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WO2018159430A1 - Heat-insulating body, heat-insulating box body, heat-insulating door, and refrigerator-freezer - Google Patents

Heat-insulating body, heat-insulating box body, heat-insulating door, and refrigerator-freezer 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
Other languages
French (fr)
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
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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/en
Priority to CN201880014526.1A priority patent/CN110382578A/en
Publication of WO2018159430A1 publication Critical patent/WO2018159430A1/en

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    • 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

A heat-insulating door (101) is provided with a foamed polyurethane resin (104) foamed and filled in a space between an outer surface material (102) and an inner surface material (103). A mixture of at least polyol, polyisocyanate, cyclopentane, and HFO1234ze, which is a hydrofluoroolefin having a boiling point of 10°C or less under atmospheric pressure, is injected into a space, foamed, and cured to form the foamed polyurethane resin (104).

Description

断熱体、断熱箱体、断熱扉及び冷凍冷蔵庫Insulation, insulation box, insulation door and refrigerator
　本開示は、内部に充填発泡された発泡ポリウレタン樹脂を有する断熱体と、断熱体を有する断熱箱体と、断熱体を有する断熱扉と、これらのうち少なくとも一つを備える冷凍冷蔵庫とに関する。 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.
　近年、地球環境保護の観点から、熱エネルギを効率的に利用する技術開発に対する社会的要望が高まっている。このような背景から、冷凍冷蔵庫において、各種部品及び機器全体の省エネルギ設計に加えて、高性能断熱技術の開発に注力されている。一般的に、冷凍冷蔵庫では、断熱材料として、発泡ポリウレタン樹脂が使用されている。 In recent years, from the viewpoint of protecting the global environment, there is an increasing social demand for technology development that efficiently uses thermal energy. From such a background, in the refrigerator-freezer, in addition to the energy-saving design of various parts and the entire device, the development of high-performance heat insulation technology is focused. In general, in a refrigerator-freezer, a polyurethane foam resin is used as a heat insulating material.
　発泡ポリウレタン樹脂は、原料であるポリオール及びポリイソシアネートに発泡剤が加えられて、発泡成形されて得られる。発泡剤として、以前は、ＣＦＣ及びＨＣＦＣが用いられていたが、オゾン層破壊及び地球温暖化の問題が指摘され、近年はノンフロンであるシクロペンタンを用いた発泡ポリウレタン樹脂が主流となっている。しかし、シクロペンタンを発泡剤とした発泡ポリウレタン樹脂は、ＣＦＣ及びＨＣＦＣに比べて、ガスの熱伝導率が高く、発泡ポリウレタン樹脂の断熱性能が劣るという問題がある。 The foamed polyurethane resin is obtained by foaming by adding a foaming agent to polyol and polyisocyanate which are raw materials. Previously, 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. However, 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.
　そこで、発泡剤として、二酸化炭素を用い、発泡気泡の微細化を図ることで輻射伝熱を小さくし、熱伝導率を低くすることで、上記問題の解決を図っているものがある（例えば、特許文献１参照）。 Therefore, carbon dioxide is used as a foaming agent, and there is a solution that solves the above problem by reducing the radiant heat transfer by reducing the size of the foamed bubbles and lowering the thermal conductivity (for example, Patent Document 1).
　しかしながら、発泡剤として二酸化炭素を用いる場合には、以下のような課題がある。二酸化炭素のガスの熱伝導率が高いため、発泡ポリウレタン樹脂の断熱性能が悪化する。また、空間に原料を注入する時に突沸し、発泡ポリウレタン樹脂に大きな気泡が生じ、断熱性能が悪化する。 However, when carbon dioxide is used as a foaming agent, there are the following problems. Since the thermal conductivity of carbon dioxide gas is high, the heat insulation performance of the polyurethane foam resin is deteriorated. In addition, when the raw material is injected into the space, it suddenly boils, large bubbles are generated in the polyurethane foam resin, and the heat insulation performance deteriorates.
特開２００９－２６２９号公報JP 2009-2629 A
　本開示は、上記のような従来の課題に鑑みてなされたものであり、発泡ポリウレタン樹脂の断熱性能の優れた断熱体を提供する。また、本開示は、上記断熱体を有する断熱箱体、上記断熱体を有する断熱扉、及び、これらうち少なくとも一つを備える冷凍冷蔵庫を提供する。 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.
　具体的には、本開示の一例による断熱体は、発泡ポリウレタン樹脂と、発泡ポリウレタン樹脂が充填発泡される空間とを備える。発泡ポリウレタン樹脂は、少なくとも、ポリオール成分と、ポリイソシアネート成分と、大気圧下における沸点が１０℃以下のハイドロフルオロオレフィンである第１の発泡剤と、シクロペンタンである第２の発泡剤との混合物が、空間に注入されて、発泡し硬化されて構成されている。 Specifically, a heat insulator according to an example of the present disclosure 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.
　このような構成により、発泡ポリウレタン樹脂の気泡内のガスの熱伝導率を低くするとともに、突沸によるフォームへの大きな気泡の生成を低減することができる。また、このような構成により、発泡ポリウレタン樹脂が、大きな気泡を生じることなく発泡することができる。よって、このような構成により、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を、向上させることができる。 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.
　また、本開示の一例による断熱体において、第１の発泡剤の熱伝導率は、好ましくは１５．０ｍＷ／ｍＫ以下である。このような構成によれば、第１の発泡剤であるＨＦＯは、二酸化炭素よりガスの熱伝導率が低いので、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を高めることができる。 In the heat insulator according to an example of the present disclosure, the thermal conductivity of the first foaming agent is preferably 15.0 mW / mK or less. According to such a configuration, 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.
　また、本開示の一例による断熱体において、第１の発泡剤は、ポリオール成分に対する溶解度が、好ましくは、ポリオール成分に対する二酸化炭素の溶解度以上である。このような構成によれば、二酸化炭素よりポリオール成分に対する溶解度が高いため、発泡ポリウレタン樹脂は、発泡時に比較的緩やかに気化し、大きな気泡を生じることなく発泡することができる。これにより、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を高めることができる。 Further, in the heat insulator according to an example of the present disclosure, 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. According to such a configuration, since 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. Thereby, 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.
　また、本開示の一例による断熱体において、第１の発泡剤は、好ましくは、ＨＦＯ１２３４ｚｅまたはＨＦＯ１２３３ｚｄである。第１の発泡剤が、二酸化炭素よりガスの熱伝導率が低いＨＦＯ１２３４ｚｅまたはＨＦＯ１２３３ｚｄで構成されているので、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を高めることができる。 In the heat insulator according to an example of the present disclosure, 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.
　また、本開示の一例による断熱体において、発泡ポリウレタン樹脂のコア密度は、好ましくは５０ｋｇ／ｍ３以下である。このような構成によれば、密度からみると、発泡ポリウレタン樹脂の熱伝導率を低くできるので、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を高めることができる。 In the heat insulator according to an example of the present disclosure, 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. .
　また、本開示の一例による断熱体において、第１の発泡剤は、発泡ポリウレタン樹脂に対する添加量が、好ましくは１％以上１０％以下である。このような構成によれば、発泡ポリウレタン樹脂の注入時に突沸することを抑えることができ、発泡ポリウレタン樹脂に大きな気泡が生じることを低減することができる。よって、このような構成により、発泡ポリウレタン樹脂の断熱性能、及び、発泡ポリウレタン樹脂を備えた断熱体の断熱性能を高めることができる。 In the heat insulator according to an example of the present disclosure, 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.
　また、本開示の一例による断熱箱体は、上記の断熱体の特徴のうち少なくともいずれか一つを有する断熱体で構成され、断熱体が箱状の形状を有していてもよい。このような構成により、優れた断熱性能を有する断熱箱体が得られる。 Further, 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.
　また、本開示の一例による断熱扉は、上記の断熱体の特徴のうち少なくともいずれか一つを有する断熱体で構成されている。このような構成により、優れた断熱性能を有する断熱扉が得られる。 In addition, 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.
　また、本開示の一例による冷凍冷蔵庫は、一方向に開口部が設けられた箱体と、箱体の開口部を閉じて密閉空間が形成されるように配設された扉と、箱体と扉とから形成される密閉空間を冷却する冷却装置とを備える。箱体は、上記の断熱体の特徴のうち少なくともいずれか一つを有する断熱箱体で構成されていてもよい。このような構成により、優れた断熱性能を有する冷凍冷蔵庫が得られる。 In addition, a refrigerator-freezer according to an example of the present disclosure 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.
　また、本開示の一例による冷凍冷蔵庫は、一方向に開口部が設けられた箱体と、箱体の開口部を閉じて密閉空間が形成されるように配設された扉と、箱体と扉とから形成される密閉空間を冷却する冷却装置とを備える。扉は、上記の断熱体の特徴のうち少なくともいずれか一つを有する断熱扉で構成されていてもよい。このような構成により、優れた断熱性能を有する冷凍冷蔵庫が得られる。 In addition, a refrigerator-freezer according to an example of the present disclosure 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. With such a configuration, a refrigerator-freezer having excellent heat insulation performance can be obtained.
図１は、本開示の実施の形態１における断熱扉の断面図である。FIG. 1 is a cross-sectional view of a heat insulating door according to the first embodiment of the present disclosure. 図２は、本開示の実施の形態１における断熱扉の製造方法を示す概略図である。FIG. 2 is a schematic diagram illustrating a method for manufacturing a heat insulating door according to the first embodiment of the present disclosure. 図３は、本開示の実施の形態２における冷凍冷蔵庫の断面図である。FIG. 3 is a cross-sectional view of the refrigerator-freezer according to the second embodiment of the present disclosure.
　以下、本開示の実施の形態の例を、図面を参照しながら説明する。なお、以下の実施の形態によって本開示が限定されるものではない。 Hereinafter, exemplary embodiments of the present disclosure will be described with reference to the drawings. Note that the present disclosure is not limited to the following embodiments.
　（実施の形態１）
　図１は、本開示の実施の形態１における断熱体である断熱扉の断面図である。図２は、本開示の実施の形態１における断熱体である断熱扉の製造方法を示す概略図である。 (Embodiment 1)
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.
　図１及び図２に示すように、本開示の実施の形態１の断熱扉１０１は、断熱扉１０１を形成する外側の外面材１０２と、内側の内面材１０３とを有する。また、本開示の実施の形態１の断熱扉１０１は、外面材１０２と内面材１０３とにより形成される閉ざされた空間を有する。また、本開示の実施の形態１の断熱扉１０１は、外面材１０２と内面材１０３との間の閉ざされた空間に発泡充填されて形成された発泡ポリウレタン樹脂１０４を有する。 As shown in FIGS. 1 and 2, 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. In addition, 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. In addition, 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.
　次に、断熱扉１０１の製造方法を説明する（図２参照）。まず、第１の発泡剤と第２の発泡剤とをポリオール１０８に混合する。第１の発泡剤は、トランス－１，１，１，３－テトラフルオロプロペン（ＨＦＯ１２３４ｚｅ）である。ＨＦＯ１２３４ｚｅは、大気圧での沸点が－１８．９５℃であり、２５℃でのガスの熱伝導率が０．０１３６Ｗ／ｍＫである。第２の発泡剤は、シクロペンタンである。 Next, a method for manufacturing the heat insulating door 101 will be described (see FIG. 2). First, 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.
　次に、ミキシングヘッド１０７において、シクロペンタン１０５とＨＦＯ１２３４ｚｅ１０６とが混合されたポリオール１０８にポリイソシアネート１０９を混合し、外面材１０２の上に注入し、その後、すぐに内面材１０３を取り付けて、外面材１０２と内面材１０３との間の空間にシクロペンタン１０５及びＨＦＯ１２３４ｚｅ１０６が発泡し成形される。これにより、断熱扉１０１が製造される。 Next, in the mixing head 107, 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.
　発泡成形は、内面材１０３及び外面材１０２が発泡ポリウレタン樹脂１０４の発泡圧で変形しないように、内面材１０３及び外面材１０２の発泡ポリウレタン樹脂１０４と逆側が、発泡治具により固定された状態（図示なし）で行われる。 In the foam molding, a state where the inner surface material 103 and the outer surface material 102 opposite to the foamed polyurethane resin 104 are fixed by a foaming jig so that the inner surface material 103 and the outer surface material 102 are not deformed by the foaming pressure of the foamed polyurethane resin 104 ( (Not shown).
　なお、外面材１０２または内面材１０３のいずれか一方に、注入口を設け、注入口から、外面材１０２と内面材１０３とが予め取り付けられて形成された空間に、発泡ポリウレタン樹脂１０４を注入してもよい。ポリオール１０８には、予め、水、整泡剤及び触媒などが混合されていてもよい。 In addition, 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. May be. The polyol 108 may be mixed with water, a foam stabilizer, a catalyst, and the like in advance.
　以上のように構成された本実施の形態の断熱扉１０１は、外面材１０２と内面材１０３との間に形成された空間を有する。また、本実施の形態の断熱扉１０１は、上記空間に充填発泡された発泡ポリウレタン樹脂１０４を有する。また、本実施の形態の断熱扉１０１において、発泡ポリウレタン樹脂１０４は、少なくとも、ポリオール１０８と、ポリイソシアネート１０９と、常温で液体の炭化水素である液状のシクロペンタン１０５と、大気圧下における沸点が１０℃以下のＨＦＯであるＨＦＯ１２３４ｚｅ１０６との混合物が、上記空間に注入されて、発泡し硬化したものである。 The heat insulating door 101 according to the present embodiment 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. In the heat insulating door 101 of the present embodiment, 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.
　また、本実施の形態の断熱扉１０１は、二酸化炭素より気体状態での熱伝導率が低いＨＦＯ１２３４ｚｅ１０６が使用された発泡ポリウレタン樹脂１０４で構成されている。 Further, 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.
　このような構成により、発泡成形された発泡ポリウレタン樹脂１０４の熱伝導率が低くなり、断熱扉１０１の断熱性能を向上させることができる。 With such a configuration, 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.
　また、ＨＦＯ１２３４ｚｅ１０６の沸点は、約－１９℃であるが、二酸化炭素よりポリオール１０８成分に対する溶解度が高いため、発泡時に比較的緩やかに気化し、大きな気泡を生じることなく、発泡することができる。これにより、発泡ポリウレタン樹脂１０４の断熱性能を高めることができ、断熱扉１０１の断熱性能を向上させることができる。 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.
　なお、ＨＦＯ１２３４ｚｅ１０６の代わりに、ＨＦＯ１３３６ｍｚｚを用いてもよい。ＨＦＯ１３３６ｍｚｚは、ＨＦＯ１２３４ｚｅ１０６よりも更にガスの熱伝導率が低いため、発泡成形された発泡ポリウレタン樹脂１０４の熱伝導率が低くなり、断熱扉１０１の断熱性能を向上させることができる。 Note that 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.
　（実施の形態２）
　図３は、本開示の実施の形態２における冷凍冷蔵庫の概略図である。 (Embodiment 2)
FIG. 3 is a schematic diagram of the refrigerator-freezer according to the second embodiment of the present disclosure.
　なお、本開示の実施の形態２の冷凍冷蔵庫の断熱扉の製造方法は、図２に示した実施の形態１の製造方法と同様であるので、ここでは説明は省略する。 In addition, since the manufacturing method of the heat insulation door of the refrigerator-freezer of Embodiment 2 of this indication is the same as the manufacturing method of Embodiment 1 shown in FIG. 2, description is abbreviate | omitted here.
　図３に示すように、本開示の実施の形態２の冷凍冷蔵庫２０１は、１方向に開口部が設けられた断熱箱体２０２と、断熱箱体２０２の開口部を閉じるように配設された断熱扉２０３と、断熱箱体２０２と断熱扉２０３とから形成される密閉空間（収納室２０４）を冷却する冷却装置２０５とで構成されている。 As shown in FIG. 3, the refrigerator-freezer 201 according to the second embodiment of the present disclosure 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.
　断熱箱体２０２と断熱扉２０３とで形成される空間は、野菜室、冷蔵室、及び冷凍室などの収納室２０４として使用される。断熱扉２０３は、断熱箱体２０２の開口部を閉じるように、複数枚、配設されている。また、断熱箱体２０２には、複数の収納室２０４が形成されている。 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.
　少なくとも冷凍冷蔵庫２０１の一番上の収納室２０４である冷蔵室の断熱扉２０３は、扉を形成する外側の外面材１０２（図１参照）と、内側の内面材１０３（図１参照）と、外面材１０２と内面材１０３との間の略閉ざされた空間に発泡充填形成された発泡ポリウレタン樹脂１０４（図１参照）とから構成されている。内面材１０３は、発泡ポリウレタン樹脂１０４と接触する面とは反対側の面の外周部に設けられた凸部を有する。 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.
　冷蔵室において、使用し易いように、ペットボトル、ビン及び卵等のものを乗せる棚が、断熱扉２０３に設置されている。内面材１０３には、棚を固定するために必要な凸部が設けられている。なお、棚を固定するために凸部だけでなく凹部が設けられていてもよい。断熱扉２０３が閉じられたとき、内面材１０３の外周部の凸部は、冷蔵室内に収まり、冷蔵室内の冷気が外部に漏れることを抑制する。さらに、図示していないが、冷気漏れ抑制のため、凸部外周にガスケットなどを装着するとより効果的である。 In the refrigerator compartment, 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. In addition, not only a convex part but the recessed part may be provided in order to fix a shelf. When the heat insulation door 203 is closed, the convex part of the outer peripheral part of the inner surface material 103 is accommodated in the refrigerator compartment, and it suppresses that the cool air in a refrigerator compartment leaks outside. Furthermore, although not shown, it is more effective to attach a gasket or the like to the outer periphery of the convex portion in order to suppress cold air leakage.
　冷却装置２０５は、圧縮機２０５ａと、凝縮器２０５ｂと、膨張手段（図示せず）と、蒸発器２０５ｃとから構成されている。凝縮器２０５ｂと蒸発器２０５ｃとの間には、キャピラリーチューブ及び膨張弁などの膨張部手段が配設されている。圧縮機２０５ａ、凝縮器２０５ｂ、及び、蒸発器２０５ｃは、互いに配管接続されて冷凍サイクルを構成している。この冷凍サイクルでつくられた冷気が、収納室２０４へ供給されて各収納室２０４内部を冷却する。 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.
　発泡ポリウレタン樹脂１０４は、上記実施の形態１と同様に、シクロペンタン１０５及びＨＦＯ１２３４ｚｅ１０６によって発泡成形されて構成されている。なお、断熱箱体２０２に発泡ポリウレタン樹脂１０４の原料を充填する場合、一般的に、断熱箱体２０２の背面または底面に注入口を設け、断熱箱体２０２を、その開口部を下にして設置して、鉛直または水平方向に原料を注入する。 The foamed polyurethane resin 104 is formed by foaming with cyclopentane 105 and HFO 1234ze 106, as in the first embodiment. In addition, when filling the raw material of the polyurethane foam resin 104 into the heat insulating box 202, generally, 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.
　以上のように構成された冷凍冷蔵庫２０１において、断熱箱体２０２及び断熱扉２０３は、上記実施の形態１で例示した断熱体１０１の特徴を少なくとも一つ有する断熱体で構成されている。具体的には、本実施の形態の断熱扉２０３は、外面材１０２と内面材との間の空間に充填発泡された発泡ポリウレタン樹脂１０４が、少なくとも、ポリオール１０８と、ポリイソシアネート１０９と、常温で液体の炭化水素である液状のシクロペンタン１０５と、大気圧下における沸点が１０℃以下のＨＦＯであるＨＦＯ１２３４ｚｅ１０６との混合物が、空間に注入されて、発泡し硬化して構成された断熱体で構成されている。 In the refrigerator-freezer 201 configured as described above, 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. Specifically, in the heat insulating door 203 of the present 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. A mixture of liquid cyclopentane 105, which is a liquid hydrocarbon, and HFO 1234ze 106, which is an HFO having a boiling point of 10 ° C. or less under atmospheric pressure, is injected into the space, and is formed of a heat insulating body configured by foaming and curing. Has been.
　本開示の冷凍冷蔵庫２０１においては、従来使われていた二酸化炭素より気体状態での熱伝導率が低いＨＦＯ１２３４ｚｅ１０６が、断熱扉２０３を構成する発泡ポリウレタン樹脂１０４に使用されている。よって、このような構成により、発泡成形された発泡ポリウレタン樹脂１０４の熱伝導率が低くなり、断熱扉２０３の断熱性能を向上させることができる。また、ＨＦＯ１２３４ｚｅ１０６の沸点は－１９℃であるが、ＨＦＯ１２３４ｚｅ１０６は、二酸化炭素よりポリオール１０８成分に対する溶解度が高いため、発泡時に比較的緩やかに気化し、大きな気泡（ボイド）を生じることなく発泡することができる。これにより、発泡ポリウレタン樹脂１０４の断熱性能、及び、断熱扉２０３の断熱性能を高くすることができ、冷凍冷蔵庫２０１の断熱性能を向上させることができる。 In the refrigerator-freezer 201 of the present disclosure, 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.
　なお、ＨＦＯ１２３４ｚｅの代わりに、Ｚ－１，１，１，４，４，４－ヘキサフルオロ－２－ブテン（ＨＦＯ１３３６ｍｚｚ）を用いてもよい。ＨＦＯ１３３６ｍｚｚは、大気圧での沸点が７℃であり、２５℃でのガスの熱伝導率が１０．５Ｗ／ｍＫである。ＨＦＯ１３３６ｍｚｚは、ＨＦＯ１２３４ｚｅ１０６よりも更にガスの熱伝導率が低いため、発泡成形された発泡ポリウレタン樹脂１０４の熱伝導率が低くなり、冷凍冷蔵庫２０１の断熱性能を向上させることができる。 Note that 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.
　以下に、冷凍冷蔵庫２０１に適用可能な発泡ポリウレタン樹脂のＨＦＯ１２３４ｚｅまたはＨＦＯ１３３６ｍｚｚの添加量に対する熱伝導率とボイドとの関係について、実施例及び比較例を挙げて説明する。 Hereinafter, the relationship between the thermal conductivity and the void with respect to the addition amount of HFO1234ze or HFO1336mzz, which is a polyurethane foam resin applicable to the refrigerator-freezer 201, will be described with examples and comparative examples.
　評価は、冷凍冷蔵庫２０１から発泡ポリウレタン樹脂１０４を切り出し、熱伝導率及びボイドを評価することで行われる。 Evaluation is performed by cutting out the foamed polyurethane resin 104 from the refrigerator-freezer 201 and evaluating the thermal conductivity and voids.
　ボイドとは、発泡ポリウレタン樹脂１０４の気泡の平均径より大きい気泡である。ボイドの数は、発泡ポリウレタン樹脂１０４を発泡方向に切断し、断面を観察して、ボイドの数を数えることにより測定したものである。冷凍冷蔵庫２０１の場合、発泡方向とは壁厚に垂直な方向のことである。 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. In the case of the refrigerator-freezer 201, the foaming direction is a direction perpendicular to the wall thickness.
　実施例を（表１）に示す。 Examples are shown in (Table 1).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　ここで記載する添加量は、発泡ポリウレタン樹脂１０４に対する重量％である。実施例１～実施例５は、第１の発泡剤として、ＨＦＯ１２３４ｚｅが用いられている。比較例１は、二酸化炭素の添加量が０．５ｗｔ％である。 The addition amount described here is wt% with respect to the polyurethane foam resin 104. In Examples 1 to 5, HFO1234ze is used as the first foaming agent. In Comparative Example 1, the amount of carbon dioxide added is 0.5 wt%.
　実施例１では、ＨＦＯ１２３４ｚｅの添加量が０．５ｗｔ％である。比較例１に対して、実施例１では、添加量が少ないため、ボイドの数は少ないが、熱伝導率はほとんど変化しない。 In 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.
　実施例２では、ＨＦＯ１２３４ｚｅの添加量が１．０ｗｔ％である。この添加量では、比較例１に対して、ボイドの数は少なく、熱伝導率を約１ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例３では、ＨＦＯ１２３４ｚｅの添加量が５．０ｗｔ％である。この添加量では、比較例１に対して、ボイドの数は少なく、熱伝導率を約１ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例４では、ＨＦＯ１２３４ｚｅの添加量が１０．０ｗｔ％である。この添加量では、ボイドの数は実施例２及び実施例３よりは少し増える。熱伝導率は、比較例１に対して、約０．７ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例５では、ＨＦＯ１２３４ｚｅの添加量が１５．０ｗｔ％である。この添加量では、ボイドの数が増えてしまう。このため、熱伝導率が、比較例１に対して、０．５ｍＷ／ｍＫ高くなってしまう。 In 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.
　総合的な評価としては、実施例２～実施例４、つまり、ＨＦＯ１２３４ｚｅの添加量が１ｗｔ％以上１０％以下であることが好ましい。実施例２～実施例４では、発泡ポリウレタン樹脂１０４のコア密度は、５０ｋｇ／ｍ３以下である。コア密度とは、発泡ポリウレタン樹脂１０４の表面のスキン層を除いた部分の密度のことである。 As a comprehensive evaluation, it is preferable that the amount of HFO 1234ze added is 1 wt% or more and 10% or less in Examples 2 to 4. 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.
　以上の結果より、ＨＦＯ１２３４ｚｅの添加量が１ｗｔ％以上１０％以下にすることで、注入時に突沸することを抑えることができ、発泡ポリウレタン樹脂１０４に大きな気泡が生じることを低減することができるので、発泡ポリウレタン樹脂１０４の断熱性能を高めることができる。これにより、冷凍冷蔵庫２０１の断熱性能を向上させることができる。 From the above results, by making the addition amount of HFO1234ze 1 wt% or more and 10% or less, it is possible to suppress bumping at the time of injection, and it is possible to reduce the occurrence of large bubbles in the polyurethane foam resin 104. The heat insulation performance of the polyurethane foam resin 104 can be enhanced. Thereby, the heat insulation performance of the refrigerator-freezer 201 can be improved.
　別の実施例を（表２）に示す。 Another example is shown in (Table 2).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　ここで記載する添加量は、発泡ポリウレタン樹脂１０４に対する重量％である。実施例６～実施例１０は、第１の発泡剤として、ＨＦＯ１３３６ｍｚｚが用いられている。比較例１は、二酸化炭素の添加量が０．５ｗｔ％である。 The addition amount described here is wt% with respect to the polyurethane foam resin 104. In Examples 6 to 10, HFO1336mzz is used as the first foaming agent. In Comparative Example 1, the amount of carbon dioxide added is 0.5 wt%.
　実施例６では、ＨＦＯ１３３６ｍｚｚの添加量が０．７ｗｔ％である。比較例１に対して、実施例６では、添加量が少ないため、ボイドの数は少ないが、熱伝導率は少ししか変化しない。 In 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.
　実施例７では、ＨＦＯ１３３６ｍｚｚの添加量が１．４ｗｔ％である。この添加量では、比較例１に対して、ボイドの数は少なく、熱伝導率を約１．３ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例８では、ＨＦＯ１３３６ｍｚｚの添加量が７．０ｗｔ％である。この添加量では、比較例１に対して、ボイドの数は少なく、熱伝導率を約１．５ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例９では、ＨＦＯ１３３６ｍｚｚの添加量が１４．０ｗｔ％である。この添加量では、ボイドの数は実施例７及び８よりは少し増える。熱伝導率は、比較例１に対して、約１．２ｍＷ／ｍＫ低くすることができる。 In 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.
　実施例１０では、ＨＦＯ１３３６ｍｚｚの添加量が２１．０ｗｔ％である。この添加量では、ボイドの数が増えてしまう。そのため、熱伝導率が、比較例１に対して、０．２ｍＷ／ｍＫ高くなってしまう。 In 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.
　総合的な評価としては、実施例７～実施例８、つまり、ＨＦＯ１３３６ｍｚｚの添加量が１．４ｗｔ％以上１４％以下であることが好ましい。実施例７～実施例８では、発泡ポリウレタン樹脂１０４のコア密度は、５０ｋｇ／ｍ３以下である。コア密度とは、発泡ポリウレタン樹脂１０４の表面のスキン層を除いた部分の密度のことである。 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. In Examples 7 to 8, 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.
　以上の結果より、ＨＦＯ１３３６ｍｚｚの添加量が１．４ｗｔ％以上１４％以下にすることで、注入時に突沸することを抑えることができ、発泡ポリウレタン樹脂１０４に大きな気泡が生じることを低減することができる。よって、発泡ポリウレタン樹脂１０４の断熱性能を高めることができる。これにより、冷凍冷蔵庫２０１の断熱性能を向上させることができる。 From the above results, by making the addition amount of HFO 1336mzz 1.4 wt% or more and 14% or less, bumping at the time of injection can be suppressed, and generation of large bubbles in the polyurethane foam resin 104 can be reduced. . Therefore, the heat insulation performance of the polyurethane foam resin 104 can be enhanced. Thereby, the heat insulation performance of the refrigerator-freezer 201 can be improved.
　本開示は、発泡ポリウレタン樹脂の熱伝導率を低減することができるとともに、突沸による発泡時の大きな気泡の生成を低減することができ、断熱性能が向上された断熱体、断熱箱体、断熱扉、及び冷凍冷蔵庫を提供する。よって、冷凍冷蔵庫はもちろん、高い断熱性能を要する容器及び貯蔵庫などにも適用することができる。 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.
　１０１　断熱扉
　１０２　外面材
　１０３　内面材
　１０４　発泡ポリウレタン樹脂
　１０５　シクロペンタン
　１０６　ＨＦＯ１２３４ｚｅ
　１０８　ポリオール
　１０９　ポリイソシアネート
　２０１　冷凍冷蔵庫
　２０２　断熱箱体
　２０３　断熱扉
　２０４　収納室
　２０５　冷却装置
　２０５ａ　圧縮機
　２０５ｂ　凝縮器
　２０５ｃ　蒸発器 DESCRIPTION OF SYMBOLS 101 Heat insulation door 102 Outer surface material 103 Inner surface material 104 Foam polyurethane resin 105 Cyclopentane 106 HFO1234ze
108 Polyol 109 Polyisocyanate 201 Refrigeration refrigerator 202 Heat insulation box 203 Heat insulation door 204 Storage chamber 205 Cooling device 205a Compressor 205b Condenser 205c Evaporator

Claims (10)

  1. 発泡ポリウレタン樹脂と、
    前記発泡ポリウレタン樹脂が充填発泡される空間とを備え、
    前記発泡ポリウレタン樹脂は、少なくとも、ポリオール成分と、ポリイソシアネート成分と、大気圧下における沸点が１０℃以下のハイドロフルオロオレフィンである第１の発泡剤と、シクロペンタンである第２の発泡剤との混合物が、前記空間に注入されて、発泡、硬化したものであることを特徴とする断熱体。     Polyurethane foam resin,
    A space in which the foamed polyurethane resin is filled and foamed,
    The foamed polyurethane resin comprises 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. A heat insulator, wherein the mixture is injected into the space and foamed and cured.
  2. 前記第１の発泡剤の熱伝導率は、１５．０ｍＷ／ｍＫ以下である
    請求項１に記載の断熱体。     The heat insulator according to claim 1, wherein the thermal conductivity of the first foaming agent is 15.0 mW / mK or less.
  3. 前記第１の発泡剤は、前記ポリオール成分に対する溶解度が、前記ポリオール成分に対する二酸化炭素の溶解度以上である
    請求項１または請求項２に記載の断熱体。     3. The heat insulating body according to claim 1, wherein the first foaming agent has a solubility in the polyol component equal to or higher than a solubility of carbon dioxide in the polyol component.
  4. 前記第１の発泡剤が、ＨＦＯ１２３４ｚｅまたはＨＦＯ１３３６ｍｚｚである
    請求項１から３のいずれか一項に記載の断熱体。     The heat insulating body according to any one of claims 1 to 3, wherein the first foaming agent is HFO1234ze or HFO1336mzz.
  5. 前記発泡ポリウレタン樹脂のコア密度が、５０ｋｇ／ｍ３以下である
    請求項１から３のいずれか一項に記載の断熱体。     The heat insulating body according to any one of claims 1 to 3, wherein a core density of the polyurethane foam resin is 50 kg / m 3 or less.
  6. 前記第１の発泡剤は、前記発泡ポリウレタン樹脂に対する添加量が、１％以上１０％以下である
    請求項１から５のいずれか一項に記載の断熱体。     6. The heat insulating body according to claim 1, wherein the first foaming agent has an addition amount of 1% to 10% with respect to the foamed polyurethane resin.
  7. 請求項１から６のいずれか一項に記載の断熱体が箱状の形状を有する断熱箱体。 The heat insulation box which the heat insulation as described in any one of Claim 1 to 6 has a box shape.
  8. 請求項１から６のいずれか一項に記載の断熱体を有する断熱扉。 The heat insulation door which has a heat insulating body as described in any one of Claim 1 to 6.
  9. 一方向に開口部が設けられた箱体と、前記箱体の前記開口部を閉じて密閉空間が形成されるように配設された扉と、前記箱体と前記扉とから形成される前記密閉空間を冷却する冷却装置とからなる冷凍冷蔵庫において、前記箱体が請求項７に記載の断熱箱体である冷凍冷蔵庫。 A box provided with an opening in one direction; a door disposed to close the opening of the box to form a sealed space; and the box and the door. The refrigerator-freezer which consists of a cooling device which cools airtight space, The refrigerator-freezer whose said box is the heat insulation box of Claim 7.
  10. 一方向に開口部が設けられた箱体と、前記箱体の前記開口部を閉じて密閉空間が形成されるように配設された扉と、前記箱体と前記扉とから形成される前記密閉空間を冷却する冷却装置とからなる冷凍冷蔵庫において、前記扉が請求項８に記載の断熱扉である冷凍冷蔵庫。 A box provided with an opening in one direction; a door disposed to close the opening of the box to form a sealed space; and the box and the door. A refrigerator-freezer comprising a cooling device for cooling a sealed space, wherein the door is a heat-insulating door according to claim 8.
PCT/JP2018/006347 2017-03-01 2018-02-22 Heat-insulating body, heat-insulating box body, heat-insulating door, and refrigerator-freezer WO2018159430A1 (en)

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