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WO2018159430A1 - Corps calorifuge, corps d'enceinte calorifuge, porte calorifuge et refrigerateur-congélateur - Google Patents

Corps calorifuge, corps d'enceinte calorifuge, porte calorifuge et refrigerateur-congélateur Download PDF

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Publication number
WO2018159430A1
WO2018159430A1 PCT/JP2018/006347 JP2018006347W WO2018159430A1 WO 2018159430 A1 WO2018159430 A1 WO 2018159430A1 JP 2018006347 W JP2018006347 W JP 2018006347W WO 2018159430 A1 WO2018159430 A1 WO 2018159430A1
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WO
WIPO (PCT)
Prior art keywords
heat
door
box
heat insulating
refrigerator
Prior art date
Application number
PCT/JP2018/006347
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English (en)
Japanese (ja)
Inventor
卓人 柴山
Original Assignee
パナソニックＩｐマネジメント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to JP2019502919A priority Critical patent/JPWO2018159430A1/ja
Priority to CN201880014526.1A priority patent/CN110382578A/zh
Publication of WO2018159430A1 publication Critical patent/WO2018159430A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • 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
    • F25D23/02—Doors; Covers
    • 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

Definitions

  • the present disclosure relates to a heat insulator having a foamed polyurethane resin filled and foamed inside, a heat insulating box having a heat insulator, a heat insulating door having a heat insulator, and a refrigerator / freezer including at least one of them.
  • the foamed polyurethane resin is obtained by foaming by adding a foaming agent to polyol and polyisocyanate which are raw materials.
  • a foaming agent CFC and HCFC were used as the foaming agent, but problems of ozone layer destruction and global warming have been pointed out, and in recent years, foamed polyurethane resins using cyclopentane, which is non-fluorocarbon, have become mainstream.
  • the foamed polyurethane resin using cyclopentane as a foaming agent has a problem that the thermal conductivity of the gas is higher than that of CFC and HCFC, and the heat insulation performance of the foamed polyurethane resin is inferior.
  • the present disclosure has been made in view of the conventional problems as described above, and provides a heat insulator having excellent heat insulation performance of a polyurethane foam resin. Moreover, this indication provides the heat insulation box which has the said heat insulating body, the heat insulating door which has the said heat insulating body, and a refrigerator-freezer provided with at least one of these.
  • a heat insulator includes a polyurethane foam resin and a space in which the polyurethane foam resin is filled and foamed.
  • the foamed polyurethane resin is a mixture of at least a polyol component, a polyisocyanate component, a first foaming agent that is a hydrofluoroolefin having a boiling point of 10 ° C. or less under atmospheric pressure, and a second foaming agent that is cyclopentane. Is injected into the space, foamed and cured.
  • Such a configuration can reduce the thermal conductivity of the gas in the foamed polyurethane resin bubbles and reduce the formation of large bubbles in the foam due to bumping. Further, with such a configuration, the foamed polyurethane resin can be foamed without generating large bubbles. Therefore, with such a configuration, the heat insulating performance of the polyurethane foam resin and the heat insulating performance of the heat insulator provided with the polyurethane foam resin can be improved.
  • the thermal conductivity of the first foaming agent is preferably 15.0 mW / mK or less.
  • the first foaming agent HFO has a lower thermal conductivity of gas than carbon dioxide, so that the heat insulation performance of the foamed polyurethane resin and the heat insulation performance of the heat insulator provided with the foamed polyurethane resin. Can be increased.
  • the first blowing agent has a solubility in the polyol component, preferably higher than or equal to the solubility of carbon dioxide in the polyol component.
  • the solubility with respect to the polyol component is higher than that of carbon dioxide, the polyurethane foam resin is vaporized relatively slowly at the time of foaming, and can be foamed without generating large bubbles.
  • the heat insulation performance of a polyurethane foam resin and the heat insulation performance of the heat insulating body provided with the foam polyurethane resin can be improved.
  • the first foaming agent is preferably HFO1234ze or HFO1233zd. Since the first foaming agent is composed of HFO1234ze or HFO1233zd whose gas thermal conductivity is lower than that of carbon dioxide, the heat insulation performance of the polyurethane foam resin and the heat insulation performance of the heat insulator provided with the polyurethane foam resin are improved. Can do.
  • the core density of the foamed polyurethane resin is preferably 50 kg / m 3 or less. According to such a configuration, from the viewpoint of density, the thermal conductivity of the polyurethane foam resin can be lowered, so that the heat insulation performance of the polyurethane foam resin and the heat insulation performance of the heat insulator provided with the polyurethane foam resin can be improved. .
  • the first foaming agent is preferably added in an amount of 1% to 10% with respect to the polyurethane foam resin. According to such a configuration, it is possible to suppress bumping when the polyurethane foam resin is injected, and it is possible to reduce the occurrence of large bubbles in the polyurethane foam resin. Therefore, with such a configuration, the heat insulation performance of the foamed polyurethane resin and the heat insulation performance of the heat insulator provided with the foamed polyurethane resin can be enhanced.
  • the heat insulating box according to an example of the present disclosure may be configured by a heat insulating body having at least one of the characteristics of the heat insulating body, and the heat insulating body may have a box shape. With such a configuration, a heat insulation box having excellent heat insulation performance can be obtained.
  • a heat insulating door according to an example of the present disclosure is configured by a heat insulating body having at least one of the characteristics of the heat insulating body. With such a configuration, a heat insulating door having excellent heat insulating performance can be obtained.
  • a refrigerator-freezer includes a box provided with an opening in one direction, a door disposed so as to close the opening of the box and form a sealed space, and the box, And a cooling device for cooling the sealed space formed by the door.
  • the box may be formed of a heat insulating box having at least one of the features of the heat insulator. With such a configuration, a refrigerator-freezer having excellent heat insulation performance can be obtained.
  • a refrigerator-freezer includes a box provided with an opening in one direction, a door disposed so as to close the opening of the box and form a sealed space, and the box, And a cooling device for cooling the sealed space formed by the door.
  • the door may be formed of a heat insulating door having at least one of the features of the heat insulator.
  • FIG. 1 is a cross-sectional view of a heat insulating door according to the first embodiment of the present disclosure.
  • FIG. 2 is a schematic diagram illustrating a method for manufacturing a heat insulating door according to the first embodiment of the present disclosure.
  • FIG. 3 is a cross-sectional view of the refrigerator-freezer according to the second embodiment of the present disclosure.
  • FIG. 1 is a cross-sectional view of a heat insulating door that is a heat insulating body in Embodiment 1 of the present disclosure.
  • FIG. 2 is a schematic diagram illustrating a method for manufacturing a heat insulating door that is a heat insulating body according to the first embodiment of the present disclosure.
  • the heat insulating door 101 according to the first embodiment of the present disclosure includes an outer surface material 102 that forms the heat insulating door 101, and an inner surface material 103.
  • the heat insulating door 101 according to the first embodiment of the present disclosure has a closed space formed by the outer surface material 102 and the inner surface material 103.
  • the heat insulating door 101 according to the first embodiment of the present disclosure includes a polyurethane foam resin 104 formed by foam filling in a closed space between the outer surface material 102 and the inner surface material 103.
  • the first foaming agent and the second foaming agent are mixed with the polyol 108.
  • the first blowing agent is trans-1,1,1,3-tetrafluoropropene (HFO1234ze).
  • HFO1234ze has a boiling point of ⁇ 18.95 ° C. at atmospheric pressure, and a thermal conductivity of gas at 25 ° C. of 0.0136 W / mK.
  • the second blowing agent is cyclopentane.
  • the polyisocyanate 109 is mixed with the polyol 108 in which the cyclopentane 105 and the HFO 1234ze 106 are mixed and injected onto the outer surface material 102, and then the inner surface material 103 is immediately attached to the outer surface material.
  • Cyclopentane 105 and HFO 1234ze 106 are foamed and molded in the space between 102 and the inner surface material 103. Thereby, the heat insulation door 101 is manufactured.
  • an injection port is provided in either the outer surface material 102 or the inner surface material 103, and the polyurethane foam resin 104 is injected from the injection port into a space formed by attaching the outer surface material 102 and the inner surface material 103 in advance.
  • the polyol 108 may be mixed with water, a foam stabilizer, a catalyst, and the like in advance.
  • the heat insulating door 101 configured as described above has a space formed between the outer surface material 102 and the inner surface material 103. Moreover, the heat insulation door 101 of this Embodiment has the polyurethane foam resin 104 by which the said space was filled and foamed.
  • the polyurethane foam resin 104 has at least a polyol 108, a polyisocyanate 109, a liquid cyclopentane 105 that is a liquid hydrocarbon at room temperature, and a boiling point under atmospheric pressure.
  • a mixture with HFO1234ze106 which is HFO at 10 ° C. or lower, is injected into the space, foamed and cured.
  • the heat insulating door 101 of the present embodiment is made of a polyurethane foam resin 104 using HFO 1234ze 106 having a lower thermal conductivity in a gaseous state than carbon dioxide.
  • the thermal conductivity of the foamed polyurethane resin 104 formed by foaming is lowered, and the heat insulating performance of the heat insulating door 101 can be improved.
  • the boiling point of HFO1234ze106 is about ⁇ 19 ° C., but since the solubility in the polyol 108 component is higher than that of carbon dioxide, it can be foamed without causing large bubbles by vaporizing relatively slowly during foaming. Thereby, the heat insulation performance of the polyurethane foam resin 104 can be improved, and the heat insulation performance of the heat insulation door 101 can be improved.
  • HFO1336mzz may be used instead of HFO1234ze106. Since HFO1336mzz has a lower thermal conductivity of gas than HFO1234ze106, the thermal conductivity of the foamed polyurethane resin 104 is reduced, and the thermal insulation performance of the thermal insulation door 101 can be improved.
  • FIG. 3 is a schematic diagram of the refrigerator-freezer according to the second embodiment of the present disclosure.
  • the refrigerator-freezer 201 is disposed so as to close the heat insulating box 202 provided with an opening in one direction, and the opening of the heat insulating box 202.
  • the heat insulating door 203 includes a cooling device 205 that cools a sealed space (storage chamber 204) formed by the heat insulating box 202 and the heat insulating door 203.
  • the space formed by the heat insulation box 202 and the heat insulation door 203 is used as a storage room 204 such as a vegetable room, a refrigerator room, and a freezer room.
  • a plurality of the heat insulating doors 203 are disposed so as to close the opening of the heat insulating box 202.
  • a plurality of storage chambers 204 are formed in the heat insulating box 202.
  • At least the heat insulating door 203 of the refrigerator compartment which is the uppermost storage chamber 204 of the refrigerator / freezer 201, includes an outer surface member 102 (see FIG. 1) on the outside and an inner surface member 103 (see FIG. 1) on the inner side. It is comprised from the foaming polyurethane resin 104 (refer FIG. 1) foam-filled and formed in the substantially closed space between the outer surface material 102 and the inner surface material 103.
  • FIG. The inner surface material 103 has a convex portion provided on the outer peripheral portion of the surface opposite to the surface in contact with the polyurethane foam resin 104.
  • a shelf on which things such as plastic bottles, bottles and eggs are placed is installed on the heat insulating door 203 so as to be easy to use.
  • the inner surface material 103 is provided with convex portions necessary for fixing the shelf.
  • not only a convex part but the recessed part may be provided in order to fix a shelf.
  • the cooling device 205 includes a compressor 205a, a condenser 205b, expansion means (not shown), and an evaporator 205c. Expansion means such as a capillary tube and an expansion valve are disposed between the condenser 205b and the evaporator 205c.
  • the compressor 205a, the condenser 205b, and the evaporator 205c are connected to each other by pipes to constitute a refrigeration cycle. The cool air produced by this refrigeration cycle is supplied to the storage chambers 204 to cool the interior of each storage chamber 204.
  • the foamed polyurethane resin 104 is formed by foaming with cyclopentane 105 and HFO 1234ze 106, as in the first embodiment.
  • an inlet is provided on the back or bottom of the heat insulating box 202, and the heat insulating box 202 is installed with its opening facing down. Then, the raw material is injected vertically or horizontally.
  • the heat insulating box 202 and the heat insulating door 203 are formed of a heat insulating body having at least one feature of the heat insulating body 101 exemplified in the first embodiment.
  • the foamed polyurethane resin 104 filled and foamed in the space between the outer surface material 102 and the inner surface material is at least a polyol 108, a polyisocyanate 109, and a normal temperature.
  • the HFO 1234ze 106 having a lower thermal conductivity in the gas state than carbon dioxide that has been conventionally used is used for the polyurethane foam resin 104 constituting the heat insulating door 203. Therefore, with such a configuration, the thermal conductivity of the foamed polyurethane resin 104 is reduced, and the heat insulating performance of the heat insulating door 203 can be improved.
  • HFO1234ze106 has a boiling point of ⁇ 19 ° C., but HFO1234ze106 has a higher solubility in the polyol 108 component than carbon dioxide, and therefore it vaporizes relatively slowly during foaming, and foams without generating large bubbles (voids). it can. Thereby, the heat insulation performance of the polyurethane foam resin 104 and the heat insulation performance of the heat insulation door 203 can be made high, and the heat insulation performance of the refrigerator-freezer 201 can be improved.
  • HFO1336mzz Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) may be used instead of HFO1234ze.
  • HFO1336mzz has a boiling point of 7 ° C. at atmospheric pressure, and a thermal conductivity of gas at 25 ° C. of 10.5 W / mK. Since HFO1336mzz has a lower gas thermal conductivity than HFO1234ze106, the thermal conductivity of the foamed polyurethane resin 104 is low, and the heat insulating performance of the refrigerator-freezer 201 can be improved.
  • HFO1234ze or HFO1336mzz which is a polyurethane foam resin applicable to the refrigerator-freezer 201
  • Evaluation is performed by cutting out the foamed polyurethane resin 104 from the refrigerator-freezer 201 and evaluating the thermal conductivity and voids.
  • the void is a bubble larger than the average diameter of the foamed polyurethane resin 104.
  • the number of voids was measured by cutting the polyurethane foam resin 104 in the foaming direction, observing the cross section, and counting the number of voids.
  • the foaming direction is a direction perpendicular to the wall thickness.
  • the addition amount described here is wt% with respect to the polyurethane foam resin 104.
  • HFO1234ze is used as the first foaming agent.
  • the amount of carbon dioxide added is 0.5 wt%.
  • Example 1 the amount of HFO1234ze added is 0.5 wt%. In contrast to Comparative Example 1, in Example 1, since the addition amount is small, the number of voids is small, but the thermal conductivity hardly changes.
  • Example 2 the amount of HFO1234ze added is 1.0 wt%. With this addition amount, the number of voids is smaller than that of Comparative Example 1, and the thermal conductivity can be lowered by about 1 mW / mK.
  • Example 3 the amount of HFO1234ze added is 5.0 wt%. With this addition amount, the number of voids is smaller than that of Comparative Example 1, and the thermal conductivity can be lowered by about 1 mW / mK.
  • Example 4 the amount of HFO1234ze added is 10.0 wt%. With this addition amount, the number of voids is slightly greater than in Example 2 and Example 3. The thermal conductivity can be lowered by about 0.7 mW / mK compared to Comparative Example 1.
  • Example 5 the amount of HFO1234ze added is 15.0 wt%. With this addition amount, the number of voids increases. For this reason, the thermal conductivity is higher than that of Comparative Example 1 by 0.5 mW / mK.
  • the amount of HFO 1234ze added is 1 wt% or more and 10% or less in Examples 2 to 4.
  • the core density of the polyurethane foam resin 104 is 50 kg / m 3 or less.
  • the core density is the density of the portion excluding the skin layer on the surface of the polyurethane foam resin 104.
  • the addition amount described here is wt% with respect to the polyurethane foam resin 104.
  • HFO1336mzz is used as the first foaming agent.
  • the amount of carbon dioxide added is 0.5 wt%.
  • Example 6 the amount of HFO 1336mzz added is 0.7 wt%. In contrast to Comparative Example 1, in Example 6, since the addition amount is small, the number of voids is small, but the thermal conductivity changes only slightly.
  • Example 7 the amount of HFO1336mzz added is 1.4 wt%. With this addition amount, the number of voids is smaller than that of Comparative Example 1, and the thermal conductivity can be lowered by about 1.3 mW / mK.
  • Example 8 the amount of HFO1336mzz added is 7.0 wt%. With this addition amount, the number of voids is smaller than that in Comparative Example 1, and the thermal conductivity can be lowered by about 1.5 mW / mK.
  • Example 9 the amount of HFO 1336mzz added is 14.0 wt%. With this added amount, the number of voids is slightly greater than in Examples 7 and 8. The thermal conductivity can be lowered by about 1.2 mW / mK compared to Comparative Example 1.
  • Example 10 the amount of HFO 1336mzz added is 21.0 wt%. With this addition amount, the number of voids increases. Therefore, the thermal conductivity is higher than that of Comparative Example 1 by 0.2 mW / mK.
  • Example 7 to Example 8 As a comprehensive evaluation, it is preferable that the addition amount of Example 7 to Example 8, that is, HFO 1336mzz is 1.4 wt% or more and 14% or less.
  • the core density of the polyurethane foam resin 104 is 50 kg / m 3 or less.
  • the core density is the density of the portion excluding the skin layer on the surface of the polyurethane foam resin 104.
  • the present disclosure can reduce the thermal conductivity of the polyurethane foam resin and can reduce the generation of large bubbles during foaming due to bumping, and has improved heat insulation performance, heat insulation box, heat insulation door And a refrigerator-freezer. Therefore, it can be applied not only to refrigerators and refrigerators but also to containers and storages that require high heat insulation performance.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Refrigerator Housings (AREA)
  • Thermal Insulation (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une porte calorifuge (101) comprenant une résine de polyuréthanne expansé (104), expansée et remplissant un espace entre un matériau (102) de surface extérieure et un matériau (103) de surface intérieure. Un mélange d'au moins un polyol, un polyisocyanate, un cyclopentane et l'HFO1234ze, qui est une hydrofluorooléfine présentant un point d'ébullition de 10 °C ou moins sous la pression atmosphérique, est injecté dans un espace, expansé, et durci pour former la résine de polyuréthanne expansée (104).
PCT/JP2018/006347 2017-03-01 2018-02-22 Corps calorifuge, corps d'enceinte calorifuge, porte calorifuge et refrigerateur-congélateur WO2018159430A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019502919A JPWO2018159430A1 (ja) 2017-03-01 2018-02-22 断熱体、断熱箱体、断熱扉及び冷凍冷蔵庫
CN201880014526.1A CN110382578A (zh) 2017-03-01 2018-02-22 隔热体、隔热箱体、隔热门和冷冻冷藏库

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-038345 2017-03-01
JP2017038345 2017-03-01

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WO2018159430A1 true WO2018159430A1 (fr) 2018-09-07

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JP (1) JPWO2018159430A1 (fr)
CN (1) CN110382578A (fr)
WO (1) WO2018159430A1 (fr)

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JP2023085796A (ja) * 2021-12-09 2023-06-21 株式会社ジェイエスピー ポリスチレン系樹脂押出発泡板の製造方法
JP2023105071A (ja) * 2019-02-27 2023-07-28 旭有機材株式会社 ポリオール薬液組成物

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JP2016074912A (ja) * 2009-12-16 2016-05-12 ハネウェル・インターナショナル・インコーポレーテッド シス−１，１，１，４，４，４−ヘキサフルオロ−２−ブテンの組成物及び使用
JP2015500362A (ja) * 2011-12-09 2015-01-05 ハネウェル・インターナショナル・インコーポレーテッド 発泡体、およびｈｃｆｏまたはｈｆｏ発泡剤を含む発泡体から作られる物品
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023105071A (ja) * 2019-02-27 2023-07-28 旭有機材株式会社 ポリオール薬液組成物
JP7733060B2 (ja) 2019-02-27 2025-09-02 旭有機材株式会社 ポリオール薬液組成物
JP2023085796A (ja) * 2021-12-09 2023-06-21 株式会社ジェイエスピー ポリスチレン系樹脂押出発泡板の製造方法
JP7667730B2 (ja) 2021-12-09 2025-04-23 株式会社ジェイエスピー ポリスチレン系樹脂押出発泡板の製造方法

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JPWO2018159430A1 (ja) 2019-12-19

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