JP2006064087A - Heat insulator, refrigerating equipment, and chilled/hot equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat insulator capable of holding excellent heat insulating performance over a long time by using a metal complex having excellent performance as a core material and as an adsorbing material. <P>SOLUTION: The heat insulator 7 is provided with the core material 8, a moisture adsorbing material 9, and a cover material for covering the core material 8 and the moisture adsorbing material 9 and formed of a pair of two pieces and having gas barrier performance. The core material 8 comprises the metal complex having porous structure. The heat insulator having excellent initial heat insulating performance and adsorbing performance can be obtained by using the metal complex having porous structure as the core material 8. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat insulator and a refrigeration apparatus and a cooling / heating apparatus related to the heat insulating body.

  In recent years, energy saving is strongly desired from the viewpoint of preventing global warming, and energy saving is an urgent issue for household appliances. In particular, a heat insulating material having excellent heat insulating performance is required from the viewpoint of efficiently using heat in a heat and cold insulation device such as a refrigerator, a freezer, and a vending machine.

  As general heat insulating materials, fiber materials such as glass wool and foams such as urethane foam are used. However, in order to improve the heat insulation performance of these heat insulating materials, it is necessary to increase the thickness of the heat insulating material, and there is a limit to the space that can be filled with the heat insulating material, so when space saving and effective use of the space are necessary It cannot be applied.

  Therefore, a vacuum heat insulator has been proposed as a high performance heat insulating material. This is a heat insulating body in which a core material serving as a spacer is inserted into a jacket material having gas barrier properties and the inside is sealed under reduced pressure.

  By increasing the degree of vacuum inside the vacuum heat insulating body, high performance heat insulating performance can be obtained, but the gas existing inside the vacuum heat insulating body is roughly divided into the following three types. One is the gas that cannot be evacuated when the vacuum heat insulator is manufactured, and the other is the gas generated from the core material and the jacket material after being vacuum-sealed (adsorbed to the core material and the jacket material). The remaining gas is a gas that permeates through the jacket material and enters from the outside.

  In order to adsorb these gases, a method of filling a vacuum heat insulating material with an adsorbent has been devised.

  For example, there exists what adsorb | sucks nitrogen in a vacuum heat insulating body with a Ba-Li alloy (for example, refer patent document 1).

  Further, a vacuum heat insulator has been proposed in which a resin powder having a gas adsorbing ability is bonded with a binder as a core material (see, for example, Patent Document 2). For example, by using an ion exchange resin powder bonded with a binder made of ethyl cellulose, it has a function of maintaining the initial heat insulating characteristics over a long period of time while maintaining the shape against pressure by atmospheric pressure. It is a vacuum heat insulator provided with a core material.

  In recent years, a method for adsorbing and desorbing a gas on a metal complex has been devised for the purpose of storing methane in a natural gas vehicle.

For example, by contacting a dicarboxylic acid metal complex with methane under pressurized conditions, gas is adsorbed and stored, and methane is released by reducing the pressure (for example, see Patent Document 3).
Japanese National Patent Publication No. 9-512088 Japanese Patent Laid-Open No. 11-351493 Japanese Patent Laid-Open No. 10-316684

  However, in the above-described conventional configuration described in Patent Document 1, it is conceivable that the heat insulation performance of the portion to which the adsorbent is applied is deteriorated because the heat conduction of the adsorbent itself is high.

  Further, in the conventional configuration described in Patent Document 2, since a resin is used as the core material and the adsorbent, it is difficult to uniformly polymerize the monomer to obtain a uniform polymer. It is difficult to make the pore diameter small and uniform. Therefore, there are pores that are larger or smaller than the desired size, and such pores cannot adsorb the target gas or the amount of gas adsorption decreases as a whole. Can be considered.

  Further, since the resin powder has a large particle size of 10 to 200 μm and a small thermal resistance, it is considered that the solid heat conduction increases and the heat insulation performance deteriorates.

  Moreover, in the said conventional structure of patent document 3, it is gas adsorption on pressurization conditions, and there is no description as a heat insulating body.

  The present invention solves the above-mentioned conventional problems, and provides a heat insulator having excellent heat insulation performance in the initial stage and over time by using a metal complex having excellent performance as both a core material and an adsorbent. The purpose is to do.

  In order to solve the above-described conventional problems, the heat insulator of the present invention includes at least a core material and a jacket material having gas barrier properties, and the main component of the core material is a metal complex having a porous skeleton. It is characterized by.

  A metal complex having a porous skeleton, particularly one having a three-dimensional structure, can be easily designed and synthesized with a structure having uniform and fine pores, and can be an adsorbent that selectively adsorbs a target gas. For example, for the purpose of nitrogen adsorption, it is possible to design a metal complex having an optimum pore diameter for nitrogen adsorption in consideration of how many molecules of nitrogen are adsorbed in one pore.

  At this time, if the pore diameter is too large, gas molecules cannot be adsorbed efficiently, so the pore diameter is desirably 20 mm or less. In particular, the gas can be adsorbed more by having an active metal in the complex. Moreover, since the wall having a porous skeleton and partitioning the pores is thin, the specific surface area can be increased, so that the adsorbent has a large capacity and becomes an excellent heat insulator over time.

  In addition, since the wall thickness is thin as described above, it is possible to increase the pore volume and increase the thermal resistance between the particles by using the metal complex as a secondary particle that is an aggregate of primary particles. Therefore, solid heat conduction can be reduced, and a core material having excellent initial heat insulation performance can be obtained.

  As described above, by using a metal complex having a porous skeleton as a core material and an adsorbing material, a heat insulating material excellent in heat insulating performance can be obtained in the initial stage and over time.

  In addition, since some metal complexes are weak against moisture, it is possible to obtain a more reliable heat insulator by applying a moisture adsorbent.

  Moreover, although only a metal complex can be used as a core material, by adding a fiber material, the core material becomes stronger and a core material excellent in workability and flatness can be obtained. In particular, a core material with better handleability can be obtained by including an inorganic fiber material and making the bending elastic modulus 0.2 MPa or more by performing press working or the like.

  Further, by using the core material having the metal complex as described above between the walls of the heat insulating box, a heat insulating box having excellent heat insulating performance and excellent productivity can be obtained.

  The heat insulator of the present invention is excellent in initial thermal conductivity as a core material by using a metal complex having a porous skeleton as a core material, and functions as a large capacity adsorbent. A heat insulator that can be held for a long time can be obtained.

  The invention according to claim 1 is a heat insulator characterized in that it comprises at least a core material and a jacket material having gas barrier properties, and the main component of the core material is a metal complex having a porous skeleton. .

  A metal complex having a porous skeleton, particularly one having a three-dimensional structure, can be easily designed and synthesized with a structure having uniform and fine pores, and can be an adsorbent that selectively adsorbs a target gas. For example, for the purpose of nitrogen adsorption, it is possible to design a metal complex having an optimum pore diameter for nitrogen adsorption in consideration of how many molecules of nitrogen are adsorbed in one pore.

  At this time, if the pore diameter is too large, gas molecules cannot be adsorbed efficiently, so the pore diameter is desirably 20 mm or less. In particular, the gas can be adsorbed more by having an active metal in the complex. Moreover, since the wall having a porous skeleton and partitioning the pores is thin, the specific surface area can be increased, so that the adsorbent has a large capacity and becomes an excellent heat insulator over time.

  In addition, since the wall thickness is thin as described above, it is possible to increase the pore volume and increase the thermal resistance between the particles by using the metal complex as a secondary particle that is an aggregate of primary particles. Therefore, solid heat conduction can be reduced, and a core material having excellent initial heat insulation performance can be obtained.

  As described above, by using a metal complex having a porous skeleton as a core material and an adsorbing material, a heat insulating material excellent in heat insulating performance can be obtained in the initial stage and over time.

  In addition, since some metal complexes are weak against moisture, it is possible to obtain a more reliable heat insulator by applying a moisture adsorbent.

  Moreover, although only a metal complex can be used as a core material, by adding a fiber material, the core material becomes stronger and a core material excellent in workability and flatness can be obtained. In particular, a core material with better handleability can be obtained by including an inorganic fiber material and making the bending elastic modulus 0.2 MPa or more by performing press working or the like.

  Further, by using the core material having the metal complex as described above between the walls of the heat insulating box, a heat insulating box having excellent heat insulating performance and excellent productivity can be obtained.

  A metal complex having a one-dimensional, two-dimensional or three-dimensional structure can be used, but one having a three-dimensional structure is preferable.

  Moreover, what can adsorb | suck nitrogen, oxygen, hydrogen, a carbon dioxide, water, carbon monoxide etc. as gas is preferable.

  Moreover, it is also possible to use together the core material which consists of a metal complex, and another adsorption material, for example, a well-known chemical adsorption material and a physical adsorption material.

  Further, as the covering material, a known material having gas barrier properties, such as a laminate film having at least a heat sealing layer, a gas barrier layer, and a protective layer, or a container made of metal, plastic, glass, or the like can be used.

  According to a second aspect of the present invention, the metal complex in the first aspect of the present invention adsorbs a gas under reduced pressure, and a metal complex having a porous skeleton is used as a core material and an adsorbent. It is possible to obtain a heat insulating material excellent in heat insulating performance in the initial stage and over time.

  The invention described in claim 3 is such that the metal complex in the invention described in claim 1 or 2 has a three-dimensional structure, and a metal complex having a porous skeleton, particularly one having a three-dimensional structure, It is easy to design and synthesize a structure having uniform and fine pores, and can be an adsorbent that selectively adsorbs the target gas. For example, for the purpose of nitrogen adsorption, it is possible to design a metal complex having an optimum pore diameter for nitrogen adsorption in consideration of how many molecules of nitrogen are adsorbed in one pore.

  A porous skeleton in which a metal complex has a three-dimensional structure and is laminated by intimately entwining a double sheet structure by coordination bond as a strong and stable structure that can maintain the structure even when gas is not adsorbed Alternatively, a structure having a skeleton connected by a coordinate bond in three dimensions is required.

  As a structure of the metal complex applied to these heat insulators of the present invention, for example, as shown in FIG. 1, there is a metal complex 1 having an interpenetrating structure in which its skeletons are mutually penetrated. In FIG. 1, complexes having a planar structure penetrate each other, but a complex having a three-dimensional lattice structure may penetrate each other. The gas 2 can be adsorbed in a hole formed by a gap between the skeletons penetrating each other.

  Alternatively, as shown in FIG. 2, there is a metal complex 3 having a pillar layer structure in which the pillar structures 5 are linked by coupling the layer structures 4.

  Alternatively, as shown in FIG. 3, there is a metal complex 6 having a connecting lattice layer structure having a skeleton connected in a lattice form.

Examples of the structure of such a complex include [Cu ₂ (2,5-dihydroxybenzoic acid) ₂ (4,4′-bipyridyl)] n and [Cu ₂ (terephthalic acid) ₂ (4,4′-bipyridyl). )] N.

  The invention according to claim 4 is the metal complex according to any one of claims 1 to 3, wherein the metal complex has a pore diameter of 20 mm or less. If the pore diameter is too large, the gas molecules are efficiently removed. Since it cannot adsorb, the pore diameter is desirably 20 mm or less.

  Invention of Claim 5 applies the water | moisture-content adsorption material with the said metal complex in the invention as described in any one of Claim 1 to 4, and a metal complex has a weak thing with respect to a water | moisture content. Therefore, by applying the moisture adsorbing material, it is possible to obtain a more reliable heat insulator.

  The moisture adsorbent used with the core material may be a physical adsorbent such as zeolite, activated alumina, or silica gel, or a chemical adsorbent such as calcium oxide, calcium sulfate, magnesium oxide, magnesium sulfate, calcium chloride, or barium oxide. it can.

  The invention according to claim 6 is the core material according to any one of claims 1 to 5, wherein the core material contains 5 to 20% of an inorganic fiber material with respect to the metal complex. The bending elastic modulus of the material is 0.2 MPa or more, and even a metal complex alone can be used as a core material, but the core material becomes stronger by adding fiber materials such as glass wool, glass fiber, and silica fiber. Thus, a core material excellent in workability and flatness can be obtained. In particular, a core material with better handleability can be obtained by including an inorganic fiber material and making the bending elastic modulus 0.2 MPa or more by performing press working or the like.

  The invention according to claim 7 includes an outer box and an inner box, and arranges the heat insulator according to any one of claims 1 to 6 in a space formed by the outer box and the inner box. A refrigeration apparatus and a cooling / heating apparatus, wherein the space other than the heat insulator is filled with a foam heat insulator.

  For example, when applied to a refrigerator, a vacuum insulator is attached to the outer box side or the inner box side of the space between the outer box and the inner box of the refrigerator, and other spaces are filled with a foam insulator, or a vacuum insulator And a foamed heat insulating body can be used by a method such as disposing in a space between the outer box and the inner box of the refrigerator.

  The invention according to claim 8 includes an outer box and an inner box, a metal complex having a porous skeleton is arranged in a space formed by the outer box and the inner box, and the metal complex is arranged in the space. Is a refrigeration device and a cooling / heating device characterized by having a reduced pressure space, and the space between the outer box and the inner box made of a stainless steel plate can be filled with a metal complex to reduce the pressure inside. At this time, it is also possible to enclose the moisture adsorbing material together or to use it mixed with a metal complex.

  In addition, the refrigeration equipment and the cooling / heating equipment are shown as representatives of equipment that requires heat insulation from the operating temperature range of −30 ° C. to room temperature, and can be used for, for example, a cold car. It also refers to cold / hot equipment that uses hot / cold heat up to higher temperatures, such as vending machines. Moreover, the apparatus which does not require motive power, such as a gas apparatus or a cooler box, is also included.

  Furthermore, it can also be used for personal computers, jar pots, rice cookers, and the like.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 4 shows a cross-sectional view of a heat insulator 7 to which a core material 8 made of a metal complex is applied in Embodiment 1 of the present invention.

  The heat insulator 7 includes a core material 8 made of a metal complex, a moisture adsorbing material 9, and a pair of outer jacket materials 10 having a gas barrier property covering the core material 8 and the moisture adsorbing material 9. The inside of the material 10 is decompressed.

  As the core material 8, a metal complex having a three-dimensional structure composed of terephthalic acid, 4,4′-bipyridine and copper, calcium oxide as the moisture adsorbing material 9, and as the jacket material 10 from the core material 8 side (inner side) in order. Then, a heat insulating body was produced using a laminate film composed of a heat fusion layer, a gas barrier layer, and a surface protective layer.

(Embodiment 2)
FIG. 5 shows a cross-sectional view of a heat insulator 11 in which a core material 12 in which an inorganic fiber material 14 is mixed with a metal complex 13 is applied in Embodiment 2 of the present invention.

  The heat insulator 11 includes a core material 12 composed of a metal complex 13 and an inorganic fiber material 14, a moisture adsorbing material 9, and a jacket material 10 having a pair of gas barrier properties covering the core material 12 and the moisture adsorbing material 9. And the inside of the jacket material 10 is decompressed.

  As the core material 12, a metal complex 13 having a three-dimensional structure composed of 2,5-dihydroxybenzoic acid, 4,4'-bipyridine and copper and an inorganic fiber material 14 composed of glass wool are mixed and pressed, and the core material 12 is pressed. It is used as. The bending elastic modulus of the core material 12 was 0.8 MPa. The jacket material 10 is the same as that of the first embodiment.

(Embodiment 3)
FIG. 6 shows a cross-sectional view of a heat insulating box used in a refrigerator as a refrigeration device and a cooling / heating device in Embodiment 3 of the present invention.

  The heat insulating box 15 has the inner box 16 made of ABS resin and the outer box 17 made of a press-molded iron plate, in which the heat insulating body 7 described in the first embodiment is disposed in advance, and other than the heat insulating body 7 Are filled with foam insulation 18 made of rigid urethane foam.

(Embodiment 4)
FIG. 7: shows sectional drawing of the heat insulation box used for the refrigerator as refrigeration equipment and cold / warm equipment in Embodiment 4 of this invention.

  The heat insulation box 19 includes a core material 8 made of a metal complex and a moisture adsorbing material 9 inside a box body 20 made of stainless steel, and the inside of the box body 20 is decompressed.

  By using a metal complex as the core 8 inside the box and reducing the pressure inside, the heat insulation performance at the initial stage and over time is improved, and a separate heat insulating material is attached to the inside of the box to provide foam insulation in other spaces. The production man-hours of the box body can be greatly reduced and productivity can be improved compared with the method of filling the container.

  As described above, the heat insulator according to the present invention can exhibit excellent heat insulation performance and long-term reliability improvement by applying a metal complex having a porous skeleton as a core material. It can be applied to all kinds of heat insulation applications such as equipment and other hot and cold equipment, and physical objects to be protected from heat and cold.

Schematic diagram of an adsorbent made of a metal complex with an interpenetrating structure Schematic diagram of adsorbent made of metal complex with pillar layer structure Schematic diagram of an adsorbent consisting of a metal complex with a connected lattice layer structure Sectional drawing of the heat insulating body in Embodiment 1 of this invention Sectional drawing of the heat insulating body in Embodiment 2 of this invention Sectional drawing of the heat insulation box in Embodiment 3 of this invention Sectional drawing of the heat insulation box in Embodiment 4 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Metal complex with interpenetrating structure 2 Gas 3 Metal complex with pillar layer structure 4 Layer structure 5 Pillar molecule 6 Metal complex with connecting lattice layer structure 7 Heat insulator 8 Metal complex 9 Moisture absorbing material 10 Cover material 11 Heat insulator DESCRIPTION OF SYMBOLS 12 Core material 13 Metal complex 14 Inorganic fiber material 15 Heat insulation box 16 Inner box 17 Outer box 18 Foam insulation 19 Heat insulation box 20 Box

Claims (8)

  A heat insulator comprising at least a core material and a jacket material having gas barrier properties, wherein the main component of the core material is a metal complex having a porous skeleton.   The heat insulator according to claim 1, wherein the metal complex adsorbs a gas under reduced pressure.   The heat insulator according to claim 1, wherein the metal complex has a three-dimensional structure.   The heat insulating body according to any one of claims 1 to 3, wherein the metal complex has a pore diameter of 20 mm or less.   The heat insulator according to any one of claims 1 to 4, wherein a moisture adsorbent is applied together with the metal complex.   The core material containing 5 to 20% of inorganic fiber material with respect to the metal complex, wherein the core material has a flexural modulus of 0.2 MPa or more. The heat insulation body as described in a term.   An outer box and an inner box are provided, the heat insulator according to any one of claims 1 to 6 is disposed in a space formed by the outer box and the inner box, and foamed in the space other than the heat insulator. A refrigeration apparatus and a cooling / heating apparatus filled with a heat insulator.   An outer box and an inner box, wherein a metal complex having a porous skeleton is arranged in a space formed by the outer box and the inner box, and the space in which the metal complex is arranged is a decompressed space, Refrigeration equipment and cooling / heating equipment.

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