WO2015115149A1 - Matériau d'isolation thermique sous vide, boîte d'isolation thermique utilisant ledit matériau d'isolation thermique sous vide, et procédé de fabrication de matériau d'isolation thermique sous vide - Google Patents

Matériau d'isolation thermique sous vide, boîte d'isolation thermique utilisant ledit matériau d'isolation thermique sous vide, et procédé de fabrication de matériau d'isolation thermique sous vide Download PDF

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Publication number
WO2015115149A1
WO2015115149A1 PCT/JP2015/050403 JP2015050403W WO2015115149A1 WO 2015115149 A1 WO2015115149 A1 WO 2015115149A1 JP 2015050403 W JP2015050403 W JP 2015050403W WO 2015115149 A1 WO2015115149 A1 WO 2015115149A1
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WO
WIPO (PCT)
Prior art keywords
heat insulating
vacuum heat
less
insulating material
fiber
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PCT/JP2015/050403
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English (en)
Japanese (ja)
Inventor
貴祥 向山
一正 藤村
犬塚　隆之
洋輔 藤森
尚平 安孫子
浩明 高井
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三菱電機株式会社
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Application filed by 三菱電機株式会社 filed Critical 三菱電機株式会社
Priority to CN201580006850.5A priority Critical patent/CN105992902B/zh
Priority to RU2016135626A priority patent/RU2658725C1/ru
Priority to SG11201605643YA priority patent/SG11201605643YA/en
Publication of WO2015115149A1 publication Critical patent/WO2015115149A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/06—Arrangements using an air layer or vacuum
    • F16L59/065—Arrangements using an air layer or vacuum using vacuum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00—Insulation
    • F25D2201/10—Insulation with respect to heat
    • F25D2201/14—Insulation with respect to heat using subatmospheric pressure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2500/00—Problems to be solved
    • F25D2500/02—Geometry problems

Definitions

  • the present invention relates to a vacuum heat insulating material and a heat insulating box using the vacuum heat insulating material, in particular, a vacuum heat insulating material and a heat insulating box suitable for use in a cooling / heating device, and a manufacturing method.
  • a core material formed of an aggregate of glass fibers is covered with an outer packaging material having a gas barrier property, and the inside of the outer packaging material is decompressed. And sealed (see, for example, Patent Document 1).
  • the vacuum heat insulating material in which the inside of the outer packaging material is depressurized is thinned by covering the bulky glass fiber aggregate with the outer packaging material and sealing under reduced pressure, and the convection and heat conduction of the gas inside the outer packaging material are reduced.
  • the effect is reduced to improve the heat insulation performance.
  • the heat transfer mechanism of a heat insulating material is caused by heat conduction, radiation, and convection of solid and gas components.
  • the vacuum heat insulating material whose inside of the outer packaging material is sealed under reduced pressure has little effect on the heat conduction and convection of the gas component. Further, there is almost no influence of radiation when used in a temperature range below room temperature.
  • glass fibers are heated and pressed by a dry method using a binder, and the glass fibers are not only oriented perpendicular to the heat transfer direction, but also contain 40 to 70% of short fibers with a length of 100 ⁇ m or less. As a result, the heat transmitted through the fibers is interrupted to reduce the solid thermal conductivity (for example, see Patent Document 3).
  • the shot (dama) mixing rate is 0.5 mass% or less
  • the average particle diameter of the shot is 150 ⁇ m or less.
  • Japanese Patent No. 3580315 (Summary, FIG. 1) Japanese Patent Laid-Open No. 9-4785 (Abstract) Japanese Patent No. 3513143 (paragraph [0006]) JP 2009-155172 A (summary)
  • the glass fibers constituting the vacuum heat insulating material are oriented and laminated in a direction perpendicular to the heat insulating direction, but the glass fibers are perpendicular to the heat insulating direction. If the layers are simply oriented and laminated, the heat transmitted through the glass fiber is present, so that the solid thermal conductivity is increased, and there is a limit to the reduction of the initial thermal conductivity in the vacuum heat insulating material.
  • the method of binding glass fibers by heat and pressure molding using a binder increases the power cost for heating and the material cost of the binder, and not only can the vacuum heat insulating material be obtained at low cost, but also over time. There was a problem that the thermal conductivity was greatly deteriorated. This is because when a vacuum heat insulating material is used, a low molecular gas component is released from the binder in vacuum, and the degree of vacuum is lowered.
  • the dry method that does not use a binder has a problem that even if the length of the glass fiber and the weight ratio of the short fiber can be controlled, the fiber angle cannot be controlled in the vacuum heat insulating material.
  • the present invention has been made to solve the above-mentioned problems, and can control the weight ratio of short fibers, the average fiber angle, and the standard deviation thereof, and is excellent in heat insulation performance.
  • Heat insulation box using a vacuum heat insulation material And it aims at providing the manufacturing method of a vacuum heat insulating material.
  • a vacuum heat insulating material according to the present invention is a vacuum heat insulating material that includes a core material composed of a fiber assembly and an outer packaging material that covers the core material, and the inside of the outer packaging material is hermetically sealed under reduced pressure.
  • the weight ratio of fibers having a fiber length of 1.85 mm or less is 11 wt% or less of the entire core material.
  • the weight ratio of the fiber having a fiber length of 1.85 mm or less is 11 wt% or less of the entire core material, the heat path path in the heat insulating direction of the core material is shortened and heat insulation The influence of fibers having a fiber length of 1.85 mm or less, which is a factor that deteriorates performance, can be minimized. For this reason, high heat insulation performance can be obtained.
  • the weight ratio of the fibers having a fiber length of 1.85 mm or less can be easily oriented perpendicular to the heat insulating direction of the core material.
  • FIG. The vacuum heat insulating material according to Embodiment 1 of the present invention is such that the weight ratio of fibers having a fiber length of 1.85 mm or less (hereinafter sometimes referred to as “short fibers”) in the fiber assembly serving as the core is the core. It is 11 wt% or less of the material, and preferably 8 wt% or less of the core material.
  • the weight ratio of fibers (short fibers) having a fiber length of 1.85 mm or less means a measured value measured by the following method.
  • FIG. 1 is a graph showing the relationship between the weight ratio of fibers having a fiber length of 1.85 mm or less and the thermal conductivity of the core material of the vacuum heat insulating material according to Embodiment 1 of the present invention, and the vertical axis represents the thermal conductivity [mW / M ⁇ K], and the horizontal axis represents the weight ratio [wt%] of fibers having a fiber length of 1.85 mm or less.
  • the thermal conductivity was almost constant at 2.0 mW / m ⁇ K or less in the range where the weight ratio of the fiber having a fiber length of 1.85 mm or less was 11 wt% or less of the core material.
  • the weight ratio of fibers having a fiber length of 1.85 mm or less exceeds 11 wt% of the core material, the thermal conductivity increases to 2.0 mW / m ⁇ K or more. From the above results, the weight ratio of the fibers having a fiber length of 1.85 mm or less constituting the vacuum heat insulating material having a thermal conductivity of 2.0 mW / m ⁇ K or less is 11 wt% or less of the core material.
  • the average fiber length of the short fibers in the measurement method was determined by the following method.
  • FIG. 2 is an optical micrograph in the measurement of the average fiber length of the core material of the vacuum heat insulating material according to Embodiment 1 of the present invention.
  • the average fiber length was 0.50 mm and the standard deviation ⁇ was 0.45 mm. That is, the core material constituting the vacuum heat insulating material having a thermal conductivity of 2.0 mW / m ⁇ K or less has an average short fiber length + 3 ⁇ of fiber length of 1.85 mm or less, and the weight ratio of the core material is 11 wt% or less. It is.
  • the standard deviation ⁇ is one measure for looking at the spread width (variation) of the data distribution. 99.73% of the total length data of the collected short fibers is distributed within the range of the fiber length that is 1.85 mm long as the average short fiber length + 3 ⁇ .
  • the average value of the fiber angle ⁇ with respect to the plane perpendicular to the heat insulating direction of the core material is 14 ° or less.
  • the average value (average fiber angle) of the fiber angle ⁇ with respect to the plane perpendicular to the heat insulating direction of the core means a measured value measured by the following method.
  • FIG. 3 is an optical micrograph in the measurement of the average fiber angle of the core material of the vacuum heat insulating material according to Embodiment 1 of the present invention, and a measurement example is shown in the figure. That is, in order to maintain the thickness of the vacuum heat insulating material, the outside of the vacuum heat insulating material was hardened with an epoxy resin, and then the epoxy resin was poured into the core material under vacuum to be cured. After curing, the central part of the vacuum heat insulating material is cut by a horizontal surface along the heat insulating direction, the cut surface is polished, and the surface perpendicular to the heat insulating direction of the core material is used as a horizontal plane (0 °) as a reference for the angle.
  • the angle ⁇ is an angle between the major axis of the ellipse and the horizontal plane
  • the fiber angle ⁇ is an angle including the angle between the major axis of the ellipse and the horizontal plane and the angle formed with the cut surface. is there.
  • FIG. 4 is a graph showing the relationship between the average fiber angle of the core material of the vacuum heat insulating material according to Embodiment 1 of the present invention and the thermal conductivity, and the vertical axis represents the thermal conductivity [mW / m ⁇ K], The horizontal axis shows the average fiber angle [°].
  • the thermal conductivity was almost constant at 2.0 mW / m ⁇ K or less in the range where the average fiber angle was 14 ° or less.
  • the average fiber angle exceeds 14 °, the thermal conductivity increases to 2.0 mW / m ⁇ K or more. From the above results, the average fiber angle of the core material constituting the vacuum heat insulating material having a thermal conductivity of 2.0 mW / m ⁇ K or less is 14 ° or less.
  • FIG. 5 is a graph showing the relationship between the fiber angle standard deviation of the core material of the vacuum heat insulating material according to Embodiment 1 of the present invention and the thermal conductivity, and the vertical axis represents the thermal conductivity [mW / m ⁇ K].
  • the horizontal axis is the fiber angle standard deviation [°].
  • each having an inflection point can be explained by percolation theory.
  • percolation theory For example, consider the weight ratio of fibers with a fiber length of 1.85 mm or less.
  • VIP Vauum Insulation Panel
  • One factor that deteriorates the thermal insulation performance of VIP is a fiber oriented in the thermal insulation direction of VIP. The shorter the fibers, the higher the probability that they will be oriented in the heat insulating direction of VIP. Therefore, it is considered that the heat insulating performance is higher when there are fewer short fibers.
  • the influence on the heat insulation performance is small.
  • fibers having a fiber length of 1.85 mm or less are defined as short fibers, and it is considered that the heat insulation is higher when the number of short fibers is smaller.
  • the weight ratio of the short fibers is 11 wt% or less of the core material, the thermal conductivity is constant, and when the weight ratio of the short fibers exceeds 11 wt% of the core material, the thermal conductivity increases rapidly.
  • the weight ratio of the fiber having a fiber length of 1.85 mm or less is 11 wt% of the core material, and a plurality of fibers oriented in the heat insulation direction overlap, and the connection of the heat path path in the heat insulation direction increases rapidly.
  • the point is a critical point (percolation critical point).
  • percolation critical point there is an inflection point in the relationship between the weight ratio of fibers having a fiber length of 1.85 mm or less and the thermal conductivity.
  • the average fiber angle, the fiber angle standard deviation, and the thermal conductivity it can be similarly considered that each has an inflection point.
  • FIG. 6 is a cross-sectional view showing a vacuum heat insulating material according to Embodiment 1 of the present invention.
  • the vacuum heat insulating material 1 is deteriorated with time by adsorbing a core material 2 composed of a fiber assembly, a gas barrier outer packaging material 3 covering the core material 2, and moisture inside the outer packaging material 3. And a moisture adsorbent 4 to be suppressed.
  • the inside of the outer packaging material 3 is sealed by, for example, a heat-sealing welding seal portion 5 in a state where the pressure is reduced to a vacuum of 1 to 3 Pa (Pascal).
  • the core material 2 can be made of glass fiber, alumina fiber, silica alumina fiber, silica fiber, rock wool, silicon carbide fiber, or nonwoven fabric, and is not particularly specified.
  • the outer packaging material 3 has at least a gas barrier layer and a heat welding layer, and may be provided with a surface protective layer as necessary.
  • a gas barrier layer a metal film, a metal oxide, or a plastic film or metal foil on which diamond-like carbon is deposited can be used as long as it can be used for the purpose of reducing gas permeation, and is not particularly specified.
  • silica or alumina can be used as a material for metal oxide vapor deposition on the plastic film, and is not particularly specified.
  • the heat welding layer of the outer packaging material 3 is the portion having the highest gas permeability in the film constituting the outer packaging material 3, and the properties of the heat welding layer greatly affect the heat insulation performance of the vacuum heat insulating material over time.
  • the thickness of the heat-welded layer is the stability of the sealing quality in the reduced-pressure sealing process, the suppression of gas intrusion from the end face of the heat-welded part, and the heat from the surface due to heat conduction when a metal foil is used as the gas barrier layer. In consideration of leakage, 25 ⁇ m to 60 ⁇ m is suitable.
  • an unstretched polypropylene film, a high-density polyethylene film, or a linear low-density polyethylene film can be used and is not particularly specified.
  • a surface protective layer outside the gas barrier layer.
  • a stretched product of a polyethylene terephthalate film, a polypropylene film, or a nylon film can be used. Further, when a nylon film is used on the outer side, the bending resistance and the puncture resistance are improved.
  • the bag shape of the outer packaging material 3 includes a four-side seal bag, a gusset bag, a three-side seal bag, a pillow bag, and a center tape seal bag, but is not particularly specified.
  • the moisture adsorbent 4 is, for example, calcium oxide (CaO) inserted in a bag having good air permeability.
  • the moisture adsorbent 4 is not limited to CaO, and is not particularly limited as long as it has moisture adsorption properties such as zeolite.
  • the core material 2 used for the vacuum heat insulating material 1 of this embodiment is comprised with the glass fiber aggregate manufactured by the dry method which does not use a binder, for example.
  • the core material 2 composed of this glass fiber aggregate has a low bulk density and poor handling properties when inserting the vacuum heat insulating material 1 and insertability into the outer packaging material 3. Therefore, in order to handle as the core material 2, it is necessary to increase the bulk density by processing.
  • FIG. 7 is a schematic view showing a method for manufacturing a vacuum heat insulating material according to Embodiment 1 of the present invention.
  • the processing device 6 includes a compression mechanism 7 that compresses the core material 2.
  • the core material 2 is installed in the processing device 6 after being aligned with the width and length necessary for the vacuum heat insulating material 1. At this time, the thickness of the core material 2 is 10 times or more that of the vacuum heat insulating material 1.
  • the pressure when compressing is preferably 0.02 to 0.07 MPa, more preferably 0.02 to 0.04 MPa.
  • the number of compressions is preferably 50 to 1000 times.
  • the fiber breaks, the weight ratio of the fiber having a fiber length of 1.85 mm or less becomes 11 wt% or more of the core material 2, and vacuum insulation with excellent heat insulation performance The material is not obtained.
  • the cause is that short fibers are filled between the main fibers or entangled between the main fibers, causing heat conduction between the fibers, and heat conduction along the thickness direction of the core material. It is considered that the heat insulation performance is lowered by causing
  • the core material 2 processed with a high bulk density is inserted into the outer packaging material 3, and after passing through a drying process for removing moisture, the moisture adsorbent 4 is inserted, and the interior of the outer packaging material 3 is 1 to 3 Pa (
  • the vacuum heat insulating material 1 is obtained by sealing the opening by heat sealing in a state where the pressure is reduced to Pascal).
  • heating may be performed at 100 ° C. for 2 hours, which is a condition capable of removing moisture from the core material 2 and the outer packaging material 3 covering the core material 2, but the heating condition is limited to this.
  • the core material 2 and the outer packaging material 3 covering the core material 2 may be removed under any conditions.
  • the moisture adsorbent 4 is not limited to being inserted after the drying process, but compresses the core material 2 and the outer packaging material 3 covering the core material 2 before the drying process or by the processing device 6. It may be inserted before.
  • thermal conductivity the weight ratio of the fiber of 1.85 mm or less of fiber length, the average value of fiber angle (phi) with respect to a surface perpendicular
  • the thermal conductivity was measured with a thermal conductivity meter by a steady method. The measurement conditions were a high temperature side of 37.7 ° C., a low temperature side of 10 ° C., and an average temperature of 23.85 ° C.
  • the weight ratio of the fibers having a fiber length of 1.85 mm or less is 11 wt% or less of the core material 2, the average value of the fiber angle ⁇ with respect to the plane perpendicular to the heat insulation direction of the core material 2 is 14 ° or less, and the standard deviation is 12 °.
  • the thermal conductivity was 2.0 mW / m ⁇ K or less. From the above results, it was found that the vacuum heat insulating material satisfying the above conditions processed by the method of the present embodiment was excellent in heat insulating performance.
  • FIG. 8 is a schematic view showing a heat insulation box according to the second embodiment of the present invention (in this embodiment, a heat insulation box of a refrigerator).
  • the heat insulating box 8 includes an inner box 9 made of ABS resin, an outer box 10 made of a steel plate, and one side of the space between the inner box 9 and the outer box 10 (inner box 9 side).
  • the inner box 9 and the outer box 10 each have an opening (not shown) formed on a common surface, and an opening / closing door (not shown) is provided in the opening.
  • Other parts are the same as the heat insulation box used in a general refrigerator, and thus illustration and description thereof are omitted.
  • the range in which the vacuum heat insulating material 1 is disposed is not limited, and may be the entire space formed between the inner box 9 and the outer box 10, or It may be a part, and may be arranged inside the opening / closing door.
  • the refrigerator heat insulating box 8 configured as described above uses the vacuum heat insulating material 1 of the present invention embedded in the urethane foam heat insulating material 11 and uses it in combination. An effect is obtained.
  • Vacuum insulation material 1 Vacuum insulation material, 2 core material, 3 outer packaging material, 4 moisture adsorbent, 5 weld seal part, 6 processing equipment, 7 compression mechanism, 8 heat insulation box, 9 inner box, 10 outer box, 11 foamed urethane heat insulation material.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Thermal Insulation (AREA)

Abstract

La présente invention concerne un matériau (1) d'isolation thermique sous vide équipé d'un matériau central (2) formé d'un agrégat de fibres, et d'un matériau de recouvrement (3) externe recouvrant le matériau central (2), l'intérieur du matériau de recouvrement (3) externe étant scellé sous une pression réduite. Le matériau central (2) est formé de sorte qu'un rapport pondéral de fibres présentant une longueur de fibre inférieure ou égale à 1,85 mm soit inférieur ou égal à 11 % en poids du matériau central (2), et, par conséquent, les fibres présentant une longueur de fibre supérieure ou égale à 1,85 mm s'agencent plus facilement de manière perpendiculaire à la direction d'isolation thermique du matériau central, réduisant ainsi à un minimum l'effet des fibres présentant une longueur de fibre inférieure ou égale à 1,85 mm, qui s'agencent dans la direction d'isolation thermique du matériau central, d'où une dégradation des performances d'isolation thermique.
PCT/JP2015/050403 2014-02-03 2015-01-08 Matériau d'isolation thermique sous vide, boîte d'isolation thermique utilisant ledit matériau d'isolation thermique sous vide, et procédé de fabrication de matériau d'isolation thermique sous vide WO2015115149A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580006850.5A CN105992902B (zh) 2014-02-03 2015-01-08 真空绝热材料的制造方法
RU2016135626A RU2658725C1 (ru) 2014-02-03 2015-01-08 Вакуумный теплоизоляционный материал, теплоизоляционный короб, использующий теплоизоляционный материал, и способ производства теплоизоляционного материала
SG11201605643YA SG11201605643YA (en) 2014-02-03 2015-01-08 Vacuum heat insulating material, heat insulating box using vacuum heat insulating material, and manufacturing method of vacuum heat insulating material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-018160 2014-02-03
JP2014018160A JP6192554B2 (ja) 2014-02-03 2014-02-03 真空断熱材の製造方法

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CN (1) CN105992902B (fr)
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AU2015405840B2 (en) * 2015-08-19 2019-02-21 Mitsubishi Electric Corporation Vacuum thermal insulator and thermal insulation container
CN109690164A (zh) * 2016-09-08 2019-04-26 三菱电机株式会社 真空隔热件以及隔热箱
WO2018211906A1 (fr) * 2017-05-15 2018-11-22 パナソニックＩｐマネジメント株式会社 Matériau d'isolation thermique et structure d'isolation thermique utilisant celui-ci
WO2019150478A1 (fr) * 2018-01-31 2019-08-08 三菱電機株式会社 Matériau d'isolation sous vide et boîte isotherme
CN118076829A (zh) * 2021-10-08 2024-05-24 日东电工株式会社 绝热材和绝热材的制造方法

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JP4183657B2 (ja) * 2004-06-04 2008-11-19 日立アプライアンス株式会社 冷蔵庫
JP4713566B2 (ja) * 2007-12-28 2011-06-29 シャープ株式会社 真空断熱材用芯材、真空断熱材、および、これらの製造方法
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JP2004011756A (ja) * 2002-06-06 2004-01-15 Matsushita Refrig Co Ltd 真空断熱材、および真空断熱材を用いた冷蔵庫
JP2005220954A (ja) * 2004-02-04 2005-08-18 Matsushita Electric Ind Co Ltd 真空断熱材とその製造方法、真空断熱材を具備する保温保冷機器、および断熱ボード
JP2006017169A (ja) * 2004-06-30 2006-01-19 Asahi Fiber Glass Co Ltd 真空断熱材、真空断熱材用芯材およびその製造方法
JP2010007683A (ja) * 2008-06-24 2010-01-14 Mitsubishi Electric Corp 真空断熱材

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CN105992902B (zh) 2018-06-26
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CN105992902A (zh) 2016-10-05
JP2015145696A (ja) 2015-08-13
SG11201605643YA (en) 2016-08-30

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