JP2006105286A - Heat insulating body, freezing apparatus, and cooling-heating apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easy-to-handle heat insulating body capable of maintaining a superior heat insulation property for a long period of time by mixing conductive powder in a metal complex having superior performance as a core material and even as an adsorbent, and using it. <P>SOLUTION: The heat insulating body 7 is provided with a core material 8, a moisture adsorbent 9, and a covering material 10 having gas barrier performance and covering the core material 8 and the moisture adsorbent 9, and it is characterized by that the core material 8 includes the conductive powder and the metal complex having a porous frame. By using the conductive powder and the metal complex having the porous frame as the core material 8, the conductive powder can suppress adhesion to an apparatus for suppressing static electricity generated by the metal complex, and aggregation of metal complexes, and fixed heat conduction is reduced in the metal complex acting as the core material and the adsorbent. As a result, the heat insulating body 7 with superior handling, initial heat insulating property, and heat insulating property over time can be provided. <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 exhausted when the vacuum heat insulator is produced, and the other is the gas generated from the core material and the jacket material after being vacuum-sealed (adsorbed on 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 insulation panel has been proposed in which a porous resin powder having a gas adsorbing ability is bonded to a part or all of a core material with a binder (see, for example, Patent Document 2).

  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, a porous resin is used as the core material and the adsorbent, but it is difficult to uniformly polymerize the monomer to obtain a uniform polymer. It is difficult to make the pore diameter of the resin completely uniform and fine. 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.

  In addition, since the resin has a property of being easily charged with static electricity, the resin itself is aggregated due to static electricity or adheres to a device in the manufacturing process, so that it is very difficult to handle. Therefore, the adhesive treatment is performed with the binder, but there is also a problem that the gas generation from the binder and the solid heat conduction of the binder itself are high.

  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. In general, a metal complex is synthesized as a powder. However, in order to use this material as a heat insulator, the material itself is likely to be charged like a resin, and it is very difficult to handle.

  The present invention solves the above-mentioned conventional problems, and by using a means for suppressing static electricity in a metal complex having excellent performance as a core material and an adsorbent, an initial stage including an easy-to-handle core material and It aims at providing the heat insulating body which has the heat insulation performance excellent also over time.

  In order to achieve the above object, the heat insulator of the present invention comprises at least a core material and a jacket material having gas barrier properties and covering the core material, wherein the core material is a metal complex having a porous skeleton. The core material further includes at least one kind of conductive powder.

  By including a conductive powder that suppresses static electricity in a metal complex having a porous skeleton that has excellent performance as both a core material and an adsorbent material, it is possible to provide an easy-to-handle core material at an initial stage and over time. A heat insulator having excellent heat insulation performance can be provided.

  The heat insulator of the present invention uses a metal complex having a porous skeleton as a core material and a conductive powder, so that the conductive powder adheres to the device of the manufacturing process due to static electricity of the metal complex, In order to prevent the metal complexes from aggregating, handling becomes easy. At the same time, since the reduction of solid heat conduction can be obtained by crushing the aggregation of metal complexes that act as both a core and an adsorbent, heat insulation that is excellent in initial heat insulation performance and can maintain good heat insulation performance for a long period of time You can get a body.

  The invention of the heat insulator according to claim 1 of the present invention is a metal complex comprising at least a core material and a jacket material having gas barrier properties and covering the core material, wherein the core material has a porous skeleton. The core material further includes at least one kind of conductive powder.

  Metal complexes with a porous skeleton, especially those with a three-dimensional structure, are easy to design and synthesize a structure with uniform and fine pores, and the pore diameter formed is less than the mean free path of the gas When used as a core material of a heat insulator, there is almost no gas heat conduction due to gas collision in the pores, and it can act as a core material that can exhibit excellent heat insulation performance that is not affected by gas heat conduction Is.

  In addition, since the metal complex has a very large gas phase ratio as compared with zeolite or the like having a thin wall thickness and an inorganic porous material, low solid thermal conductivity can be realized.

  Further, the metal complex and the conductive powder are included as a core material, and the metal powder is produced by the process of suppressing the static electricity of the metal complex by desirably using a mixture of these. It is easy to handle because it adheres to the instrument and prevents aggregation of metal complexes.

  Furthermore, the solid heat conduction can be reduced, and a core material having excellent initial heat insulation performance can be obtained. This phenomenon is presumably due to the fact that the charge of the conductive powder gives rise to electrical repulsion to the cohesive force of the metal complex powder, thereby breaking up the aggregation. Aggregation is refined by crushing and the solid contact point per unit volume is increased. As a result, it is considered that the solid thermal resistance increases and the thermal conductivity of the solid decreases.

  In addition, since the agglomeration is crushed, the voids formed by the metal complex powder are refined, and a core material structure that is less affected by gas thermal conductivity is formed, improving reliability over time. is there.

  As described above, by using a core material including a metal complex having a porous skeleton and at least one type of conductive powder, a heat insulating material that is easy to handle and excellent in heat insulating performance in the initial stage and over time can be obtained. Obtainable.

  In addition, metal complexes having a one-dimensional, two-dimensional, or three-dimensional structure can be used, but those having a three-dimensional structure are preferable.

  Moreover, it is also possible to use together the core material which consists of a metal complex and electroconductive powder, 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.

In addition, the conductive powder refers to a powder having a specific resistance value of less than 1 × 10 ⁸ Ω / cm, preferably a powder specific resistance value of 1 × 10Ω such as carbon powder or tin oxide composition. / Cm or less. In particular, carbon black is industrially inexpensive and is suitable because it has a powder specific resistance value of less than 0.1 Ω / cm. The effect is obtained when the addition rate of the conductive powder is 0.1 wt% or more, but it is preferably less than 40 wt% because the conductive powder itself has an adverse effect on solid heat conduction as the addition rate increases. More preferably, it is in the range of 5 wt% to 30 wt%.

  In addition, the core material can be used by being sealed in a container or bag, or can be used by pressing, but it is further mixed with inorganic fiber materials such as glass wool, glass fiber, silica fiber, pressed and solidified for heat insulation. It can also be used as a material.

  Moreover, even if the inside of a heat insulating body is pressure-reduced, it can also be used by a normal pressure.

  By using a core material including the metal complex and conductive powder as described above as the core material of the heat insulator, it is easy to handle, has excellent heat insulation performance, and obtains a highly reliable heat insulator. Can do.

  The invention of a heat insulator according to claim 2 is characterized in that the metal complex in the invention according to claim 1 adsorbs a gas under reduced pressure.

  Metal complexes with a porous skeleton, especially those with a three-dimensional structure, can be easily designed and synthesized with a structure with 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. 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, gas can be more adsorbed by supporting an active metal in the complex. In addition, 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.

  As the adsorbed gas species, those capable of adsorbing nitrogen, oxygen, hydrogen, carbon dioxide, water, carbon monoxide and the like are preferable.

  The invention of the heat insulator according to claim 3 is characterized in that the metal complex in the invention according to claim 1 or 2 has a three-dimensional structure.

  When the metal complex has a three-dimensional structure, the structure is maintained even when no gas is adsorbed, and the metal complex can be used stably. Examples of a strong and stable structure include a porous skeleton in which a double sheet structure by coordination bonds is closely entangled and laminated, or a structure having a skeleton connected by coordination bonds in three dimensions.

  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 molecules 2 can be adsorbed into the holes formed by the gaps 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.

As the structure of such a complex, for example, [Cu ₂ (2,5 1-dihydroxybenzoic acid) ₂ (4,4′-bipyridyl)] n or [Cu ₂ (terephthalic acid) ₂ (4,4′-bibipyridyl) )] N.

  The invention of the heat insulator according to claim 4 is characterized in that the metal complex in the invention according to any one of claims 1 to 3 has a pore diameter of 20 mm or less.

  When the pore diameter of the metal complex is 20 mm or less, a pore structure suitable for adsorption of nitrogen, oxygen, etc. is obtained. Therefore, when the inner space of the heat insulator is used as a reduced pressure, the core material can adsorb oxygen and nitrogen. It also acts as an adsorbent, and its reliability over time is improved.

  The invention of a heat insulator according to claim 5 is characterized in that, in the invention according to any one of claims 1 to 4, a moisture adsorbent is applied together with the metal complex.

  Some metal complexes are highly reactive with moisture, and the porous structure may be destroyed by reaction with moisture. Therefore, by applying a moisture adsorbing material to remove moisture, a more reliable heat insulator can be obtained.

  As the moisture adsorbent, 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 can be used.

  The invention of the refrigeration apparatus and the cooling / heating apparatus according to claim 6 includes an outer box and an inner box, and a space formed by the outer box and the inner box is any one of claims 1 to 5. The heat insulator described in the paragraph is arranged, and the space other than the heat insulator is filled with a foam heat insulator.

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

  Note that the refrigeration equipment and the cold / hot 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 or the like. 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.

  The invention of the refrigeration equipment and the cooling / heating equipment according to claim 7 includes an outer box and an inner box, and a metal complex having a porous skeleton and at least one kind in a space formed by the outer box and the inner box A material in which a conductive powder is mixed is disposed, and the space in which the metal complex having a porous skeleton and the material in which at least one kind of conductive powder is mixed is disposed is a decompressed space. Is.

  At this time, it is also possible to enclose the moisture adsorbing material together or to use it mixed with a metal complex.

  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 having a porous skeleton and conductive powder is applied in Embodiment 1 of the present invention.

  The heat insulator 7 includes a core material 8 made of a metal complex and conductive powder, a moisture adsorbing material 9, and a covering material 10 having a gas barrier property and covering the core material 8 and the moisture adsorbing material 9. The inside of the jacket 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, carbon black as the conductive powder, calcium oxide as the moisture adsorbing material 9, and the core as the jacket material 10 A heat insulator 7 was produced using a laminate film composed of a heat fusion layer, a gas barrier layer, and a surface protective layer in this order from the material 8 side (inner side).

(Embodiment 2)
FIG. 5 shows a cross-sectional view of a heat insulating box used in a refrigerator as an example of a refrigeration apparatus and a cooling / heating apparatus in Embodiment 2 of the present invention.

  The heat insulating box 11 is provided with the heat insulating body 7 described in the first embodiment in advance inside a box made up of an inner box 12 made of ABS resin and an outer box 13 made of press-formed iron plate. The space other than the above is foam-filled with a foam insulation 14 made of rigid urethane foam.

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

  The heat insulating box 15 includes a core 8 made of a metal complex and conductive powder and a moisture adsorbing material 9 inside a box 16 made of stainless steel, and the inside of the box 16 is decompressed. .

  By using a metal complex and conductive powder as the core material 8 inside the box body 16, more preferably using a core material 8 in which these are mixed, and making the inside of the box body 16 a decompressed space, the handling property is excellent, In addition to improving the heat insulation performance over time and over time, the number of man-hours for producing the box body 16 is greatly reduced compared with the method of attaching a separate heat insulating material inside the box body 16 and filling the other space with foam insulation. It is possible to improve the performance.

  As described above, the heat insulator according to the present invention improves handling and improves heat insulation performance and long-term reliability by applying a metal complex having a porous skeleton to the core material and conductive powder. It can be expressed, and can be applied to all types of heat insulation applications such as hot and cold equipment such as refrigerators and refrigerators, 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 insulation box in Embodiment 2 of this invention Sectional drawing of the heat insulation box in Embodiment 3 of this invention

Explanation of symbols

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

Claims (7)

  At least a core material and a jacket material having gas barrier properties and covering the core material, wherein the core material is a metal complex having a porous skeleton, and the core material has at least one kind of conductive powder. A heat insulator characterized by including a body.   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 a pore diameter of the metal complex is 20 mm or less.   The heat-insulating material according to any one of claims 1 to 4, wherein a moisture adsorbing material is applied together with the metal complex.   An outer box and an inner box are provided, and the heat insulator according to any one of claims 1 to 5 is disposed in a space formed by the outer box and the inner box, and other than the heat insulator. A refrigeration apparatus and a cooling / heating apparatus, wherein the space is filled with a foam insulation.   An outer box and an inner box are provided, and in the space formed by the outer box and the inner box, a material in which a metal complex having a porous skeleton and at least one kind of conductive powder are mixed is disposed, and is porous A refrigerating apparatus and a cooling / heating apparatus, wherein the space in which the metal complex having a skeleton and the material mixed with at least one kind of conductive powder are arranged is a decompressed space.

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