viewpoint of further suppressing the occurrence of defects in the heat storage body during handling. Is more preferable.
  • the lower limit of the porosity of the heat storage body is not particularly limited, but may be 0% by volume.
  • the porosity of the heat storage body is less than 10% by volume, the amount of heat storage per unit volume can be further improved.
  • the method of reducing the porosity of the heat storage body to less than 10% by volume is not particularly limited, but the material and resin of the capsule wall of the microcapsules are the same while using the microcapsules having a thin wall thickness and a high deformation rate. Examples thereof include a method of adjusting to have a functional group.
  • the void ratio of the heat storage body is calculated based on image data obtained by a known X-ray CT apparatus using an X-ray CT (X-ray Computed Tomography) method as a measurement principle. Specifically, an arbitrary region of 1 mm ⁇ 1 mm in the in-plane direction of the heat storage body is scanned along the film thickness direction of the heat storage body by the X-ray CT method, and the gas (air) and the others (solid and solid) are scanned. Distinguish from liquid). Then, from the three-dimensional image data obtained by image processing a plurality of scanning layers obtained by scanning along the film thickness direction, the volume of the gas (void portion) existing in the scanned region and the scanned region are obtained. (Total volume of gas, solid and liquid) and the total volume of. Then, the ratio of the volume of the gas to the total volume of the scanned regions is defined as the porosity (volume%) of the heat storage body.
  • X-ray CT X-ray Computed Tomography
  • the microcapsules contained in the heat storage body are preferably deformed.
  • the aspect ratio of the microcapsules is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 2.0 or more.
  • the filling rate of the microcapsules is improved, the contact area between the microcapsules is widened, the strength of the heat storage body is improved, and defects of the heat storage body are generated during handling. Can be further suppressed.
  • the amount of the heat storage material can be increased, and more excellent heat storage can be realized.
  • the upper limit of the aspect ratio of the microcapsules is not particularly limited, but may be, for example, 10 or less.
  • the aspect ratio of the microcapsules can be obtained by the following method from the SEM cross-sectional image of the heat storage body. After observing the cross section of the heat storage body using SEM and obtaining an SEM cross section image, 20 microcapsules are selected from the obtained images. Of the two parallel tangents circumscribing the outer circumference of each selected microcapsule, the distance between the two parallel tangents selected so as to maximize the distance between the tangents is defined as the length L of the long side. Further, of the two parallel tangents orthogonal to the two parallel tangents giving the length L and circumscribing the outer circumference of the microcapsule, the distance between the tangents selected so as to maximize the distance between the tangents is selected.
  • the length of the short side be S.
  • the aspect ratio was calculated using the following formula, and the average value of the aspect ratios of 20 microcapsules was obtained. The obtained average value is used as the aspect ratio of the microcapsules.
  • Aspect ratio L ( ⁇ m) / S ( ⁇ m)
  • the method described as a method of reducing the porosity of the heat storage body can be mentioned.
  • the microcapsules contained in the heat storage body preferably have flat portions or recesses formed by contact with other microcapsules or the like. Specifically, it is preferable that the microcapsules in the heat storage body observed by the following method have two or more flat portions and recesses. After obtaining an SEM cross-sectional image by the same method as the aspect ratio calculation method described above, 20 microcapsules are selected. Then, from the SEM cross-sectional image, the selected microcapsules form a portion in which at least two or more microcapsules are adjacent to each other, and in the outer shape of the selected microcapsules, the outer shape of the adjacent microcapsules.
  • the condition of having two or more linear or concave portions formed along the above condition is satisfied.
  • the number of microcapsules satisfying the above conditions is preferably 5 or more, more preferably 10 or more, and even more preferably 20.
  • the elastic modulus (tensile elastic modulus) of the heat storage body is not particularly limited, but is preferably 50 MPa or more, more preferably 100 MPa or more, further preferably 500 MPa or more, and particularly preferably 1000 MPa or more.
  • the upper limit of the elastic modulus of the heat storage body is not particularly limited, but is preferably 10,000 MPa or less.
  • the elastic modulus (tensile elastic modulus) of the heat storage body is measured according to JIS K 7161-1: 2014.
  • the method for producing the heat storage body is not particularly limited, and a known method can be mentioned.
  • a method of producing a heat storage body by using the above-mentioned microcapsule, a resin, and a composition for forming a heat storage body containing water can be mentioned.
  • a method for producing a heat storage body by applying the heat storage body forming composition on a predetermined substrate and drying it, forming the heat storage body in a gap between members A method of filling a heat storage composition and drying it to produce a heat storage body, a method of dropping a heat storage body forming composition onto a substrate to form a lump, and a mold for the heat storage body forming composition.
  • the microcapsules and the resin contained in the composition for forming a heat storage body are as described above.
  • the method for preparing the composition for forming a heat storage body is not particularly limited, and for example, a dispersion liquid in which microcapsules are dispersed (for example, an aqueous dispersion liquid) and a dispersion liquid in which particulate resin is dispersed (for example, an aqueous dispersion liquid, so-called). , Latex.), And a method of mixing powdery microcapsules and a dispersion liquid in which particulate resin is dispersed.
  • Examples of the method for obtaining powdered microcapsules include a method for recovering microcapsules by removing a solvent from the above-mentioned dispersion liquid in which microcapsules are dispersed.
  • the method for recovering the microcapsules is not particularly limited, and examples thereof include a method for recovering the microcapsules in the dispersion liquid in which the microcapsules are dispersed by decantation.
  • the base material examples include a resin base material, a glass base material, and a metal base material.
  • the resin contained in the resin base material include polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polyolefin (eg, polyethylene, polypropylene), and polyurethane.
  • polyester eg, polyethylene terephthalate, polyethylene naphthalate
  • polyolefin eg, polyethylene, polypropylene
  • polyurethane it is preferable to add a function to improve the thermal conductivity in the in-plane direction or the film thickness direction and to quickly dissipate heat from the heat generating portion to the heat storage portion to the base material.
  • a base material made by combining a metal base material and a heat conductive material such as a graphite sheet or a graphene sheet is more preferable.
  • the thickness of the base material is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 25 ⁇ m, still more preferably 3 to 15 ⁇ m.
  • the base material is preferably treated on the surface of the base material for the purpose of improving the adhesion to the heat storage body. Examples of the surface treatment method include corona treatment, plasma treatment, and application of a thin layer which is an easy-adhesion layer.
  • the material constituting the easy-adhesion layer is not particularly limited, and examples thereof include resin, and more specific examples thereof include styrene-butadiene rubber, urethane resin, acrylic resin, silicone resin, and polyvinyl resin.
  • the thickness of the easy-adhesion layer is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.5 to 2 ⁇ m.
  • a peelable temporary base material may be used as the base material.
  • Examples of the coating method include a die coating method, an air knife coating method, a roll coating method, a blade coating method, a gravure coating method, and a curtain coating method.
  • the preferable range of the drying temperature depends on the amount of water at the time of drying, but when water is contained in the composition for forming the heat storage body, 20 to 130 ° C. is preferable because the porosity of the heat storage body can be further lowered. , 30 to 120 ° C. is more preferable, and 33 to 100 ° C. is even more preferable.
  • the drying time is preferably completed immediately before the moisture in the membrane is completely dried, but in that range, 30 seconds or more is preferable and 1 minute or more is more preferable from the viewpoint that the porosity of the heat storage body can be further lowered. The shorter the upper limit of the drying time, the better from the viewpoint of the production efficiency of the heat storage body.
  • the coating film may be subjected to a flattening treatment.
  • the flattening treatment method include a method of applying pressure to the coating film with a roller, a nip roller, a calendar, or the like to increase the filling rate of microcapsules in the film.
  • microcapsules that are easily deformed large deformation rate
  • slowly dry the coating film or thicken the film at one time. It is preferable to apply the coating film in a plurality of times without forming a suitable coating film.
  • the heat storage body of the present invention can be applied to various uses, for example, electronic devices (for example, mobile phones (particularly smartphones), mobile information terminals, personal computers (particularly portable personal computers), game machines, and (Remote control, etc.); Automobiles (for example, batteries (particularly lithium ion batteries), control devices such as power ICs (Integrated Circuits), car navigation systems, liquid crystal monitors, LED (Light Emitting Diode) lamps, heat insulation of canisters, etc.); Building materials suitable for temperature control during rapid temperature rise in the room or indoor heating and cooling (for example, floor materials, roofing materials, wall materials, etc.); Changes in environmental temperature or changes in body temperature during exercise or rest, etc. Clothes suitable for temperature control according to the temperature (for example, underwear, jacket, cold protection clothes, gloves, etc.); Air conditioner; Bedding; Exhaust heat utilization system that stores unnecessary exhaust heat and uses it as heat energy, etc. Can be used for.
  • electronic devices for example, mobile phones (particularly smartphones), mobile information terminals, personal computers (particularly portable personal computers),
  • the heat storage member of the present invention has the above-mentioned heat storage body.
  • the heat storage member preferably has another layer (for example, a protective layer) as described later.
  • the heat storage member may have a base material on the heat storage body in terms of handling.
  • the heat storage member may have a protective layer.
  • the protective layer is a layer arranged on the heat storage body, and when the heat storage member has a base material, the protective layer is arranged on the surface side of the heat storage body opposite to the base material.
  • the protective layer has a function of protecting the heat storage body.
  • the protective layer may be arranged so as to be in contact with the heat storage body, or may be arranged on the heat storage body via another layer.
  • the material constituting the protective layer is not particularly limited, and a resin is preferable, and a resin selected from the group consisting of a fluororesin and a siloxane resin is preferable in that water resistance and flame retardancy are better.
  • fluororesin examples include known fluororesins.
  • examples of the fluororesin include polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyethylene trifluorochloride, and polytetrafluoropropylene.
  • the fluororesin may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer of two or more types. Further, a copolymer of these monomers and other monomers may be used.
  • copolymer examples include a copolymer of tetrafluoroethylene and tetrafluoropropylene, a copolymer of tetrafluoroethylene and vinylidene fluoride, a copolymer of tetrafluoroethylene and ethylene, and tetrafluoroethylene and propylene.
  • fluororesin examples include Obligato (registered trademark) SW0011F, SIFCLEAR-F101, F102 (manufactured by JSR), KYNAR AQUATEC (registered trademark) ARC, and FMA-12 (both manufactured by Arkema) manufactured by AGC Cortec. ..
  • the siloxane resin is a polymer having a repeating unit having a siloxane skeleton, and a hydrolyzed condensate of a compound represented by the following formula (1) is preferable.
  • Equation (1) Si (X) n (R) 4-n X represents a hydrolyzable group.
  • the hydrolyzable group include an alkoxy group, a halogen group, an acetoxy group, and an isocyanate group.
  • R represents a non-hydrolyzable group.
  • non-hydrolytable group examples include an alkyl group (for example, a methyl group, an ethyl group, and a propyl group), an aryl group (for example, a phenyl group, a trill group, and a mesityl group), and an alkenyl group (for example, vinyl).
  • alkyl group for example, a methyl group, an ethyl group, and a propyl group
  • aryl group for example, a phenyl group, a trill group, and a mesityl group
  • an alkenyl group for example, vinyl
  • haloalkyl group eg ⁇ -chloropropyl group
  • aminoalkyl group eg ⁇ -aminopropyl group and ⁇ - (2-aminoethyl) aminopropyl group
  • epoxyalkyl group For example, ⁇ -glycidoxypropyl group and ⁇ - (3,4-epoxycyclohexyl) ethyl group
  • ⁇ -mercaptoalkyl group (meth) acryloyloxyalkyl group ( ⁇ -methacryloyloxypropyl group
  • a hydroxyalkyl group eg, ⁇ -hydroxypropyl group.
  • n represents an integer of 1 to 4, preferably 3 or 4.
  • the hydrolyzed condensate is intended to be a compound obtained by hydrolyzing a hydrolyzable group in the compound represented by the formula (1) and condensing the obtained hydrolyzate.
  • the hydrolyzed condensate may be partially hydrolyzed even if all hydrolyzable groups are hydrolyzed and all the hydrolyzated products are condensed (completely hydrolyzed condensate).
  • the sex group may be hydrolyzed and a part of the hydrolyzate may be condensed (partially hydrolyzed condensate). That is, the hydrolyzed condensate may be a completely hydrolyzed condensate, a partially hydrolyzed condensate, or a mixture thereof.
  • the protective layer for example, a layer containing a known hard coat agent or a hard coat film described in JP-A-2018-202696, JP-A-2018-18387, and JP-A-2018-111793 may be used. good. Further, from the viewpoint of heat storage property, a protective layer having a polymer having heat storage property described in International Publication No. 2018/207387 and JP-A-2007-031610 may be used.
  • the protective layer may contain components other than the resin.
  • Other components include thermally conductive materials, flame retardants, UV absorbers, antioxidants, and preservatives.
  • the flame retardant is not particularly limited, and a known material can be used.
  • a flame retardant or the like described in "Techniques for Utilizing Flame Retardants / Flame Retardants” (CMC Publishing) can be used, and halogen-based flame retardants, phosphorus-based flame retardants, or inorganic flame retardants are preferable.
  • phosphorus-based flame retardants or inorganic flame retardants are preferable.
  • Phosphorus-based flame retardants include phosphate-based materials such as triphenyl phosphate, tricresyl phosphate, trixilenyl phosphate, cresylphenyl phosphate, and 2-ethylhexyldiphenyl phosphate, other aromatic phosphate esters, and aromatic condensed phosphorus. Examples thereof include acid esters, polyphosphates, phosphinic acid metal salts, and red phosphorus. It is also preferable to include a flame retardant aid in combination with the flame retardant. Examples of the flame retardant aid include pentaerythritol, phosphorous acid, and 22-oxidized tetrasalt 12boron heptahydrate.
  • the thickness of the protective layer is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 0.01 to 25 ⁇ m, still more preferably 0.5 to 15 ⁇ m.
  • the cut surface obtained by cutting the protective layer in parallel with the thickness direction is observed by SEM, 5 arbitrary points are measured, and the thickness of the 5 points is averaged.
  • the method for forming the protective layer is not particularly limited, and known methods can be mentioned.
  • a method of bonding the layers on the heat storage body can be mentioned.
  • the method of using the composition for forming a protective layer will be described in detail.
  • the resin contained in the protective layer forming composition is as described above.
  • the resin precursor means a component that becomes a resin by curing treatment, and examples thereof include a compound represented by the above-mentioned formula (1).
  • the composition for forming a protective layer may contain a solvent (for example, water and an organic solvent), if necessary.
  • the method of contacting the protective layer forming composition with the heat storage body is not particularly limited, and the method of applying the protective layer forming composition onto the heat storage body and the method of immersing the heat storage body in the protective layer forming composition are immersed.
  • the method can be mentioned.
  • a dip coater, a die coater, a slit coater, a bar coater, an extrusion coater, a curtain flow coater, a known coating device such as spray coating, and gravure printing are used. , Screen printing, offset printing, and a method using a printing device such as inkjet printing.
  • an adhesion layer is arranged on the side opposite to the heat storage body of the base material for the purpose of improving the adhesion between the heating element and the heat storage element, which will be described later.
  • the adhesive layer include an adhesive layer and an adhesive layer.
  • the material of the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include known pressure-sensitive adhesives.
  • Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.
  • the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a polymer of (meth) acrylic monomer ((meth) acrylic polymer).
  • the adhesive layer may further contain a tackifier.
  • the material of the adhesive layer is not particularly limited, and examples thereof include known adhesives.
  • Examples of the adhesive include urethane resin adhesives, polyester adhesives, acrylic resin adhesives, ethylene vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyamide adhesives, and silicone adhesives.
  • the method for forming the adhesion layer is not particularly limited, and for example, a method of transferring the adhesion layer onto the heat storage body and a method of applying a composition containing an adhesive or an adhesive onto the heat storage body to form the adhesion layer. Can be mentioned.
  • the thickness of the adhesion layer is not particularly limited, but is preferably 0.5 to 100 ⁇ m, more preferably 1 to 25 ⁇ m, still more preferably 1 to 15 ⁇ m.
  • the heat storage member When the heat storage body is in the form of a sheet, a plate, or a film, the heat storage member may have a flame-retardant layer. Further, the heat storage body may have a flame-retardant component.
  • the position of the flame-retardant layer is not particularly limited, and may be integrated with the protective layer or may be provided as a separate layer. When it is provided as a separate layer, it is preferably laminated between the protective layer and the heat storage body. When it is integrated with the protective layer, it means that the protective layer has a flame-retardant function.
  • the entire heat storage member can be made flame-retardant by having a flame-retardant protective layer or a flame-retardant layer.
  • the flame-retardant protective layer and the flame-retardant layer are not particularly limited as long as they are flame-retardant, but are flame-retardant organic resins such as polyetheretherketone resin, polycarbonate resin, silicone resin, and fluorine-containing resin, as well. , It is preferably formed from an inorganic material such as a glass film.
  • the glass film can be formed by, for example, applying a silane coupling agent or a siloxane oligomer on a heat storage body and heating or drying the glass film.
  • a flame retardant may be mixed and formed in the protective layer.
  • the flame retardant the above-mentioned flame retardant and inorganic particles such as silica are preferable.
  • the amount and type of the inorganic particles can be adjusted including the type of the resin depending on the surface shape and / or the film quality.
  • the size of the inorganic particles is preferably 0.01 to 1 ⁇ m, more preferably 0.05 to 0.3 ⁇ m, still more preferably 0.1 to 0.2 ⁇ m.
  • the content of the inorganic particles is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, based on the total mass of the protective layer.
  • the content of the flame retardant is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and 1 to 5% by mass with respect to the total mass of the protective layer from the viewpoint of heat storage amount and flame retardancy. Is more preferable.
  • the thickness of the flame-retardant protective layer is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 15 ⁇ m, and even more preferably 0.5 to 10 ⁇ m from the viewpoint of heat storage amount and flame retardancy.
  • the heat storage member When the heat storage body is in the form of a sheet, a plate, or a film, the heat storage member may have a colored layer. Further, the heat storage body may have a coloring component. By providing the colored layer, it is possible to suppress the change in the appearance of the heat storage member even when the color of the heat storage body changes. In addition, rubbing during handling or invasion of water or the like into the heat storage body can be suppressed, physical or chemical changes in the microcapsules can be suppressed, and as a result, color change of the heat storage body itself can be suppressed.
  • the colored layer may be integrated with the protective layer, or may be arranged as a separate layer so as to be in contact with the heat storage body.
  • the colored layer preferably contains a colorant in order to obtain the desired hue.
  • the colorant include pigments and dyes, and pigments are preferable, black pigments are more preferable, and carbon black is further preferable, because they have excellent weather resistance and can further suppress the change in the appearance of the heat storage member. preferable. When carbon black is used, the thermal conductivity of the colored layer is further improved.
  • the pigment include various conventionally known inorganic pigments and organic pigments. Specific examples of the inorganic pigment include white pigments such as titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, and carbon black, titanium black, and titanium. Examples thereof include black pigments such as carbon, iron oxide, and graphite.
  • Examples of the organic pigment include the organic pigment described in paragraph 0093 of JP-A-2009-256572.
  • Examples of the organic pigment include C.I. I. Pigment Red 177, 179, 224, 242, 254, 255, 264 and other red pigments, C.I. I. Pigment Yellow 138, 139, 150, 180, 185 and other yellow pigments, C.I. I. Pigment Orange 36, 38, 71 and other orange pigments, C.I. I. Pigment Green 7, 36, 58 and other green pigments, C.I. I. Blue pigments such as Pigment Blue 15: 6 and C.I. I. Examples include purple pigments such as Pigment Violet 23.
  • the colorant may be used alone or in combination of two or more.
  • the content of the colorant (for example, black pigment) in the colored layer is not particularly limited, but is 2 to 30% by volume with respect to the total volume of the colored layer in that the change in the appearance of the heat storage member can be further suppressed. It is preferable, 5 to 25% by volume is more preferable.
  • the colored layer may contain a binder.
  • the type of the binder is not particularly limited, and known materials can be mentioned, and a resin is preferable.
  • a resin is preferable.
  • the resin a resin selected from the group consisting of fluororesins and siloxane resins is preferable because it has better water resistance and flame retardancy.
  • the resin selected from the group consisting of fluororesin and siloxane resin having good water resistance in the colored layer the chemical change of the microcapsules can be suppressed and the color change of the heat storage body can be suppressed.
  • Specific examples of the fluororesin and the siloxane resin are as described above.
  • the content of the binder in the colored layer is not particularly limited, but is preferably 50 to 98% by volume, preferably 75 to 95% by volume, based on the total volume of the colored layer, in that the change in the appearance of the heat storage member can be further suppressed. Is more preferable.
  • the binder in the colored layer may be used alone or in combination of two or more.
  • the colored layer may contain other components other than the colorant and the binder.
  • Other components include thermally conductive materials, flame retardants, UV absorbers, antioxidants, and preservatives.
  • the thickness of the colored layer is not particularly limited, but is preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the cut surface obtained by cutting the colored layer in parallel with the thickness direction is observed by SEM, 5 arbitrary points are measured, and the thickness of the 5 points is averaged.
  • One of the preferred forms of the colored layer is a form in which the film thickness of the colored layer is 15 ⁇ m or less and the optical density of the colored layer is 1.0 or more.
  • the optical density is preferably 1.2 or more.
  • the upper limit is not particularly limited, but 6.0 or less is preferable.
  • X-rite eXact manufactured by X-Rite
  • the density status is measured at ISO status T and D50 / 2 ° without a filter.
  • the K value is adopted as the OD value of Xrite.
  • the method for forming the colored layer is not particularly limited, and known methods can be mentioned.
  • a composition for forming a colored layer containing a colorant and a binder or a precursor thereof is brought into contact with a heat storage body, and a coating film formed on the heat storage body is subjected to a curing treatment as necessary.
  • a curing treatment as necessary.
  • the colorants and binders contained in the composition for forming a colored layer are as described above.
  • the precursor of the binder contained in the composition for forming a colored layer means a component that becomes a binder by a curing treatment, and examples thereof include a compound represented by the above-mentioned formula (1).
  • the colored layer forming composition may contain a solvent (for example, water and an organic solvent), if necessary.
  • the method of contacting the colored layer forming composition with the heat storage body is not particularly limited, and the method of applying the colored layer forming composition onto the heat storage body and the method of immersing the heat storage body in the colored layer forming composition are immersed.
  • the method can be mentioned.
  • the method of applying the composition for forming a colored layer is the same as the method described in the method of applying the composition for forming a protective layer.
  • the colored layer may be provided on the entire surface of the heat storage body, or may be provided in a pattern on a part thereof.
  • the heat storage member When the heat storage member is in the form of a sheet, a plate, or a film, the heat storage member has a base material arranged on the surface side opposite to the protective layer in the heat storage body and a surface opposite to the heat storage body in the above base material. It may have an adhesion layer arranged on the side and a temporary substrate arranged on the surface side of the adhesion layer opposite to the substrate. As a result, it is possible to suppress damage to the heat storage body during storage and transportation of the heat storage member.
  • the base material and the adhesive layer are as described above.
  • the specific example of the temporary base material is the same as the specific example of the base material. It is preferably a base material having a peeled surface. When using the heat storage member, the temporary base material is peeled off from the heat storage member.
  • the electronic device of the present invention has the above-mentioned heat storage member or heat storage body and a heating element.
  • the heat storage member is as described above.
  • the heating element is a member that may generate heat in an electronic device, and is, for example, a SoC such as a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), a SRAM (Static Random Access Memory), and an RF (Radio Frequency) device. (Systems on a Chip), cameras, LED packages, power electronics, and batteries (especially lithium ion secondary batteries).
  • the heating element may be arranged so as to be in contact with the heat storage member, or may be arranged on the heat storage member via another layer (for example, a heat conductive material described later).
  • the electronic device further preferably has a thermally conductive material.
  • the heat conductive material means a material having a function of conducting heat generated from a heating element to another medium.
  • the thermal conductivity is 10 Wm -1 K -1 or more. That is, the heat conductive material is preferably a material having a thermal conductivity of 10 Wm -1 K -1 or more.
  • the thermal conductivity (unit: Wm -1 K -1 ) is a value measured by a flash method at a temperature of 25 ° C. by a method compliant with Japanese Industrial Standards (JIS) R1611.
  • Examples of the heat conductive material that the electronic device may have include a metal plate, a heat radiating sheet, and silicon grease, and a metal plate or a heat radiating sheet is preferably used.
  • the electronic device preferably has the above-mentioned heat storage member, a heat conductive material arranged on the heat storage member, and a heating element arranged on the surface side of the heat conductive material opposite to the heat storage member. Further, it is more preferable that the electronic device has the above-mentioned heat storage member, a metal plate arranged on the heat storage member, and a heating element arranged on the surface side of the metal plate opposite to the heat storage member.
  • one of the preferred embodiments of the electronic device is a above-mentioned heat storage member, a metal plate arranged on the surface side of the above-mentioned heat storage member opposite to the above-mentioned protective layer, and the above-mentioned heat storage member.
  • An embodiment having a heating element arranged on the surface side of the metal plate opposite to the heat storage member can be mentioned.
  • the protective layer, the heat storage body, the metal plate, and the heat generating body are laminated in this order.
  • the metal plate has a function of protecting the heating element and conducting heat generated from the heating element to the heat storage element.
  • the surface of the metal plate opposite to the surface on which the heating element is provided may be in contact with the heat storage element, or heat may be stored via another layer (for example, a heat dissipation sheet, an adhesion layer, or a base material).
  • the body may be arranged. Examples of the material constituting the metal plate include aluminum, copper, and stainless steel.
  • the heat radiating sheet is a sheet having a function of conducting heat generated from a heating element to another medium, and preferably has a heat radiating material.
  • the heat radiating material include carbon, metal (for example, silver, copper, aluminum, iron, platinum, stainless steel, and nickel), and silicon.
  • Specific examples of the heat radiating sheet include a copper foil sheet, a metal film resin sheet, a metal-containing resin sheet, and a graphene sheet, and a graphene sheet is preferably used.
  • the thickness of the heat radiating sheet is not particularly limited, but is preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m.
  • the electronic device preferably further comprises a heat transport member selected from the group consisting of heat pipes and vapor chambers.
  • Both the heat pipe and the vapor chamber are made of metal or the like and include at least a member having a hollow structure and a working fluid which is a heat transfer medium enclosed in the internal space thereof, and the working fluid in a high temperature part (evaporation part). Evaporates (vaporizes) and absorbs heat, and the vaporized working fluid condenses in the low temperature part (condensed part) and releases heat.
  • the heat pipe and the vapor chamber have a function of transporting heat from a member in contact with a high temperature portion to a member in contact with a low temperature portion due to a phase change of the working fluid inside the heat pipe and the vapor chamber.
  • the heat storage member and the heat pipe or the vapor chamber are in contact with each other, and the heat storage member is a heat pipe.
  • the vapor chamber is in contact with the low temperature portion.
  • the phase change temperature of the heat storage material contained in the heat storage body of the present invention possessed by the heat storage member and heat. It is preferable that the temperature range in which the pipe or vapor chamber operates overlaps.
  • the temperature range in which the heat pipe or the vapor chamber operates includes, for example, a range of temperatures in which the working fluid can undergo a phase change.
  • the heat pipe has at least a tubular member and a working fluid enclosed in its internal space.
  • the heat pipe preferably has a wick structure on the inner wall of the tubular member as a flow path for the working fluid based on the capillary phenomenon, and has a cross-sectional structure in which an internal space for the passage of the vaporized working fluid is provided inside the wick structure. ..
  • Examples of the shape of the tubular member include a circular tube, a square tube, and a flat elliptical tube.
  • the tubular member may have a bent portion.
  • the heat pipe may be a loop heat pipe having a structure in which tubular members are connected in a loop shape.
  • the vapor chamber has at least a flat plate-shaped member having a hollow structure and a working fluid enclosed in the internal space thereof.
  • the vapor chamber preferably has a wick structure similar to that of a heat pipe on the inner surface of a flat plate-shaped member. In the vapor chamber, heat is generally absorbed from a member in contact with one main surface of the flat plate-shaped member, and heat is released to the member in contact with the other main surface to transport heat.
  • the material constituting the heat pipe and the vapor chamber is not particularly limited as long as it is a material having high thermal conductivity, and examples thereof include metals such as copper and aluminum.
  • Examples of the working fluid enclosed in the internal space of the heat pipe and the vapor chamber include water, methanol, ethanol and CFC substitutes, which are appropriately selected and used according to the temperature range of the electronic device to be applied.
  • the electronic device may include a protective layer, a heat storage body, a heat conductive material, a heating element, and other members other than the heat transport member described above.
  • Examples of other members include a base material and an adhesion layer. The base material and the adhesive layer are as described above.
  • the electronic device may have at least one member selected from the group consisting of a heat radiating sheet, a base material, and an adhesion layer between the heat storage body and the metal plate.
  • a heat radiating sheet When two or more members of the heat dissipation sheet, the base material, and the close contact layer are arranged between the heat storage body and the metal plate, the base material and the close contact are made from the heat storage body side toward the metal plate side. It is preferable that the layers and the heat dissipation sheets are arranged in this order. Further, the electronic device may have a heat radiating sheet between the metal plate and the heating element.
  • Example 1> preparation of microcapsule dispersion 100 parts by mass of icosane (latent heat storage material; an aliphatic hydrocarbon having a melting point of 37 ° C. and 20 carbon atoms) was heated and dissolved at 60 ° C. to obtain a solution A to which 120 parts by mass of ethyl acetate was added. Next, 0.1 part by mass of N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine (ADEKApolyether EDP-300, ADEKA CORPORATION) is added to the stirring solution A to make a solution. B was obtained.
  • icosane latent heat storage material; an aliphatic hydrocarbon having a melting point of 37 ° C. and 20 carbon atoms
  • the thickness of the capsule wall of the microcapsules was 0.1 ⁇ m. Further, the deformation rate of the microcapsules taken out from the obtained dispersion was measured by the above method using an HM2000 type microhardness meter manufactured by Fisher Instruments Co., Ltd. as an indentation hardness tester. As a result, the deformation rate of the microcapsules was obtained. Was 41%.
  • microcapsule aggregates After separating the upper layer and the lower layer which is the aqueous phase, the operation of removing the lower layer which is the aqueous phase was repeated four times.
  • the obtained microcapsule agglomerates were wrapped in a non-woven fabric and dried by applying cold air while rubbing to obtain microcapsule powder.
  • the obtained heat storage body forming composition 1 (5 cc) was dropped onto a release film, dried at 85 ° C. for 2 hours to a size of 30 mm in diameter, and the heat storage body without cracks (thickness: 5400 ⁇ m). ) was manufactured.
  • the porosity of the obtained heat storage body was 5% by volume.
  • the heat absorption amount of the heat storage body was 160 J / cc.
  • Example 1 A heat storage body was produced according to the same procedure as in Example 1 except that the type of material used was changed as shown in Table 1.
  • the heat absorption amount of the obtained heat storage body was calculated from the differential scanning calorimetry.
  • the heat absorption amount of the heat storage body itself from which the release film was peeled off was measured.
  • the heat storage body was cut into 15 mm ⁇ 25 mm to prepare a measurement sample.
  • the appearance of defects (cracks and chips) in the heat storage body was visually observed. .. Evaluation was made according to the following criteria. Practically, "0" or "1" is preferable. The case where no defect occurred was set as “0”, the case where cracks occurred very slightly was set as "1”, and the case where cracks and chips occurred was set as "2".
  • the "solid content (%)” column in the “resin” column represents the solid content concentration (mass%) in each commercially available product described in the "type” column in the “resin” column.
  • the “Tg (° C.)” column in the “resin” column in Table 1 represents the glass transition temperature (° C.) of the resin in the commercially available product used.
  • the “breaking elongation” column in the “resin” column in Table 1 represents the breaking elongation (%) of the resin in the commercially available product used.
  • the “resin content (mass%)” column in Table 1 represents the resin content (mass%) with respect to the total mass of the heat storage body.
  • the “heat storage material content (mass%)” column in Table 1 represents the content (mass%) of the heat storage material with respect to the total mass of the heat storage body.
  • the Superflex E2000 shown in Table 1 is a commercially available product sold by Dai-ichi Kogyo Seiyaku Co., Ltd., and the resin contained in the Superflex E2000 is polyurethane.
  • the Superflex 300 shown in Table 1 is a commercially available product sold by Dai-ichi Kogyo Seiyaku Co., Ltd., and the resin contained in the Superflex 300 is polyurethane.
  • the Superflex E4800 shown in Table 1 is a commercially available product sold by Dai-ichi Kogyo Seiyaku Co., Ltd., and the resin contained in the Superflex E4800 is polyurethane.
  • the Kuraray Poval KL-318 shown in Table 1 is a commercially available product sold by Dai-ichi Kogyo Seiyaku Co., Ltd., and the resin contained in Kuraray Poval KL-318 is polyvinyl alcohol.

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Abstract

La présente invention concerne un corps de stockage de chaleur dans lequel l'apparition de défauts pendant la manipulation est supprimée, et un procédé de fabrication du corps de stockage de chaleur. Le corps de stockage de chaleur de la présente invention comprend une microcapsule dans laquelle un matériau de stockage de chaleur est enfermé et une résine, la teneur du matériau de stockage de chaleur par rapport à la masse totale du corps de stockage de chaleur étant supérieure ou égale à 65 % en masse, et le rapport de vide étant inférieur à 10 % en volume.
PCT/JP2021/017520 2020-05-25 2021-05-07 Corps de stockage de chaleur et procédé de fabrication de corps de stockage de chaleur WO2021241167A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023162596A1 (fr) * 2022-02-28 2023-08-31 富士フイルム株式会社 Feuille de stockage thermique, pastille de résine et article moulé

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