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WO2013077379A1 - Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur - Google Patents

Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur Download PDF

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Publication number
WO2013077379A1
WO2013077379A1 PCT/JP2012/080233 JP2012080233W WO2013077379A1 WO 2013077379 A1 WO2013077379 A1 WO 2013077379A1 JP 2012080233 W JP2012080233 W JP 2012080233W WO 2013077379 A1 WO2013077379 A1 WO 2013077379A1
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Prior art keywords
heat storage
storage material
polymer
polymer block
block
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English (en)
Japanese (ja)
Inventor
理夫 森田
島影　雅史
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JSR Corp
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JSR Corp
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Priority claimed from JP2012041570A external-priority patent/JP2013177497A/ja
Application filed by JSR Corp filed Critical JSR Corp
Publication of WO2013077379A1 publication Critical patent/WO2013077379A1/fr
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    • 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
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • 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
    • F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
    • 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 material used in a latent heat storage system that stores heat using latent heat generated with a phase change, and a heat storage device using the heat storage material. Moreover, this invention relates to the thermal storage microcapsule used suitably as a content component of the said thermal storage material.
  • Examples of such a heat storage material include a material that uses the heat capacity and specific heat (sensible heat) of a substance, a material that uses the amount of heat (latent heat) generated with the phase change of the substance, and a material that uses the chemical reaction heat of the substance.
  • Thermal storage materials that utilize latent heat associated with phase changes (melting and solidification) of organic compounds such as paraffin compounds and fatty acids are now widely used.
  • Heat storage methods are broadly divided into (1) a heat storage method in which a non-fluid heat storage material is fixed and stored in the heat storage tank, and (2) the heat storage material is made fluid and transported from the heat storage tank to the heat exchanger.
  • the heat transfer method has been attracting attention because of its superior thermal efficiency and controllability.
  • a heat storage material having fluidity a heat storage material made of an emulsion composed of a paraffin compound as a dispersoid, water as a dispersion medium, and a surfactant is known (for example, see Patent Documents 1 and 2). .
  • the heat storage material having such fluidity has a problem that the particle size of the dispersoid becomes unstable due to repeated phase changes during use, and it is difficult to maintain its shape.
  • a heat storage capsule in which a core material that performs latent heat storage is encapsulated in a coating is because a change in the amount of heat accompanying a phase change of the core material is performed in a coating that surrounds the core material. Since the core material can be handled as particles regardless of the state, it has an advantage of easy handling.
  • heat storage capsules obtained by reaction of melamine or urea with formaldehyde using a paraffin compound as a heat storage material and coated with melamine resin or urea resin see, for example, Patent Document 3
  • poly (meth) acrylate and polystyrene derivatives Thermal storage capsules (see, for example, Patent Documents 4 and 5) that use a resin obtained by radical polymerization such as a coating as a coating have been proposed.
  • a heat storage microcapsule (see, for example, Patent Document 6) having a polyurethane resin or polyurea resin film obtained by reacting a polyvalent isocyanate and an active hydrogen compound with a paraffin compound as a core substance is also thermoplastic.
  • a heat storage microcapsule (see, for example, Patent Document 7) composed of a resin outer shell and a heat storage material and a core material containing hydroxy fatty acid as a gelling agent has been proposed.
  • heat storage capsules have a problem that, since the core material is a paraffin compound or the like, an excessive external force is applied to the heat storage capsule during the use process, and the heat storage material leaks when the coating is deteriorated or broken.
  • JP-A-57-40582 JP 2000-336350 A Japanese Patent No. 2988765 JP 2002-69438 A JP 2001-181611 A JP-A-7-133479 JP 2008-297503 A
  • the present invention it is intended to provide a heat storage material such as an emulsion-type heat storage material that maintains a stable particle diameter even when phase changes are repeated during use, and withstands long-term use, and a heat storage device using the same. Let it be an issue.
  • Another object of the present invention is to provide a heat storage capsule that hardly leaks out a heat storage material even if the coating is deteriorated or broken, and a heat storage material using the same.
  • the present inventors have found that the above-mentioned problems can be solved by the following configuration, and have completed the present invention. That is, the present invention is as follows.
  • a heat storage material in which particles containing a heat storage material and an elastomer are dispersed wherein the heat storage material is a paraffin compound, a fatty acid, a fatty acid ester compound, an aliphatic ether, an aliphatic ketone, and an aliphatic
  • a heat storage material comprising at least one selected from the group consisting of alcohols.
  • At least one heat storage material selected from the group consisting of paraffin compounds, fatty acids, fatty acid ester compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols, elastomers, water, and surface activity
  • a heat storage material consisting of an emulsion containing an agent.
  • the hydrogenated conjugated diene (co) polymer includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a conjugated diene 50 masses of the polymer block (B) having a vinyl bond content of 30 to 95 mol% including the structural unit (b-1) derived from the compound and the structural unit (c-1) derived from the alkenyl aromatic compound [5], obtained by hydrogenating a block (co) polymer having at least one polymer block selected from the group consisting of The heat storage material described in 1.
  • the block (co) polymer has at least a polymer block (A) and a polymer block (B), and at least one terminal is the polymer block (A).
  • the heat storage material according to any one of [3] to [7], which is an oil-in-water emulsion in which at least the heat storage material and the elastomer are dispersoids and the water is a dispersion medium.
  • a heat storage device obtained by filling a container with the heat storage material according to any one of [1] to [8].
  • a core comprising an elastomer and at least one heat storage material selected from the group consisting of paraffin compounds, fatty acids, fatty acid ester compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols.
  • Thermal storage microcapsules in which the substance is covered by a coating.
  • the hydrogenated conjugated diene (co) polymer includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a conjugated diene 50 masses of the polymer block (B) having a vinyl bond content of 30 to 95 mol% including the structural unit (b-1) derived from the compound and the structural unit (c-1) derived from the alkenyl aromatic compound % Obtained by hydrogenating a block (co) polymer having at least one polymer block selected from the group consisting of a polymer block (C) containing more than%, and [12] Thermal storage microcapsules as described in 1.
  • the block (co) polymer has at least a polymer block (A) and a polymer block (B), and at least one terminal thereof is the polymer block (A).
  • Thermal storage microcapsule as described.
  • the film is a melamine resin, urea resin, polystyrene resin, acrylic resin, styrene- (meth) acrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, polyester resin, polyurethane resin, polyurea resin, and polyamide resin.
  • a heat storage material comprising the heat storage microcapsule according to any one of [10] to [15].
  • a heat storage material such as an emulsion-type heat storage material that maintains a stable particle size even when phase changes are repeated during use, and withstands long-term use, and a heat storage device using the same. Can do.
  • the heat storage material of the present invention is a heat storage material in which particles containing a heat storage material and an elastomer (hereinafter also referred to as “heat storage material particles”) are dispersed, and the heat storage material is an ester of a paraffin compound, a fatty acid, or a fatty acid. It contains at least one selected from the group consisting of compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols.
  • the polystyrene-equivalent weight average molecular weight of the elastomer measured by gel permeation chromatography method is preferably 10,000 to 700,000, more preferably 100,000 to 500,000, and more preferably 200,000 to Particularly preferred is 500,000.
  • the average particle diameter of the heat storage material particles is exemplified by 0.01 to 3000 ⁇ m, and the content of the heat storage material particles is typically 1 to 80% by mass, preferably 3 to 70% by mass in 100% by mass of the heat storage material. Is done.
  • the average particle diameter of the heat storage material particles can be obtained as a MV value (Mean Volume Diameter) by a laser diffraction / scattering particle size analyzer.
  • an emulsion type heat storage material made of an emulsion containing a heat storage material, an elastomer, water, and a surfactant may be mentioned.
  • a heat storage material in which the heat storage material particles are dispersed in at least one selected from the group consisting of concrete, mortar, various rubbers, synthetic resins, paints, and fibers. Can be mentioned.
  • the heat storage microcapsule of the present invention is a capsule in which a core material containing a heat storage material and an elastomer is coated with a coating.
  • the heat storage microcapsules of the present invention can be suitably used as heat storage material particles contained in the heat storage material of the second aspect.
  • the heat storage microcapsules of the present invention can be used alone or together with a heat transfer medium such as water by filling a container such as a packaging container or a metal container.
  • Heat storage material of first aspect emulsion type heat storage material
  • the emulsion-type heat storage material that is the heat storage material of the first aspect of the present invention comprises an emulsion containing a heat storage material, an elastomer, water, and a surfactant.
  • the heat storage material, the elastomer, and other components used as necessary may be collectively referred to as “dispersoid”, and water may be referred to as “dispersion medium”.
  • the heat storage material and the elastomer are mixed to form oil droplets in such a state that the elastomer encloses the heat storage material, and becomes a dispersoid and exists in the dispersion medium. .
  • These oil droplets correspond to the heat storage material particles.
  • At least one selected from the group consisting of paraffin compounds, fatty acids, fatty acid ester compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols is preferably used.
  • An elastomer is used to maintain a stable particle size even when the heat storage material repeats phase changes.
  • the emulsion type heat storage material of the present invention is an oil-in-water emulsion (hereinafter referred to as “O / O”) in which fine oil droplets of a heat storage material and an elastomer are dispersed using water as a dispersion medium in water serving as a dispersion medium. Also referred to as “W emulsion”).
  • the content of the elastomer in the dispersoid is preferably 1 to 33% by mass, more preferably 1 to 20% by mass in 100% by mass of the dispersoid. From the viewpoint of preventing instability of the emulsion and obtaining a sufficient amount of latent heat and heat storage effect, it is preferably not less than the above lower limit value, and also prevents coalescence of dispersoids during freezing of the emulsion, From the viewpoint of maintaining fluidity, the upper limit value is preferred.
  • the average particle size of the oil droplets in the emulsion is preferably from 0.1 to 30 ⁇ m, more preferably from 0.1 to 25 ⁇ m, particularly preferably from 0.3 to 20 ⁇ m. From the viewpoint of preventing instability of the emulsion and obtaining a sufficient amount of latent heat and heat storage effect, it is preferably not less than the above lower limit value, and also prevents coalescence of dispersoids during freezing of the emulsion, From the viewpoint of maintaining fluidity, the upper limit value is preferred.
  • average particle diameter of oil droplets in the present specification means a volume average particle diameter measured by a laser diffraction / scattering method.
  • the volume average particle diameter can be obtained as an MV value by measuring the obtained emulsion with a laser diffraction / scattering particle size analyzer.
  • the emulsion-type heat storage material of the present invention after mixing only the components constituting the dispersoid and the surfactant, this may be mixed and stirred together with the dispersion medium, or all the components may be mixed and stirred together. May be.
  • the mixing and stirring conditions are not particularly limited, but a known stirring means is used. From the viewpoint of obtaining an emulsion suitable for productivity and a heat storage material, the stirring speed is 1,000 to 100,000 rpm, 1 minute to 1 hour. It is preferable to mix and stir under the conditions.
  • ⁇ Surfactant> In order to mix and disperse the dispersoid and water and uniformly mix and disperse, there is a method of emulsifying using a surfactant.
  • the surfactant has an effect of protecting the oil droplets and an effect of stabilizing the oil droplets by preventing aggregation and coalescence of the oil droplets in the dispersion medium.
  • the surfactant for example, known ones such as a nonionic surfactant and an anionic surfactant can be used. From the viewpoint of the stability of the dispersoid, a nonionic surfactant is preferably used. Specifically, there are surfactants such as ether type, alkylphenol type, ester type, sorbitan ester type, sorbitan ester ether type and the like. These may be used alone or in combination of two or more.
  • the addition amount of the surfactant is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heat storage material. From the viewpoint of obtaining an emulsion in which the dispersoid is sufficiently dispersed in the dispersion medium, 0.1% is added. More preferably, it is ⁇ 10 parts by mass.
  • water used as a dispersion medium may be industrial water, but ion exchange water or distilled water is preferable because it hardly affects the heat storage material.
  • the content of the dispersoid is usually 1 to 80% by mass, preferably 3 to 70% by mass in 100% by mass of the emulsion type heat storage material.
  • the content is in the above range, it is preferable from the viewpoint of obtaining an industrially useful heat storage amount while maintaining the stability of the dispersoid.
  • the emulsion-type heat storage material of the present invention is an emulsion that is excellent in stability even when phase changes are repeated, it can be filled into a container such as a packaging container or a metal container to form a heat storage device. Further, the heat storage device alone or together with a heat transfer medium such as water can be used in various fields such as an air conditioning application, an electronic component temperature rise prevention application, and a target article heat insulation application. Moreover, the emulsion-type heat storage material of the present invention can be used as a heat source for air conditioning by filling a heat storage tank to store the amount of external heat. Furthermore, the emulsion type heat storage material is filled in an air conditioning circuit that circulates between the heat storage tank and the heat exchanger, thereby being used as a heat transfer medium (also referred to as brine).
  • a heat transfer medium also referred to as brine
  • the heat storage material according to the second aspect of the present invention is a heat storage material in which the heat storage material particles are dispersed in at least one selected from the group consisting of concrete, mortar, various rubbers, synthetic resins, paints and fibers.
  • Such heat storage materials are used for air conditioning in public facilities such as hotels; canisters for automobiles, etc .; for preventing temperature rise of electronic components such as IC chips; textiles for clothing, organ transport containers, concrete materials for buildings, etc. It can be used in various fields such as heat retention applications; antifogging applications such as curve mirrors;
  • the heat storage microcapsule of the present invention is suitably used as a component of the heat storage material of the present invention, that is, a heat storage material particle.
  • the heat storage microcapsule of the present invention has a configuration in which a core material containing a heat storage material and an elastomer is covered with a coating. That is, the heat storage microcapsule of the present invention has a configuration in which a film is formed around a core material containing a heat storage material and an elastomer.
  • the heat storage material, the elastomer, and other components used as necessary may be collectively referred to as a “core material”.
  • ⁇ Core material> As the heat storage material, at least one selected from the group consisting of paraffin compounds, fatty acids, fatty acid ester compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols is preferably used.
  • An elastomer is used to prevent leakage of the heat storage material even if the coating deteriorates or breaks.
  • the ratio of the heat storage material in the heat storage microcapsule of the present invention is the same as the heat storage microcapsule and the amount of latent heat derived from the heat storage material in the heat storage microcapsule (kJ / kg). It can be calculated as a value divided by the amount of latent heat (kJ / kg) derived from the same heat storage material ⁇ 100 (%).
  • the ratio of the heat storage material is preferably 40 to 80%, more preferably 50 to 70%. From the viewpoint of obtaining a practical amount of latent heat, 50% or more is preferable, and from the viewpoint of obtaining strength against the external force of the heat storage microcapsule, it is preferably 70% or less.
  • Examples of the resin constituting the film of the heat storage microcapsule of the present invention include melamine resin, urea resin, polystyrene resin, acrylic resin, styrene- (meth) acrylate copolymer resin, acrylonitrile-styrene copolymer resin, polyester resin. , At least one resin selected from the group consisting of polyurethane resins, polyurea resins, and polyamide resins.
  • melamine resin for example, melamine resin, urea resin, polystyrene resin, acrylic resin, styrene- (meth) acrylate copolymer resin, acrylonitrile-styrene copolymer resin are preferable.
  • melamine resin urea resin
  • polystyrene resin acrylic resin
  • styrene- (meth) acrylate copolymer resin acrylonitrile-styrene copolymer resin
  • the said resin may contain the other monomer for the purpose of providing a function, and the said resin may be bridge
  • the heat storage microcapsules of the present invention can be used in the form of powder, granules or the like.
  • the shape of the heat storage microcapsule is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a daruma shape, a weight shape, a box shape, and a rod shape.
  • the average particle size of the heat storage microcapsules of the present invention prevents breakage due to external forces such as mechanical shearing force and impact, and when the heat storage microcapsules are dispersed in a dispersion medium and used as a dispersion, the viscosity increase during dispersion is increased. From the viewpoint of prevention, it is preferably 0.01 to 3000 ⁇ m, more preferably 0.1 to 1000 ⁇ m, and particularly preferably 1.0 to 100 ⁇ m.
  • the “average particle diameter of the heat storage microcapsule” means a volume average particle diameter measured by a laser diffraction / scattering method.
  • the volume average particle diameter can be obtained as an MV value by dispersing the obtained microcapsules in an aqueous medium and using a laser diffraction / scattering particle size analyzer.
  • the average particle size of the heat storage microcapsules of the present invention can be set to a desired value by adjusting and changing the following conditions, for example.
  • Operation conditions such as the number of revolutions of stirring and time of the atomizer (also referred to as an emulsifier, a disperser, etc.),
  • Type of emulsifier anionic surfactant, nonionic surfactant, etc.
  • Monomer type surfactant such as sodium alkylbenzene sulfonate, polymer type surfactant such as sodium polyacrylate
  • concentration of surfactant (4) temperature of emulsion during emulsification, (5) Emulsification ratio (mass ratio of water phase to oil phase).
  • the heat storage microcapsule of the present invention can be used as a heat storage material for various applications by being contained in other substances.
  • the heat storage material in the present invention is not particularly limited, but the heat storage microcapsule of the present invention is used together with other components.
  • the heat storage microcapsule is applied to concrete, mortar, various rubbers, synthetic resins, paints, fibers, etc. Examples thereof include those in which the heat storage microcapsules are mixed alone or together with a heat transfer medium such as water and filled in a container such as a packaging container or a metal container.
  • Such heat storage materials are used for air conditioning in public facilities such as hotels; canisters for automobiles, etc .; for preventing temperature rise of electronic components such as IC chips; textiles for clothing, organ transport containers, concrete materials for buildings, etc. It can be used in various fields such as heat retention applications; antifogging applications such as curve mirrors;
  • the dispersion liquid in which the heat storage microcapsules of the present invention are dispersed can be filled in a heat storage tank to store the amount of external heat and used as a heat source for air conditioning. Further, the dispersion liquid is filled in an air conditioning circuit that circulates between the heat storage tank and the heat exchanger, thereby being used as a heat transfer medium.
  • the heat storage material of the present invention can be used together with other components described later.
  • anti-aging agents antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, flame retardants, antibacterial / antifungal agents, antiblocking agents, dispersants in heat transfer media used with heat storage microcapsules .
  • Anti-coloring agents rust inhibitors, specific gravity adjusting agents, thickening stabilizers, antifreezing agents, preservatives and the like.
  • a method for obtaining a film covering the core substance is not particularly limited.
  • a method of spraying a thermoplastic resin on the surface of the heat storage material particles, a submerged drying method, a spray drying method, a pan examples thereof include a coating method, a coacervation method, an orifice method, an interfacial polymerization method, and an In Situ (in situ) method.
  • the core substance can be covered with a film to obtain a desired heat storage microcapsule.
  • the In Situ method is preferred from the viewpoint of the heat resistance of the resulting coating.
  • An example of the production procedure of the heat storage microcapsule of the present invention by the In Situ method is as follows.
  • a core material is prepared by dissolving an elastomer in a heat storage material.
  • a known film forming monomer such as melamine or urea monomer is dissolved and mixed in the obtained core material.
  • a known amine catalyst, metal catalyst or the like may be added as necessary.
  • other additives such as a filler may be added in order to impart a desired function.
  • the obtained mixture (oil phase mixture) is emulsified in water in the presence of an emulsifier.
  • the mass ratio of the oil phase mixture to water during emulsification (oil phase mixture: water) is preferably 5:95 to 80:20, more preferably 10:90 to 60:40, from the viewpoint of obtaining processability.
  • the emulsifier at the time of emulsification include known anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and known protective colloid agents.
  • the concentration of the emulsifier in water is preferably 0.1% by mass to 20% by mass.
  • emulsifying device used for emulsification, turbine type, propeller type, anchor type, ribbon type and other stirring tanks, high pressure emulsifier, ultrasonic emulsifier, membrane emulsifier, homogenizer, homodisper, homomixer, line type A well-known thing, such as an emulsifier, can be used. These devices may be batch or continuous.
  • the emulsification temperature is preferably a temperature equal to or higher than the melting point of the core substance, and is preferably selected from the range of 0 ° C to 95 ° C.
  • the emulsification time (in the case of continuous emulsification, the process liquid residence time in the emulsification apparatus) is preferably 1 second to 2 hours.
  • a pH adjuster is added to obtain the desired pH. If necessary, a water-soluble catalyst may be added.
  • the resulting mixture is heated and stirred to conduct a polymerization reaction, thereby performing microencapsulation.
  • the reaction temperature is usually 0 ° C. to 95 ° C., preferably 30 ° C. to 80 ° C.
  • the reaction time may be 30 minutes to 30 hours, but it is preferable to set the amount of catalyst, reaction temperature, etc. so that the reaction is completed within 6 hours for practical use.
  • a known antifoaming agent or the like may be added to the reaction system for the purpose of promoting the reaction and defoaming.
  • the heat storage microcapsules can be obtained in a state (hereinafter also referred to as “slurry”) contained in an aqueous dispersion in which the heat storage microcapsules are suspended in water.
  • a known thickening stabilizer, antifreezing agent, preservative, dispersant, specific gravity adjusting agent, and other additives can be added to the resulting slurry as necessary. If necessary, the concentration of solids can be adjusted by adding dilution water.
  • the heat storage microcapsules of the present invention can be used as a heat storage material.
  • Heat storage microcapsules can be obtained by removing water from the slurry.
  • Examples of the method for removing water include a spray drying method, a freeze drying method, a drum drying method, and the like for a microcapsule dispersion.
  • the heat storage material used in the heat storage material and the heat storage microcapsule of the present invention will be described below.
  • the heat storage material is preferably a latent heat storage material from the viewpoint of heat storage capacity, and at least selected from the group consisting of paraffin compounds, fatty acids, fatty acid ester compounds, aliphatic ethers, aliphatic ketones, and aliphatic alcohols.
  • paraffin compounds, aliphatic alcohols and fatty acid ester compounds are preferred, and paraffin compounds are more preferred.
  • the heat storage effect by the sensible heat storage using the specific heat of the material is not excluded.
  • the heat storage material preferably has a melting point measured by the differential scanning calorimetry (DSC method) in the range of ⁇ 30 to 130 ° C. from the viewpoint of utilizing the heat storage material and the heat storage microcapsule in a wide range of fields. More preferably, the temperature is in the range of 100 ° C to 100 ° C.
  • the heat of fusion measured by the differential scanning calorimetry (DSC method) of the heat storage material is desirably 100 kJ / kg or more from the viewpoint of using latent heat due to the phase change in various fields.
  • the melting point of the heat storage material corresponds to Tim when measured according to JIS K-7121.
  • the melting point of the heat storage material having a plurality of melting peaks was the extrapolated melting start temperature of the melting peak having a larger heat of fusion, and the latent heat was the heat of fusion of the melting peak.
  • the latent heat was the heat of fusion of the melting peak.
  • thermal storage material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the heat storage material is preferably 200 to 10000 parts by mass with respect to 100 parts by mass of the elastomer, particularly 100 parts by mass of the hydrogenated conjugated diene (co) polymer, It is more preferably from ⁇ 3000 parts by mass, and still more preferably from 400 to 2,000 parts by mass. It is preferably 200 parts by mass or more from the viewpoint of securing a sufficient amount of latent heat when made into an emulsion, and 3000 parts by mass or less from the viewpoint of maintaining a stable particle size of the dispersoid even when the phase change is repeated. Is preferred.
  • the content of the heat storage material is preferably 200 to 10,000 parts by weight, more preferably 300 to 10,000 parts by weight, based on 100 parts by weight of the elastomer, particularly 100 parts by weight of the hydrogenated conjugated diene (co) polymer.
  • the amount is more preferably 4000 parts by mass, and still more preferably 400 to 2000 parts by mass. It is preferably 200 parts by mass or more from the viewpoint of securing a sufficient amount of latent heat when microcapsules are used, and is 4000 parts by mass or less from the viewpoint of maintaining a stable particle size of the microcapsules even when the phase change is repeated. It is preferable.
  • paraffin compounds examples include paraffin compounds having 8 to 100 carbon atoms.
  • a paraffin compound may be used individually by 1 type, and may use 2 or more types together. By using a combination of paraffin compounds having different carbon numbers, the melting point or freezing point of the heat storage material and the heat storage microcapsule can be set to a desired value.
  • paraffin compound a compound having an alkylene group having 10 to 30 carbon atoms is more preferable.
  • linear paraffins such as n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-icosane, and branched paraffins. Can be mentioned.
  • the paraffin compound is preferably a linear paraffin, that is, n-paraffin, from the viewpoint of further increasing the amount of latent heat.
  • the n-paraffin is preferably contained in an amount of 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 99% by mass or more, based on the total paraffin compound. Is preferred.
  • petroleum wax can be used as an embodiment of a paraffin compound having 8 to 100 carbon atoms.
  • Examples of petroleum waxes include paraffin wax (a wax that is solid at room temperature, which is produced by separating and refining oil or natural gas as a raw material from a vacuum distillation distillate), and microcrystalline wax (a reduced pressure using petroleum as a raw material).
  • paraffin wax a wax that is solid at room temperature, which is produced by separating and refining oil or natural gas as a raw material from a vacuum distillation distillate
  • microcrystalline wax a reduced pressure using petroleum as a raw material.
  • Aliphatic hydrocarbons such as wax produced at a normal temperature by separation and purification from distillation residue oil or heavy distillate oil.
  • paraffin wax having about 20 to 40 carbon atoms and microcrystalline wax having about 30 to 60 carbon atoms are preferable.
  • paraffin wax products include “HNP-9”, “FNP-0090”, and “FT115” (all manufactured by Nippon Seiwa Co., Ltd.).
  • the paraffin compound preferably has a melting point measured by a differential scanning calorimetry (DSC method) in the range of ⁇ 30 to 130 ° C. from the viewpoint of effective use of heat in the living temperature range and the high temperature range, and 0 to 100 More preferably in the range of ° C.
  • the heat of fusion measured by the differential scanning calorimetry (DSC method) of the paraffin compound is preferably 100 kJ / kg or more from the viewpoint of utilizing latent heat due to the phase change in various fields.
  • the melting point of the paraffin compound in the present specification corresponds to Tim when measured according to JIS K-7121.
  • n-undecane ( ⁇ 27 ° C., 160 kJ / kg), n-dodecane ( ⁇ 10 ° C., 185 kJ / kg), n-tridecane ( ⁇ 7 ° C., 150 kJ / kg), n-tetradecane (6 ° C., 230 kJ / kg) N-pentadecane (9 ° C., 165 kJ / kg), n-hexadecane (18 ° C., 230 kJ / kg), n-heptadecane (21 ° C., 170 kJ / kg), n-octadecane (28 ° C., 240 kJ / kg), n Nonadecane (32 ° C., 170 kJ / kg), n-icosane (37 ° C., 250
  • fatty acid for example, a fatty acid having 8 to 30 carbon atoms can be used, and is roughly classified into a linear saturated fatty acid, a linear unsaturated fatty acid, a branched saturated fatty acid, and a branched unsaturated fatty acid. Of these, linear saturated fatty acids are preferably used in the present invention.
  • linear saturated fatty acids examples include octanoic acid (C8), nonanoic acid (C9), decanoic acid (capric acid) (C10), dodecanoic acid (lauric acid) (C12), and tetradecanoic acid (myristic acid) (C14).
  • a linear saturated fatty acid having 10 to 18 carbon atoms is preferably used from the viewpoint of availability.
  • fatty acid ester compound for example, a long-chain fatty acid ester having 8 to 30 carbon atoms can be used. Specifically, vinyl stearate, dimethyl sebacate, butyl stearate, isopropyl stearate, isopropyl palmitate, Examples include propyl palmitate and myristyl myristate.
  • fatty acid ester compounds methyl, ethyl, propyl, butyl and tetradecyl esters of linear saturated fatty acids having 10 to 18 carbon atoms are preferably used from the viewpoint of availability.
  • an aliphatic ether having 14 to 60 carbon atoms can be used, and specific examples include heptyl ether, octyl ether, tetradecyl ether, hexadecyl ether and the like.
  • an ether compound (symmetric ether compound) having a single oxygen atom and having a symmetric structure is preferably used from the viewpoint of having a high latent heat amount and being easily synthesized.
  • aliphatic ketones for example, aliphatic ketones having 8 to 30 carbon atoms can be used. Specifically, 2-nonanone, tridecanal, 2-pentadecanone, 3-hexadecanone, 8-pentadecanone, 4, 4-bicyclohexanone and the like can be mentioned. Among these, an aliphatic ketone having one oxygen atom is preferably used from the viewpoint of having a latent heat amount suitable for industrial use and being easily synthesized.
  • aliphatic alcohol for example, an aliphatic alcohol having 8 to 60 carbon atoms can be used. Specifically, 2-dodecanol, 1-tetradecanol, 7-tetradecanol, 1-octadecanol are used. 1-eicosanol, 1,10-decanediol and the like. Among these, from the viewpoint of obtaining a latent heat amount suitable for industrial use, an alcohol compound (terminal alcohol compound) in which a hydroxyl group is present at the molecular end is preferably used.
  • ⁇ Elastomer> The elastomer used in the heat storage material and the heat storage microcapsule of the present invention will be described below.
  • an elastomer is used to maintain a stable particle size of the dispersoid even when the heat storage material repeats phase changes.
  • an elastomer is used to prevent leakage of the heat storage material from the film even if the film is deteriorated or broken.
  • the elastomer encloses the heat storage material because leakage of the heat storage material from the coating can be suppressed.
  • elastomer examples include conjugated diene rubber (excluding hydrogenated conjugated diene (co) polymer; the same applies hereinafter), ethylene / ⁇ -olefin copolymer rubber, and hydrogenated conjugated diene (co) polymer.
  • conjugated diene rubber excluding hydrogenated conjugated diene (co) polymer; the same applies hereinafter
  • ethylene / ⁇ -olefin copolymer rubber ethylene / ⁇ -olefin copolymer rubber
  • hydrogenated conjugated diene (co) polymer examples include ethylene / vinyl acetate copolymers. These may be used alone or in combination of two or more.
  • Elastomers have rubber elasticity and work as a binder component that satisfactorily encloses the heat storage material, so that it is preferable for maintaining the shape stability of the dispersoid in the heat storage material, and in the heat storage microcapsule, the heat storage material leaks from the coating. Can be prevented.
  • thermoplastic elastomers are preferred because they can be repeatedly molded during production, and hydrogenated conjugated dienes (co-polymers) from the viewpoints of phase separation, prevention of bleed of heat storage materials, and long-term durability. ) A polymer is more preferred.
  • the elastomer preferably has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by a gel permeation chromatography method of 10,000 to 700,000, more preferably 100,000 to 500,000. The number is preferably 200,000 to 500,000.
  • Mw polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 10,000 to 700,000, more preferably 100,000 to 500,000. The number is preferably 200,000 to 500,000.
  • Mw polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography method of 10,000 to 700,000, more preferably 100,000 to 500,000. The number is preferably 200,000 to 500,000.
  • Mw is 10,000 or more, and ensure fluidity for molding the heat storage material. Therefore, it is preferable that Mw is 700,000 or less.
  • Conjugated diene rubbers include, for example, natural rubber; butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), isoprene rubber (IR) ) And synthetic rubber such as butyl rubber (IIR).
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • IR isoprene rubber
  • IIR butyl rubber
  • ethylene / ⁇ -olefin copolymer rubber examples include a binary copolymer rubber of ethylene and ⁇ -olefin (eg, ethylene / propylene copolymer rubber (EPM)), non-conjugated with ethylene and ⁇ -olefin. And terpolymer rubber with diene (eg, ethylene / propylene / diene copolymer rubber (EPDM)).
  • EPM ethylene / propylene copolymer rubber
  • EPDM terpolymer rubber with diene
  • ⁇ -olefins examples include ⁇ -olefins having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms such as propylene and 1-octene.
  • the ⁇ -olefin may be used alone or in combination of two or more.
  • non-conjugated diene examples include ethylidene-2-norbornene.
  • a nonconjugated diene may be used individually by 1 type, and may use 2 or more types together.
  • hydrogenated conjugated diene (co) polymer examples include styrene-ethylene / butylene-styrene block (co) polymer (SEBS), styrene-ethylene / propylene-styrene block (co) polymer (SEPS), and styrene- Hydrogenated products of block (co) polymers of alkenyl aromatic compounds and conjugated diene compounds such as ethylene / butylene block (co) polymer (SEB) and styrene-ethylene / propylene block (co) polymer (SEP); styrene Alkenyl aromatic compounds such as ethylene / butylene-olefin crystal block (co) polymer (SEBC), olefin crystal block (co) polymer, olefin crystal, ethylene / butylene-olefin crystal block (co) polymer (CEBC) Olefin crystal block (
  • the hydrogenated conjugated diene (co) polymer contains a structural unit (a-1) derived from a conjugated diene compound (hereinafter also referred to as “structural unit (a-1)”), and has a vinyl bond content of less than 30 mol%. And a structural unit (b-1) derived from a conjugated diene compound (hereinafter also referred to as “structural unit (b-1)”) and having a vinyl bond content of 30 to 95 mol%.
  • a polymer block containing more than 50 mass% of the polymer block (B) and the structural unit (c-1) derived from an alkenyl aromatic compound (hereinafter also referred to as “structural unit (c-1)”) ( The polymer is preferably a polymer obtained by hydrogenating a block (co) polymer having at least one polymer block selected from the group consisting of C).
  • structural unit derived from a compound usually means a structural unit based on the reaction of a polymerizable double bond moiety of the compound.
  • Polymer block (A) is a polymer block containing a structural unit (a-1) derived from a conjugated diene compound.
  • the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, Examples include 4,5-diethyl-1,3-octadiene and chloroprene.
  • 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable from the viewpoint of obtaining a heat storage material and a heat storage microcapsule excellent in availability and physical properties.
  • a conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.
  • the structural unit (a-1) is preferably a structural unit containing 95 to 100% by mass of a structural unit derived from 1,3-butadiene, and is a structural unit composed only of a structural unit derived from 1,3-butadiene. It is particularly preferred.
  • the content ratio of the structural unit (a-1) in the polymer block (A) is 95% by mass or more based on the polymer block (A) from the viewpoint of maintaining fluidity during the molding process of the heat storage material and the heat storage microcapsule.
  • the polymer block (A) is more preferably composed of only the structural unit (a-1).
  • the vinyl bond content in the polymer block (A) is less than 30 mol%, preferably less than 20 mol%, more preferably from the viewpoint of maintaining shape retention when the heat storage material and the heat storage microcapsule are formed. Is 18 mol% or less.
  • the lower limit of the vinyl bond content in the polymer block (A) is not particularly limited.
  • the vinyl bond content is a conjugated diene compound incorporated in a polymer block before hydrogenation in a 1,2-bond, 3,4-bond and 1,4-bond bond mode.
  • the total ratio (based on mol%) of those incorporated by 1,2-bonds and 3,4-bonds.
  • the polymer block (B) is a polymer block containing the structural unit (b-1) derived from the conjugated diene compound, and has an effect of imparting softening to the heat storage material and the heat storage microcapsule, or the polymer block From the viewpoint of preventing crystallization of (B), it may be a polymer block further comprising a structural unit derived from an alkenyl aromatic compound (hereinafter also referred to as “structural unit (b-2)”).
  • conjugated diene compound for example, compounds similar to the conjugated diene compounds listed in the structural unit (a-1) can be used, and preferred compounds are also the same.
  • the conjugated diene compounds in the structural units (a-1) and (b-1) may be the same or different.
  • the structural unit (b-1) is preferably a structural unit containing a total of 95 to 100% by mass of structural units derived from 1,3-butadiene and / or isoprene, and includes 1,3-butadiene and / or isoprene. More preferably, it is a structural unit consisting only of the derived structural unit.
  • the content ratio of the structural unit (b-1) in the polymer block (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to the polymer block (B). .
  • the content ratio of the structural unit (b-2) is heavy from the viewpoint of maintaining fluidity during the molding process of the heat storage material and the heat storage microcapsule. It is preferable that it is 50 mass% or less with respect to a unification block (B).
  • the mass ratio of the structural unit (b-1) / structural unit (b-2) in the polymer block (B) is preferably 100/0 to 50/50, more preferably 100/0 to 70/30, and even more preferably. Is 100/0 to 80/20.
  • alkenyl aromatic compound examples include styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p-aminostyrene, and vinylpyridine.
  • styrene and ⁇ -methylstyrene are preferable from the viewpoint of availability and ease of polymerization.
  • the distribution of the structural unit (b-1) is random, tapered ( The structural unit (b-1) increases or decreases along the molecular chain), a partial block shape, or any combination thereof.
  • the vinyl bond content in the polymer block (B) is 30 to 95 mol%, preferably 30 to 85 mol%, more preferably 40 to 75 mol%. From the viewpoint of preventing bleeding of the heat storage material when the heat storage material and the heat storage microcapsule are formed, the vinyl bond content in the polymer block (B) is preferably 30 mol% or more.
  • the polymer block (C) is a polymer block containing more than 50% by mass of the structural unit (c-1) derived from the alkenyl aromatic compound, and preferably a polymer block consisting of only the structural unit (c-1). It is a coalesced block.
  • the alkenyl aromatic compound in the structural unit (c-1) include the same compounds as the alkenyl aromatic compound in the structural unit (b-2), and preferred compounds are also the same.
  • the block (co) polymer does not have the polymer block (C)
  • the mass conversion of the polymer block (A) and the polymer block (B) is usually 5/95 to 50/50, preferably 10/90 to 40/60. From the viewpoint of ensuring shape retention when the heat storage material and the heat storage microcapsules are formed, the ratio of the polymer block (A) is preferably 5 or more and the ratio of the polymer block (B) is 95 or less.
  • the ratio of the polymer block (A) is 50 or less, and the ratio of the polymer block (B) is 50 or more. preferable.
  • the block (co) polymer has the polymer block (C) and does not have the polymer block (C) at both ends
  • the mass conversion ratio ( ⁇ (A) + (B) ⁇ / (C)) with the polymer block (C) is usually 80/20 to 99/1, preferably 85/15 to 95/5. is there.
  • the ratio of the polymer block (C) is preferably 20 or less from the viewpoint of maintaining the workability during melting (fluidity during molding).
  • the polymer block (A) and the ratio in terms of mass of the polymer block (B) and the polymer block (C) (A ) / (B) / (C) is usually from 0/80/20 to 49.5 / 49.5 / 1.
  • the ratio of the polymer block (C) is preferably 20% by mass or less from the viewpoint of maintaining the workability during melting (fluidity during molding).
  • the content ratio of the structural unit derived from the alkenyl aromatic compound is 20 with respect to the block (co) polymer from the viewpoint of maintaining fluidity during the molding process of the heat storage material and the heat storage microcapsule. It is preferable that it is mass% or less, and it is more preferable that it is 15 mass% or less.
  • the content ratio of the structural unit derived from the alkenyl aromatic compound is, for example, that of the structural unit (b-2) in the polymer block (B) and the structural unit (c-1) in the polymer block (C). Refers to the total content (of course, either may not be included).
  • the structure of the block (co) polymer in the hydrogenated conjugated diene (co) polymer may be any as long as it satisfies the above requirements.
  • Structural formula (1) (AB) n1 Structural formula (2): (AB) n2-A Structural formula (3): (BA) n3-B Structural formula (4): (ABC) n4 Structural formula (5): A- (BC) n5 Structural formula (6): (AB) n6-C Structural formula (7): (CBC) n7 Structural formula (8): (CB) n8
  • A represents a polymer block (A)
  • B represents a polymer block (B)
  • C represents a polymer block (C)
  • n1 to n8 are 1 or more. Indicates an integer.
  • each polymer block may be the same or different.
  • the structure of the block (co) polymer is such that the (co) polymer block extends or is coupled via a coupling agent residue as in the structures represented by the following structural formulas (9) to (15). It may be branched.
  • A represents a polymer block (A)
  • B represents a polymer block (B)
  • C represents a polymer block (C)
  • m represents an integer of 2 or more.
  • X represents a coupling agent residue.
  • the structure of the block (co) polymer is represented by the structural formula (1), (2), (3), (4) or (9).
  • the structure represented is preferred.
  • the coupling rate in the block (co) polymer is preferably 50 to 90% in consideration of processability and bleeding properties of the heat storage material.
  • numerator is connected through a coupling agent be a coupling rate.
  • the coupling agent examples include 1,2-dibromoethane, methyldichlorosilane, dimethyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene- 1,2,4-triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4 -Chloromethylbenzene, bis (trichlorosilyl) ethane.
  • block (co) polymer the above block (co) polymers can be used alone, or two or more block (co) polymers can be mixed and used.
  • Examples of combinations of block (co) polymers include: ABA / AB, (AB) 2-X / AB, (AB) 4-X / AB, ( AB) 4-X / (AB) 2-X / AB, (AB) 4-X / (AB) 3-X / (AB) 2-X / A- B, ABC / AB, (ABC) 2 / AB, (ABC) 2-X / AB, CBC / AB ( However, A shows a polymer block (A), B shows a polymer block (B), C shows a polymer block (C), X shows a coupling agent residue.
  • a block (co) polymer can be manufactured by the method of patent 3134504 and patent 3360411, for example.
  • the hydrogenated conjugated diene (co) polymer has a polystyrene equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of preferably 10,000 to 700,000, more preferably 100,000 to 500,000. Particularly preferred is 200,000 to 500,000. In order to obtain the required mechanical properties, Mw is preferably equal to or greater than the lower limit, and in order to ensure fluidity during processing, Mw is preferably equal to or less than the upper limit.
  • Mw polystyrene equivalent weight average molecular weight
  • the hydrogenated conjugated diene (co) polymer preferably has a melting point measured by differential scanning calorimetry (DSC method) in the range of 70 to 140 ° C., more preferably in the range of 80 to 120 ° C. preferable.
  • the melting point of the hydrogenated conjugated diene (co) polymer corresponds to Tim when measured according to JIS K-7121.
  • the value of the melt flow rate (hereinafter also referred to as “MFR”) of the hydrogenated conjugated diene (co) polymer is not particularly limited, but is generally preferably 0.01 to 100 g / 10 min.
  • the MFR of the hydrogenated conjugated diene (co) polymer is a value measured under a load of 230 ° C. and 10 kg in accordance with JIS K-7210.
  • the hydrogenated conjugated diene (co) polymer can be used alone, or two or more hydrogenated conjugated diene (co) polymers can be mixed and used.
  • Examples of combinations of hydrogenated conjugated diene (co) polymers include: ABA hydrogenated product / AB hydrogenated product, (AB) 2-X hydrogenated product / AB Hydrogenated product, (AB) 4-X hydrogenated product / AB hydrogenated product, (AB) 4-X hydrogenated product / (AB) 2-X hydrogenated product / AB hydrogenated product, (AB) 4-X hydrogenated product / (AB) 3-X hydrogenated product / (AB) 2-X hydrogenated product / A -B hydrogenated product, ABC-hydrogenated product / AB hydrogenated product, (ABBC) 2 hydrogenated product / AB hydrogenated product, (AB -C) 2-X hydrogenated product / AB hydrogenated product, CBC hydrogenated product / AB hydrogenated product (where A represents a polymer block (A), B represents a polymer block (B), C
  • the structure of the block (co) polymer is preferably a structure represented by the structural formula (1), (2), (3), (4) or (9). Since the polymer block (A) is a polymer block having a vinyl bond content of less than 30 mol%, it becomes a polymer block having a good crystallinity and having a structure similar to polyethylene by hydrogenation. Since the polymer block (B) is a polymer block having a vinyl bond content of 30 to 95 mol%, the polymer block (B) can be converted into, for example, a conjugated diene compound in the structural unit (b-1) by hydrogenation.
  • the block (co) polymer has at least a polymer block (A) and a polymer block (B), and at least one terminal is a polymer block (A). It is more preferable that the polymer block (A) is present at both ends and the polymer block (B) is present in the middle.
  • the conjugated diene compound in the structural units (a-1) and (b-1) is 1,3-butadiene, it has a structure similar to an olefin crystal-ethylene / butylene-olefin crystal block polymer structure.
  • a hydrogenated conjugated diene (co) polymer with such a structure, it has good affinity with the heat storage material, and together with the heat storage material, the heat storage material forms a dispersoid, and the heat storage microcapsule forms a core material. Even when the phase change is repeated, it is possible to obtain a heat storage material that maintains a stable particle size and a heat storage microcapsule that maintains a stable particle size.
  • the production method of the hydrogenated conjugated diene (co) polymer is not particularly limited, and the block (co) polymer may be produced by hydrogenating the prepared block (co) polymer. it can.
  • the block (co) polymer is obtained, for example, by subjecting the conjugated diene compound in the structural unit (a-1) to living anion polymerization in an inert organic solvent using an organic alkali metal compound as a polymerization initiator, and then the structural unit (b-1). It can be prepared by further adding a conjugated diene compound and optionally an alkenyl aromatic compound and performing living anionic polymerization.
  • inert organic solvent examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; benzene, xylene, toluene, An aromatic hydrocarbon solvent such as ethylbenzene can be used.
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane
  • alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane
  • benzene xylene, toluene
  • An aromatic hydrocarbon solvent such as ethylbenzene can be used.
  • the coupling agent When a coupling agent residue is introduced into the block (co) polymer, the coupling agent is used without performing an operation such as isolation after living anion polymerization of the conjugated diene compound in the structural unit (b-1). In addition, it can be easily introduced by reacting.
  • the vinyl bond content of polymer block (A) and polymer block (B) is combined with ether compounds, tertiary amines, alkoxides of alkali metals (sodium, potassium, etc.), phenoxides, sulfonates, etc. And it can control easily by selecting the kind, usage-amount, etc. suitably.
  • a hydrogenated conjugated diene (co) polymer can be easily prepared by hydrogenating this block (co) polymer.
  • the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time.
  • Examples of the hydrogenation catalyst include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924.
  • JP 2000-37632 A JP 59-133203 A, JP 62-218403 A, JP 7-90017 A, JP 43-19960 A, and JP 47-40473 A.
  • a hydrogenation catalyst is mentioned.
  • the said hydrogenation catalyst may be used only 1 type, and can also use 2 or more types together.
  • the hydrogenation rate of the double bond derived from the conjugated diene compound (including the conjugated diene compound in the structural units (a-1) and (b-1)) in the hydrogenated conjugated diene (co) polymer is determined by shape retention and In order to satisfy the mechanical properties, 90% or more is preferable, and 95% or more is more preferable.
  • the catalyst residue is removed, or a phenol-based or amine-based anti-aging agent is added, and then the hydrogenated conjugated diene (co) polymer solution is added to the hydrogenated conjugated diene (co).
  • the polymer is isolated. Isolation of the hydrogenated conjugated diene (co) polymer can be carried out, for example, by adding acetone or alcohol to the hydrogenated conjugated diene (co) polymer solution and precipitating, or by adding the hydrogenated conjugated diene (co) polymer solution to hot water.
  • the heat storage material and emulsion-type heat storage material of the present invention are for the purpose of imparting functions according to the application, anti-aging agents, antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, flame retardants, antibacterial / You may contain other components, such as a fungicide, a dispersing agent, a coloring inhibitor, a rust inhibitor, a thickener, and a specific gravity adjuster, in the range which does not impair the effect of the present invention.
  • the heat storage material and emulsion-type heat storage material of the present invention can further contain a crystal nucleating agent (nucleating agent) for the purpose of facilitating the phase change of the heat storage material.
  • a crystal nucleating agent nucleating agent
  • a more preferable form is to contain a nucleating agent in the heat storage material, and it is preferable to add the nucleating agent to the heat storage material and dissolve and mix them.
  • the nucleating agent only needs to be a substance that can become a crystal nucleus when the heat storage material solidifies, but is preferably a material having a crystal structure similar to that of the heat storage material, and has a higher melting point than the heat storage material. A substance that causes coagulation is preferred. More preferably, the nucleating agent is a substance having a phase change temperature that is 10 to 100 ° C. higher than the melting point of the heat storage substance.
  • the amount of the crystal nucleating agent added is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heat storage material. From the viewpoint of sufficiently solidifying the heat storage material, the lower limit value or higher is preferable, and from the viewpoint of clarifying the heat storage temperature region due to latent heat, the lower limit value or lower is preferable.
  • the emulsion-type heat storage material of the present invention can further contain a supercooling inhibitor for the purpose of lowering the melting point (freezing point) of the dispersion medium.
  • a hydrophilic substance used as the supercooling preventive agent, any can be used as long as it does not destabilize the emulsion by reacting with a surfactant or the like.
  • the hydrophilic substance non-electrolyte and electrolyte substances can be used.
  • the amount of the supercooling inhibitor added is not particularly limited, but it is preferably added so that the melting point when water is added is -2 ° C to -15 ° C.
  • the dispersion medium can be a heat storage material having a freezing point lower than that of the dispersoid. However, a heat storage material that does not impair the fluidity of the emulsion can be obtained.
  • non-electrolytic hydrophilic substances examples include urea.
  • a cryogen represented by general electrolyte salts can be used, and examples thereof include sodium chloride, calcium chloride, magnesium chloride, and ammonium nitrate. Particularly preferred is a non-electrolyte system having low reactivity with an ionic surfactant.
  • the emulsion-type heat storage material of the present invention uses a surfactant, bubbles may be easily generated during use.
  • an antifoaming agent to the emulsion type heat storage material.
  • a known material can be used as the antifoaming agent.
  • the addition amount of the antifoaming agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the heat storage material excluding the antifoaming agent.
  • the heat storage microcapsule of the present invention may contain a filler as another component.
  • fillers include colorants such as titanium oxide and carbon black, metal powders such as ferrite, inorganic fibers such as glass fibers and metal fibers, organic fibers such as carbon fibers and aramid fibers, aluminum nitride, boron nitride, and hydroxide.
  • Heat transfer agents such as aluminum, alumina, magnesium oxide, carbon nanotubes, expanded graphite, glass beads, glass balloons, glass flakes, glass fibers, asbestos, calcium carbonate, magnesium carbonate, potassium titanate whiskers, zinc oxide whiskers, etc.
  • Examples include fillers such as whisker, talc, silica, calcium silicate, kaolin, diatomaceous earth, montmorillonite, graphite, pumice, evo powder, cotton flock, cork powder, barium sulfate, and fluororesin. From the viewpoint of heat conductivity, carbon fiber and expanded graphite are preferable. These may be used alone or in combination of two or more.
  • the filler content varies depending on the purpose of the function to be imparted and the type of filler, but from the viewpoint of maintaining the fillability during processing, the content that allows the core material to maintain fluidity above the melting point of the elastomer It is desirable that Specifically, the content of the filler is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass with respect to 100% by mass of the core substance, and 1 to 30%. Mass% is particularly preferred. From the viewpoint of imparting the desired function to the heat storage material, 1% by mass or more is particularly preferable, and from the viewpoint of maintaining fluidity, 30% by mass or less is particularly preferable.
  • the heat storage microcapsules of the present invention are anti-aging agents, antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, flame retardants, antibacterial / antifungal agents, antiblocking agents, dispersants, and coloring prevention.
  • You may contain other components, such as an agent, a rust preventive agent, a specific gravity regulator, a thickening stabilizer, an antifreezing agent, and a preservative. These may be used alone or in combination of two or more.
  • a crystal nucleating agent can be added for the purpose of facilitating the phase change of the heat storage material.
  • a more preferable form is to add a nucleating agent to the heat storage material, and it is preferable to add to the heat storage material and dissolve and mix it.
  • the nucleating agent may be any material that can become a crystal nucleus when the heat storage material is solidified, and examples thereof include graphite and carbon fiber.
  • the amount of the crystal nucleating agent added is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the heat storage material. From the viewpoint of sufficiently solidifying the heat storage material, 0.5 part by mass or more is preferable, and from the viewpoint of clarifying the heat storage temperature region due to latent heat, it is preferably 20 parts by mass or less.
  • Weight average molecular weight Using gel permeation chromatography (GPC, trade name: HLC-8120GPC, manufactured by Tosoh Finechem Corporation, column: manufactured by Tosoh Corporation, GMH-XL), the weight average molecular weight was determined in terms of polystyrene.
  • MFR (g / 10 min) Based on JIS K-7210, MFR (g / 10 min) was measured at 230 ° C. and 10 kg load.
  • the extrapolation melting start temperature of the melting peak corresponding to the blended paraffin compound is taken as the melting point of the emulsion composition, and the extrapolation crystallization of the crystallization peak corresponding to the blended paraffin compound is started.
  • the temperature was taken as the freezing point of the emulsion composition.
  • the amount of heat of fusion was defined as the amount of latent heat of the emulsion composition.
  • the heat of solidification of the crystallization peak corresponding to the paraffin compound was used as the latent heat of the emulsion composition.
  • the melting point of the heat storage material having a plurality of melting peaks was the extrapolated melting start temperature of the melting peak having a larger melting heat amount, and the latent heat amount was the melting heat amount of the melting peak.
  • the latent heat amount was the melting heat amount of the melting peak.
  • the average particle size (volume average particle size) of the oil droplets was measured by appropriately diluting the obtained emulsion with ultrapure water using a laser diffraction / scattering particle size analyzer.
  • Nanotrac UPA-EX150 (Nikkiso Co., Ltd.) was used when the particle diameter was less than 5 ⁇ m
  • Microtrac MT3000 (Nikkiso Co., Ltd.) was used when the particle diameter was 5 ⁇ m or more.
  • the dispersion medium water refractive index 1.33
  • dispersoid paraffin refractive index 1.48
  • the average value of the values obtained by three measurements was defined as the average particle diameter.
  • ⁇ AA A product whose separation could not be confirmed visually was evaluated as a non-defective product.
  • BB A product that can be visually confirmed to be separated was evaluated as a defective product.
  • the average particle diameter (volume average particle diameter) was measured by appropriately diluting the obtained microcapsules with ultrapure water using a laser diffraction / scattering particle size analyzer. Nanotrac UPA-EX150 (Nikkiso Co., Ltd.) was used when the particle diameter was less than 5 ⁇ m, and Microtrac MT3000 (Nikkiso Co., Ltd.) was used when the particle diameter was 5 ⁇ m or more.
  • the dispersion medium water refractive index 1.33
  • dispersoid paraffin refractive index 1.48
  • the average value of the values obtained by three measurements was defined as the average particle diameter.
  • Heat storage material ratio The amount of latent heat derived from the heat storage material in the heat storage microcapsule (latent heat amount 1), and the amount of latent heat derived from the same heat storage material as the heat storage material of the same mass as the heat storage microcapsule (latent heat amount 2) It was measured. From the value obtained by dividing the amount of latent heat 1 by the amount of latent heat 2, the ratio of the heat storage material in the heat storage microcapsules was calculated. The amount of latent heat is measured using a differential scanning calorimeter. The dry heat storage microcapsules are held at 40 ° C. for 10 minutes, then cooled to ⁇ 20 ° C. at a rate of 10 ° C./minute, and then to ⁇ 20 ° C.
  • the temperature was raised to 100 ° C. at a rate of 10 ° C./min.
  • the extrapolated melting start temperature of the melting peak corresponding to the blended heat storage material is taken as the melting point of the heat storage material, and the extrapolated crystallization start temperature of the crystallization peak corresponding to the blended heat storage material was the freezing point of the heat storage material.
  • the amount of heat of fusion was defined as the amount of latent heat of the heat storage material, which was defined as the amount of latent heat 1.
  • the latent heat amount of the heat storage material having the same mass as the heat storage microcapsule was measured, and this was defined as the latent heat amount 2.
  • the block (co) polymer includes a structural unit derived from 1,3-butadiene, a polymer block (A) having a vinyl bond content of 16 mol%, and a structural unit derived from 1,3-butadiene. And a block (co) polymer having a polymer block (B) having a vinyl bond content of 58 mol%.
  • the block (co) polymer had a weight average molecular weight of 380,000 and a coupling rate of 75%.
  • reaction solution containing the block (co) polymer was brought to 80 ° C., 2.5 g of bis (cyclopentadienyl) titanium furfuryloxychloride and 1.2 g of n-butyllithium were added, and the hydrogen pressure was 1.0 MPa. Was allowed to react for 2 hours.
  • reaction solution is returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent is removed by steam distillation to obtain the desired hydrogenated conjugated diene (co) polymer (H-1 )
  • the hydrogenation rate of the hydrogenated conjugated diene (co) polymer (H-1) was 98%, the MFR was 2.3 g / 10 min, and the melting point was 82.0 ° C.
  • the block (co) polymer includes a structural unit derived from 1,3-butadiene, a polymer block (A) having a vinyl bond content of 15 mol%, and a structural unit derived from 1,3-butadiene. And a block (co) polymer having a polymer block (B) having a vinyl bond content of 51 mol%.
  • the block (co) polymer had a weight average molecular weight of 320,000 and a coupling rate of 79%.
  • Example A1 10 g of the hydrogenated conjugated diene (co) polymer (H-1) prepared in Synthesis Example 1, 90 g of n-hexadecane (P-1), and 4 g of polyoxyethylene stearyl ether (S-1) are made of glass. Heated to 120 ° C. in the flask and mixed for 2 hours. After the temperature of the solution was lowered to 80 ° C., 100 g of water heated to 80 ° C. was added, and the mixture was stirred with a homogenizer at 8000 rpm for 5 minutes to prepare a white emulsion. The composition ratio of each component of the obtained emulsion is shown in Table 1.
  • oil droplets composed of hydrogenated conjugated diene (co) polymer (H-1) and n-hexadecane (P-1) were uniformly dispersed in a spherical shape in the aqueous phase. It was confirmed that The average particle size of the oil droplets was 3.4 ⁇ m.
  • Examples A2 to A14, Comparative Examples A1 to A2 An emulsion having the composition ratio shown in Table 1 was prepared in the same manner as in Example A1. In addition, it describes below about the kind of used thermal storage material, an elastomer, or a polymer (it showed as "polymer” below), surfactant, and an additive.
  • LLDPE Novatec LL UJ990 (manufactured by Nippon Polyethylene Co., Ltd.)
  • S-1 polyoxyethylene stearyl ether
  • S-2 polyoxyethylene sorbitan monooleate
  • A-1 Ethylene glycol Table 1 shows the measurement results and evaluation results of the produced heat storage materials.
  • Example B1 In a nitrogen-substituted autoclave 1, 20.6 parts of 37% formaldehyde aqueous solution and 40 parts of water are added to 16 parts of melamine powder, the pH is adjusted to 8, and the mixture is heated to about 70 ° C. and heated to about 70 ° C. Got. 100 parts of a 10% styrene maleic anhydride copolymer aqueous sodium salt solution heated to 85 ° C. and adjusted to pH 4.5 in a nitrogen-substituted autoclave 2, and a core material (C-1 70 parts were added with vigorous stirring and emulsification was carried out until the average particle size reached 3.0 ⁇ m.
  • the total amount of the melamine-formaldehyde initial condensate aqueous solution was added to this emulsion and stirred at 85 ° C. for 2 hours, and then the pH was adjusted to 9 to obtain a heat storage microcapsule dispersion. The obtained dispersion was dried to obtain heat storage microcapsules.
  • Example B1 the heat storage microcapsules were obtained in the same manner as in Example B1, except that the core substance was changed to that shown in Table 3 and emulsification was performed until the average particle size reached the value shown in Table 3. .
  • Example B19 In nitrogen-substituted autoclave 1, 40.5 parts of 37% formaldehyde aqueous solution is added to 20 parts of urea, and the pH of the reaction system is adjusted to 7.5 to 8.5 with 28% ammonia water, and then about 70 ° C. To an aqueous urea-formaldehyde precondensate aqueous solution. A core material heated to 85 ° C. in 100 parts of an aqueous sodium salt solution of a 10% styrene maleic anhydride copolymer heated to 85 ° C.
  • Examples B20 to B22 In a nitrogen-substituted autoclave 1, a predetermined amount of core material melted at 85 ° C. and a film-forming monomer were mixed and stirred, and then heated to 90 ° C., and 60% by mass of ions. A predetermined amount of sodium dodecylbenzenesulfonate dispersant was added as the exchange water and dispersant, and stirred to prepare an emulsified monomer solution. The remaining amount of ion-exchanged water was put into the autoclave 2 purged with nitrogen, and stirring was started.
  • the pressure was returned to atmospheric pressure with nitrogen to make the inside a nitrogen atmosphere, and then the emulsified monomer solution was added all at once.
  • a predetermined amount of benzoyl peroxide was added as an initiator to initiate polymerization.
  • the autoclave 2 was cooled to room temperature to obtain a heat storage microcapsule dispersion. The obtained dispersion was dried to obtain heat storage microcapsules.
  • Table 4 shows the amount of each component used.
  • the total amount of the melamine-formaldehyde initial condensate aqueous solution was added to this emulsion and stirred at 70 ° C. for 2 hours, and then the pH was adjusted to 9 to obtain a heat storage microcapsule dispersion. The obtained dispersion was dried to obtain heat storage microcapsules.
  • the total amount of the melamine-formaldehyde initial condensate aqueous solution was added to this emulsion and stirred at 70 ° C. for 2 hours, and then the pH was adjusted to 9 to obtain a heat storage microcapsule dispersion. The obtained dispersion was dried to obtain heat storage microcapsules.
  • Table 3 shows the results of measurement of the heat storage material ratio, average particle diameter, and heat storage material weight loss of the heat storage microcapsules obtained in Examples B1 to B19 and Comparative Examples B1 to B3.
  • Table 4 shows the results of measuring the heat storage material ratio, average particle diameter, and heat storage material loss of the heat storage microcapsules obtained in Examples B20 to B22.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention vise à proposer une matière de stockage de chaleur telle qu'un dispersoïde maintient un diamètre de particule stable même avec des changements de phase répétés obtenus pendant l'utilisation, et qui est apte à supporter une utilisation à long terme. L'invention concerne également un dispositif de stockage de chaleur qui utilise cette matière. A cet effet, l'invention propose une matière de stockage de chaleur obtenue par dispersion de particules contenant une substance de stockage de chaleur et un élastomère. La matière de stockage de chaleur comprend au moins une substance de stockage de chaleur choisie dans le groupe consistant en composés de paraffine, acides gras, composés esters d'acides gras, éthers aliphatiques, cétones aliphatiques et alcools aliphatiques.
PCT/JP2012/080233 2011-11-22 2012-11-21 Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur Ceased WO2013077379A1 (fr)

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JP2018030242A (ja) * 2016-08-22 2018-03-01 株式会社Ｉｈｉエアロスペース インシュレーション体、その製造方法、ロケットモータ、および蓄熱層形成体
CN108300423A (zh) * 2018-02-09 2018-07-20 苏州甫众塑胶有限公司 一种高效节能相变微胶囊的制备方法
US10626238B2 (en) 2018-07-27 2020-04-21 King Fahd University Of Petroleum And Minerals Calcium-doped magnesium carbonate-polymer-based synergistic phase change composite
JP2021511399A (ja) * 2018-01-05 2021-05-06 カストロール リミテッド 熱交換流体／冷却材の相変化材料
CN113372065A (zh) * 2021-06-23 2021-09-10 北京民佳混凝土有限公司 一种储热混凝土及其制备方法
US20210380861A1 (en) * 2020-06-03 2021-12-09 Alliance For Sustainable Energy, Llc Salt hydrate-based phase change thermal energy storage and encapsulation thereof
CN114901778A (zh) * 2019-12-27 2022-08-12 富士胶片株式会社 微胶囊、蓄热性组合物、蓄热片、微胶囊的制造方法
US20220340800A1 (en) * 2021-04-27 2022-10-27 Kyodo Yushi Co., Ltd. Cold and heat storage agent composition
US11964549B2 (en) 2018-07-04 2024-04-23 Bp P.L.C. Multiple cooling circuit systems and methods for using them
US12466983B2 (en) 2019-04-24 2025-11-11 Bp P.L.C. Dielectric thermal management fluids and methods for using them

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WO2016204108A1 (fr) * 2015-06-19 2016-12-22 株式会社ダイセル Milieu de transport de chaleur comprenant un matériau de stockage de chaleur latente, mélange pour transport de chaleur, et procédé de transport de chaleur
US10703951B2 (en) 2015-06-19 2020-07-07 Daicel Corporation Heat-transport medium including latent heat storage material, mixture for heat transport, and heat transport method
JP2018030242A (ja) * 2016-08-22 2018-03-01 株式会社Ｉｈｉエアロスペース インシュレーション体、その製造方法、ロケットモータ、および蓄熱層形成体
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JP2021511399A (ja) * 2018-01-05 2021-05-06 カストロール リミテッド 熱交換流体／冷却材の相変化材料
CN108300423A (zh) * 2018-02-09 2018-07-20 苏州甫众塑胶有限公司 一种高效节能相变微胶囊的制备方法
US11964549B2 (en) 2018-07-04 2024-04-23 Bp P.L.C. Multiple cooling circuit systems and methods for using them
US11306189B2 (en) 2018-07-27 2022-04-19 King Fahd University Of Petroleum And Minerals Polyethylene glycol phase change composite
US10626238B2 (en) 2018-07-27 2020-04-21 King Fahd University Of Petroleum And Minerals Calcium-doped magnesium carbonate-polymer-based synergistic phase change composite
US11434339B2 (en) 2018-07-27 2022-09-06 King Fahd University Of Petroleum And Minerals Method for making a PEG phase change composite
US12466983B2 (en) 2019-04-24 2025-11-11 Bp P.L.C. Dielectric thermal management fluids and methods for using them
CN114901778A (zh) * 2019-12-27 2022-08-12 富士胶片株式会社 微胶囊、蓄热性组合物、蓄热片、微胶囊的制造方法
US11560504B2 (en) * 2020-06-03 2023-01-24 Alliance For Sustainable Energy, Llc Salt hydrate-based phase change thermal energy storage and encapsulation thereof
US20210380861A1 (en) * 2020-06-03 2021-12-09 Alliance For Sustainable Energy, Llc Salt hydrate-based phase change thermal energy storage and encapsulation thereof
JP2022169156A (ja) * 2021-04-27 2022-11-09 協同油脂株式会社 蓄冷熱剤組成物
CN115247050A (zh) * 2021-04-27 2022-10-28 协同油脂株式会社 蓄冷热剂组合物
US20220340800A1 (en) * 2021-04-27 2022-10-27 Kyodo Yushi Co., Ltd. Cold and heat storage agent composition
US12291667B2 (en) * 2021-04-27 2025-05-06 Kyodo Yushi Co., Ltd. Cold and heat storage agent composition
JP7674144B2 (ja) 2021-04-27 2025-05-09 協同油脂株式会社 蓄冷熱剤組成物
CN113372065A (zh) * 2021-06-23 2021-09-10 北京民佳混凝土有限公司 一种储热混凝土及其制备方法

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