JP2007238141A - Vacuum vessel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vacuum container which is superior in thermal insulation performance and also reliability. <P>SOLUTION: The vacuum container 1 with a vacuum double-wall structure comprises an outer box 3 and an inner box 6 which are made of at least a gas barrier material and a core material 8 and a gas adsorptive material 9 at least capable of adsorbing nitrogen which are decompressed and sealed in a space 7 between the outer box 3 and the inner box 6, wherein the installation of the gas adsorptive material 9 in a high-temperature part with a comparatively high temperature in the space 7 improves the reactivity of the gas adsorptive material 9 and makes gases adsorbed by the core material 8 or the outer box 3 or the inner box 6 desorb on heating and the gas barrier functionality decrease on high temperature like a resin material, so that the gas adsorptive material 9 adsorbs the gases quickly even when a penetration volume of gases are increased. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a vacuum container that can be used as a heat insulating container such as a refrigerator, a heat insulating container, a vending machine, an electric water heater, a vehicle, or the like that requires heat insulation and heat insulation.

  In recent years, energy saving is desired because of the importance of preventing global warming, which is a global environmental problem, and energy saving is also promoted for consumer devices. In a heat-reserving liquid storage container incorporated in the circulation system of an automobile engine, it is possible to secure combustion efficiency from the initial stage of engine operation by keeping warm and effective use of heated and cooled water. In addition, in a heat retaining container such as a jar pot, it contributes to energy saving by increasing the heat retaining performance. In refrigerators, etc., heat entry is cut off, and the operating rate of the refrigeration system is reduced, contributing to energy conservation. From the above viewpoint, a vacuum vessel having improved heat insulation performance is required.

  In the case where heat conduction is performed through the presence of air, there is a mean free path of gas as a physical property affecting the heat insulation performance. The mean free path of a gas is the distance traveled until one of the molecules that make up the air collides with another molecule. If the void formed is larger than the mean free path, the molecules in the gap Collide and heat conduction by gas occurs, so that the thermal conductivity increases.

  The heat insulation principle of a vacuum heat insulator is to eliminate as much air as possible to transfer heat and reduce heat conduction by gas. On the other hand, when the void is smaller than the mean free path, the thermal conductivity is small. This is because there is almost no heat conduction due to air collision.

  As a means for solving such a problem, there is a vacuum heat insulating body constituted by a core material that holds a space and a jacket material that blocks the space and outside air. In general, powder materials, fiber materials, continuous foams, etc. are used as the core material, but in recent years, the demand for vacuum insulators has been diversified, and higher performance vacuum insulators. Is required. The vacuum heat insulator is mainly used as a vacuum heat insulation panel, but a container-like vacuum container is also required due to diversification of forms.

  For example, in a thermal storage tank that is built into the circulation system of an automobile engine and keeps cooling water, a metal vacuum double container is used as a heat insulation structure, and cooling is performed while circulating as the engine operates. Water is introduced into the main body of the vacuum vessel through the partition wall, and after the engine stops, the temperature rising cooling water stagnating in the vessel is kept warm, and the temperature rising cooling water is supplied at the next engine start to ensure combustion efficiency ( Patent Document 1). In the heat insulation structure of the vacuum double container made of metal, the degree of vacuum at the industrial level is about 10 Pa, but there is no solid conduction, and since it is made of metal, there is almost no intrusion of outside air. Further, since it is used at a low temperature of 100 ° C. or less, there is almost no influence of radiation.

  In addition, the vacuum vessel can obtain high-performance heat insulation performance by increasing the degree of vacuum inside, but the gas present inside the vacuum vessel is roughly divided into the following three types. The first is the gas that remains without being evacuated when the vacuum container is manufactured, and the second is the gas generated from the core material and the jacket material after sealing under reduced pressure (the gas adsorbed on the core material and the jacket material) The third gas is a gas that enters from the outside through the jacket material.

In order to adsorb these gases, a method of filling a vacuum heat insulating material with an adsorbent has been devised. For example, there is one that adsorbs carbon dioxide and moisture in a vacuum heat insulating body with a general-purpose adsorbent such as silica alumina (see Patent Document 2).
Japanese Patent Laid-Open No. 10-71840 JP-A-61-103090

  In the configuration of Patent Document 1, since it has a thermos structure, the degree of freedom in shape is low, and it is difficult to increase the size in terms of strength, and the box material is also advantageous for gas barrier properties in order to maintain heat insulation performance. Since the metal is limited to a metal material and has a high thermal conductivity, there is a problem that heat leak through the wall material becomes large. In addition, when leaked, the vacuum space is large, so that the heat insulation performance decreases with a slight leak amount. Furthermore, in the thermos structure, in order to remove the adsorbed moisture and gas, an adsorbent that is heated to 200 ° C. or higher at the time of sealing and operates at that temperature is used. It does not correspond to the internal pressure increase over time such as desorption of the adsorbed gas.

  Moreover, in the structure of patent document 2, gas with low activity, such as nitrogen, cannot be adsorbed under low pressure, the pressure inside the vacuum heat insulating material increases, and the heat insulation performance gradually decreases. Furthermore, the higher the temperature, the greater the amount of desorption of the intruding gas and adsorbed gas, so the life of the heat insulating performance is shortened. Moreover, the heat conductivity of the adsorbent itself also affects the heat insulation performance.

  An object of the present invention is to provide a high-performance vacuum container having a long-term reliability, which is a vacuum container having a vacuum heat insulation box structure having high heat insulation performance.

  In order to achieve the above object, the vacuum container according to the present invention includes an outer box and an inner box made of at least a gas barrier material, a core material that is vacuum-sealed in a space formed by the outer box and the inner box, and at least A vacuum vessel having a vacuum double-wall structure made of a gas adsorbent capable of adsorbing nitrogen, wherein the gas adsorbent is installed in a high temperature portion that is relatively high in the space. Is.

  The gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure. At that time, the higher the ambient temperature, the higher the adsorption activity. In a vacuum container, for example, if it is a heat insulation container that keeps hot water or the like, since the liquid heated in the inner box is kept warm, the temperature on the inner box side is high and a vacuum heat insulating layer is interposed, so the outer box side As you go, the temperature decreases.

  On the other hand, if it is a cold storage container that keeps ice or a cold storage material or the like, the temperature on the outer box side is high and the vacuum heat insulating layer is interposed, so the temperature decreases as it goes to the inner box side.

  Therefore, by installing the gas adsorbent at or near the high temperature portion, the reactivity of the gas adsorbent can be improved, the internal gas can be adsorbed quickly, and the heat insulation performance and performance maintenance of the vacuum vessel can be improved. .

  Furthermore, when the box is made of metal, the vacuum container has a high thermal conductivity of the metal, so the surface of the box in the high temperature area is desorbed from the core material and the box surface in the vicinity. Easier to vaporize. However, by installing the gas adsorbent in the high temperature part of the space, the temperature of the gas adsorbent also rises, so that the adsorption rate is improved and a sufficient reaction rate is obtained even if the amount of adsorbed gas generated increases. Thus, the degree of vacuum can be maintained.

  Further, when the box is made of resin, the gas permeability of the resin material, particularly the thermoplastic resin material, deteriorates as the temperature increases. Therefore, the amount of gas intrusion from the high temperature part increases, but the adsorption speed also increases by installing the gas adsorbent in or around the high temperature part, so it does not affect the heat insulation performance and obtains long-term reliability. Is possible.

  Moreover, since the gas permeability of the resin material becomes easier to permeate as the absolute temperature is higher, the effect becomes greater as the absolute temperature of the high temperature portion is higher.

  In addition, the vacuum container of the present invention includes an outer box and an inner box made of at least a gas barrier material, a core material that is sealed under reduced pressure in a space formed by the outer box and the inner box, and a gas that can adsorb at least nitrogen. A vacuum vessel having a vacuum double-wall structure made of an adsorbent, wherein the gas adsorbent is installed in a low temperature portion where the temperature is relatively low in the space.

  The gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, and is generally solid. In vacuum insulation, the pressure is reduced to reduce heat conduction by gas, but there is a core material to support the vacuum at the same time, and since the core material is solid, the solid thermal conductivity from the core material affects it. . The solid thermal conductivity is influenced by the solid conductivity of the adsorbent in addition to the core material, and the heat insulation performance is further improved by reducing the solid thermal conductivity as much as possible. Although it is possible to reduce the solid thermal conductivity depending on the type, amount, and shape of the adsorbent, the thermal conductivity decreases as the temperature decreases. The influence of solid thermal conductivity can be further reduced.

  This effect is more effective as the amount of adsorbent used is larger or the temperature difference between the high temperature side and the low temperature side is larger.

  In a vacuum container, for example, if it is a heat insulation container that keeps hot water or the like, since the liquid heated in the inner box is kept warm, the temperature on the inner box side is high and a vacuum heat insulating layer is interposed, so the outer box side As you go, the temperature decreases.

  On the other hand, if it is a cold storage container that keeps ice or a cold storage material or the like, the temperature on the outer box side is high and the vacuum heat insulating layer is interposed, so the temperature decreases as it goes to the inner box side.

  Therefore, by installing the gas adsorbing material in the low temperature portion or the vicinity thereof, the solid thermal conductivity of the gas adsorbing material is reduced, and the heat insulating performance of the vacuum vessel can be improved and the performance can be maintained.

  In addition, the vacuum container of the present invention includes an outer box and an inner box made of at least a gas barrier material, a core material that is sealed under reduced pressure in a space formed by the outer box and the inner box, and a gas that can adsorb at least nitrogen. A vacuum vessel having a vacuum double wall structure composed of an adsorbent, wherein the gas adsorbent is installed in an intermediate temperature portion between a high temperature portion where the temperature is relatively high and a low temperature portion where the temperature is relatively low It is characterized by being.

  The gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, and is generally solid. In the vacuum heat insulating material, in addition to the gas thermal conductivity, the solid thermal conductivity of the core material and the gas adsorbent affects. The lower the temperature, the smaller the thermal conductivity and the smaller the effect.

  On the other hand, the gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, but the higher the ambient temperature, the higher the adsorption activity. For this reason, gas is rapidly adsorbed, the gas thermal conductivity is reduced, and high performance and high reliability are obtained.

  In order to take advantage of both of these characteristics, an adsorbent is installed in the middle temperature part between the high temperature part and the low temperature part to reduce the solid thermal conductivity, increase the gas adsorption activity, and provide a vacuum vessel with high heat insulation performance and high reliability. Obtainable.

  The vacuum container of the present invention is characterized in that the gas barrier material is a composite material in which a resin material and a metal sheet are multilayered.

  As a result, it is possible to further improve the gas barrier property of the high gas barrier resin material alone, and the gas barrier property decreases as the temperature increases only with the resin material. Since the gas barrier property is remarkably improved and gas intrusion from the outside can be suppressed, the amount of the gas adsorbent used can be reduced, which is economically excellent. In addition, since the resin material is used for the basic structure, the heat leak is reduced and the heat insulation performance is further improved.

  In addition, by layering resin materials and metal sheets by insert molding, multiple layers can be formed at the same time as molding without increasing the load on equipment and processes, as in vapor deposition and plating. Can be reduced. If a resin sheet formed of a multilayer metal sheet is molded in advance, the resin and metal have different elongation rates and shrinkage rates. Therefore, deformation of the sheet or tearing of the sheet, wrinkles, and other phenomena occur. Have difficulty. In addition, the process of attaching a metal sheet to a resin molded product with an adhesive or the like has a problem that man-hours and costs increase.

  The vacuum container of the present invention improves the reactivity of the gas adsorbing material by installing the gas adsorbing material in the high temperature part, desorbs the gas adsorbed on the core material and the jacket material by heating, and resin material Thus, even if the gas barrier property is lowered and the gas intrusion amount is increased due to the high temperature as described above, the gas adsorbent can be adsorbed quickly, and a vacuum container excellent in heat insulation performance and reliability can be provided.

  The invention of the vacuum container according to claim 1 adsorbs at least nitrogen and a core material that is hermetically sealed in a space formed by at least an outer box and an inner box made of a gas barrier material, and the outer box and the inner box. A vacuum container having a vacuum double wall structure made of a possible gas adsorbing material, wherein the gas adsorbing material is installed in a high temperature portion that is relatively high in the space. By installing the gas adsorbent in a high temperature portion that is relatively high in the space, the temperature of the gas adsorbent also increases, so that the adsorption activity is increased, maintaining the degree of vacuum and improving the reliability. be able to.

  The gas adsorbent used for the vacuum heat insulating material is mainly adsorbed by chemical adsorption in order to maintain a low pressure. At that time, the higher the ambient temperature, the higher the adsorption activity. In a vacuum container, for example, if it is a heat insulation container that keeps hot water or the like, since the liquid heated in the inner box is kept warm, the temperature on the inner box side is high and a vacuum heat insulating layer is interposed, so the outer box side As you go, the temperature decreases.

  On the other hand, if it is a cold storage container that keeps ice or a cold storage material or the like, the temperature on the outer box side is high and the vacuum heat insulating layer is interposed, so the temperature decreases as it goes to the inner box side.

  Therefore, by installing the gas adsorbent in the high temperature part, the reactivity of the gas adsorbent can be improved, the internal gas can be adsorbed quickly, and the heat insulation performance of the vacuum vessel can be improved and the performance can be maintained.

  Furthermore, when the box is made of metal, the vacuum container has a high thermal conductivity of the metal, so the surface of the box in the high temperature area is desorbed from the core material and the box surface in the vicinity. Easier to vaporize. However, by installing the gas adsorbent in the high temperature part of the space, the temperature of the gas adsorbent also rises, so that the adsorption rate is improved and a sufficient reaction rate is obtained even if the amount of adsorbed gas generated increases. Thus, the degree of vacuum can be maintained and the reliability can be improved.

  Further, when the box is made of resin, the gas permeability of the resin material, particularly the thermoplastic resin material, deteriorates as the temperature increases. For this reason, the amount of gas intrusion from the high temperature part or its surrounding area increases, but the adsorption speed increases by installing the gas adsorbent in the high temperature part, so that long-term reliability is obtained without affecting the heat insulation performance. Is possible.

  Moreover, since the gas permeability of the resin material becomes easier to permeate as the absolute temperature is higher, the effect becomes greater as the absolute temperature of the high temperature portion is higher.

  The core material is not particularly limited as to the material system, and is not particularly limited to organic or inorganic fibers, powder, solidified powder, foamed resin, and the like.

  For example, in the case of a core material using fibers, inorganic fibers such as glass wool, glass fibers, alumina fibers, silica alumina fibers, silica fibers, rock wool, silicon carbide fibers, natural fibers such as cotton, synthetic fibers such as polyester and nylon, etc. Known materials such as organic fibers can be used.

  In order to use the fiber, there are methods such as compression or heat compression of the fiber, compression or heat compression using water or a binder, needling, spunlace, and papermaking.

  On the other hand, in the core material using powder, inorganic powder such as silica, pearlite and carbon black, organic powder such as synthetic resin powder, or a mixture thereof is filled as it is or filled into a breathable bag. Or solidifying with a fiber binder or an inorganic or organic liquid binder. In the foamed resin, urethane foam, phenol foam, styrene foam, or the like can be used.

  In the present invention, the high temperature portion indicates a portion having a relatively high temperature in the space between the outer box and the inner box, and it is sufficient that it is at least higher than the average temperature. Preferably, it is desirable to contact a portion having a higher absolute temperature. More preferably, the gas adsorbent is in contact with the relatively hottest portion.

  Further, if a part of the gas adsorbent is present in the high temperature part, the remaining part may be present in the low temperature part, but preferably, more part is present in the high temperature part. Preferably, the whole is in the high temperature part.

Further, the gas adsorbent capable of adsorbing at least nitrogen preferably adsorbs 1 cm ³ / g or more of nitrogen at normal pressure or reduced pressure, more preferably 1000 Pa or less, more preferably 100 Pa or less. It is desirable to adsorb moisture, carbon dioxide and the like. Further, it is desirable to adsorb these at 100 ° C. or less, more preferably at room temperature. A plurality of types of gas adsorbents may be used.

  Further, the gas adsorbent can be used as a powder or a molded body, but is not particularly specified. In addition, the molded gas adsorbent can be used in the form of compression molding, tableting, pelletizing, etc., or the powder in a separate container and the powder in the container compressed Further, the gas adsorbent may be covered with another gas adsorbent.

  As for the method of using the gas adsorbent, the heat insulating body and the container containing the gas adsorbent are evacuated in a state in which the air can be vented, and then the heat insulating body is sealed to form a vacuum heat insulating space. Maintaining the degree of vacuum in the insulator with the gas adsorbent created, or evacuating the insulator to an industrially easily reachable degree, then sealing the insulator, and the remaining insulator It acts like a two-stage pressure reduction by adsorbing the gas inside with a gas adsorbent, or the gas adsorbent is sealed in a separate container and the heat insulating body is evacuated to a predetermined pressure, and then the gas adsorbent It is possible to make the gas adsorbent work like a two-stage decompression while keeping the gas adsorbent more highly active by allowing it to communicate with the heat insulation body in some way, but the usage method is particularly specified It is not a thing.

  Further, the gas adsorbing material may be arranged at one place or at a plurality of places in order to further improve the production efficiency.

  Further, it is possible to remove the gas adsorbent at the time of dismantling such as recycling. Further, the material of the jacket material is not particularly specified.

  The invention of the vacuum container according to claim 2 adsorbs at least nitrogen and a core material which is sealed under reduced pressure in a space constituted by at least an outer box and an inner box made of a gas barrier material, and the outer box and the inner box. A vacuum vessel having a vacuum double wall structure made of a possible gas adsorbent material, wherein the gas adsorbent material is installed in a low-temperature portion where the temperature is relatively low in the space. .

  The gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, and is generally solid. In vacuum insulation, the pressure is reduced to reduce heat conduction by gas, but there is a core material to support the vacuum at the same time, and since the core material is solid, the solid thermal conductivity from the core material affects it. . The solid thermal conductivity is influenced by the solid conductivity of the adsorbent in addition to the core material, and the heat insulation performance is further improved by reducing the solid thermal conductivity as much as possible. Although it is possible to reduce the solid thermal conductivity depending on the type, amount, and shape of the adsorbent, the thermal conductivity decreases as the temperature decreases. The influence of solid thermal conductivity can be further reduced.

  This effect is more effective as the amount of adsorbent used is larger or the temperature difference between the high temperature side and the low temperature side is larger.

  In a vacuum container, for example, if it is a heat insulation container that keeps hot water or the like, since the liquid heated in the inner box is kept warm, the temperature on the inner box side is high and a vacuum heat insulating layer is interposed, so the outer box side As you go, the temperature decreases.

  On the other hand, if it is a cold storage container that keeps ice or a cold storage material or the like, the temperature on the outer box side is high and the vacuum heat insulating layer is interposed, so the temperature decreases as it goes to the inner box side.

  Therefore, by installing the gas adsorbing material in the low temperature portion or the vicinity thereof, the solid thermal conductivity of the gas adsorbing material is reduced, and the heat insulating performance of the vacuum vessel can be improved and the performance can be maintained.

  The core material is not particularly limited as to the material system, and is not particularly limited to organic or inorganic fibers, powder, solidified powder, foamed resin, and the like.

  For example, in the case of a core material using fibers, inorganic fibers such as glass wool, glass fibers, alumina fibers, silica alumina fibers, silica fibers, rock wool, silicon carbide fibers, natural fibers such as cotton, synthetic fibers such as polyester and nylon, etc. Known materials such as organic fibers can be used.

  In order to use the fiber, there are methods such as compression or heat compression of the fiber, compression or heat compression using water or a binder, needling, spunlace, and papermaking.

  On the other hand, in the core material using powder, inorganic powder such as silica, pearlite and carbon black, organic powder such as synthetic resin powder, or a mixture thereof is filled as it is or filled into a breathable bag. Or solidifying with a fiber binder or an inorganic or organic liquid binder. In the foamed resin, urethane foam, phenol foam, styrene foam, or the like can be used.

  In the present invention, the low temperature portion indicates a portion having a relatively low temperature in the space between the outer box and the inner box, and may be at least lower than the average temperature. Preferably, it is desirable to contact a portion having a lower absolute temperature. More preferably, the gas adsorbent is in contact with the relatively coldest portion.

  Further, if a part of the gas adsorbent is present in the low temperature part, the remaining part may be present in the high temperature part, but preferably, more part is present in the low temperature part. Preferably, the whole should be in the low temperature part.

Further, the gas adsorbent capable of adsorbing at least nitrogen preferably adsorbs 1 cm ³ / g or more of nitrogen at normal pressure or reduced pressure, more preferably 1000 Pa or less, more preferably 100 Pa or less. It is desirable to adsorb moisture, carbon dioxide and the like. Further, it is desirable to adsorb these at 100 ° C. or lower, more preferably at room temperature or lower. A plurality of types of gas adsorbents may be used.

  Further, the gas adsorbent can be used as a powder or a molded body, but is not particularly specified. In addition, the molded gas adsorbent can be used in the form of compression molding, tableting, pelletizing, etc., or the powder in a separate container and the powder in the container compressed Further, the gas adsorbent may be covered with another gas adsorbent.

  As for the method of using the gas adsorbent, the heat insulating body and the container containing the gas adsorbent are evacuated in a state in which the air can be vented, and then the heat insulating body is sealed to form a vacuum heat insulating space. Maintaining the degree of vacuum in the insulator with the gas adsorbent created, or evacuating the insulator to an industrially easily reachable degree, then sealing the insulator, and the remaining insulator It acts like a two-stage pressure reduction by adsorbing the gas inside with a gas adsorbent, or the gas adsorbent is sealed in a separate container and the heat insulating body is evacuated to a predetermined pressure, and then the gas adsorbent It is possible to make the gas adsorbent work like a two-stage decompression while keeping the gas adsorbent more highly active by allowing it to communicate with the heat insulation body in some way, but the usage method is particularly specified It is not a thing.

  Further, the gas adsorbing material may be arranged at one place or at a plurality of places in order to further improve the production efficiency.

  Further, it is possible to remove the gas adsorbent at the time of dismantling such as recycling. Further, the material of the jacket material is not particularly specified.

  The invention of the vacuum container according to claim 3 adsorbs at least nitrogen and a core material that is hermetically sealed in a space formed by at least an outer box and an inner box made of a gas barrier material, and the outer box and the inner box. A vacuum container having a vacuum double wall structure made of a possible gas adsorbent, wherein the gas adsorbent is an intermediate temperature between a high temperature portion where the temperature is relatively high and a low temperature portion where the temperature is relatively low It is characterized by being installed in the part.

  The gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, and is generally solid. In the vacuum heat insulating material, in addition to the gas thermal conductivity, the solid thermal conductivity of the core material and the gas adsorbent affects. The lower the temperature, the smaller the thermal conductivity and the smaller the effect.

  On the other hand, the gas adsorbent used for the vacuum heat insulating material performs adsorption mainly including chemical adsorption in order to maintain a low pressure, but the higher the ambient temperature, the higher the adsorption activity. For this reason, gas is rapidly adsorbed, the gas thermal conductivity is reduced, and high performance and high reliability are obtained.

  In order to take advantage of both of these characteristics, an adsorbent is installed in the middle temperature part between the high temperature part and the low temperature part to reduce the solid thermal conductivity, increase the gas adsorption activity, and provide a vacuum vessel with high heat insulation performance and high reliability. Obtainable.

  In a vacuum container, for example, if it is a heat insulation container that keeps hot water or the like, since the liquid heated in the inner box is kept warm, the temperature on the inner box side is high and a vacuum heat insulating layer is interposed, so the outer box side As you go, the temperature decreases.

  On the other hand, if it is a cold storage container that keeps ice or a cold storage material or the like, the temperature on the outer box side is high and the vacuum heat insulating layer is interposed, so the temperature decreases as it goes to the inner box side.

  Therefore, by installing the gas adsorbent in the intermediate temperature portion between the high temperature portion and the low temperature portion of the space, the solid thermal conductivity of the gas adsorbent is reduced, and further, the activation of the adsorbent can be achieved. Improvement of the heat insulation performance of the container and long-term reliability can be ensured.

  The core material is not particularly limited as to the material system, and is not particularly limited to organic or inorganic fibers, powder, solidified powder, foamed resin, and the like.

  For example, in the case of a core material using fibers, inorganic fibers such as glass wool, glass fibers, alumina fibers, silica alumina fibers, silica fibers, rock wool, silicon carbide fibers, natural fibers such as cotton, synthetic fibers such as polyester and nylon, etc. Known materials such as organic fibers can be used.

  In order to use the fiber, there are methods such as compression or heat compression of the fiber, compression or heat compression using water or a binder, needling, spunlace, and papermaking.

  On the other hand, in the core material using powder, inorganic powder such as silica, pearlite and carbon black, organic powder such as synthetic resin powder, or a mixture thereof is filled as it is or filled into a breathable bag. Or solidifying with a fiber binder or an inorganic or organic liquid binder. In the foamed resin, urethane foam, phenol foam, styrene foam, or the like can be used.

  In addition, the high temperature part is a space between the outer box and the inner box and indicates a relatively high temperature part, and the low temperature part is the space between the outer box and the inner box, The part where temperature is low is shown. The intermediate temperature portion refers to a temperature region in between.

  Further, if a part of the gas adsorbent is present in the intermediate temperature part, the remaining part may be present in the low temperature part or the high temperature part, but preferably, a larger part exists in the intermediate temperature part. It is better, and more preferably, the whole is in the intermediate temperature part.

Further, the gas adsorbent capable of adsorbing at least nitrogen preferably adsorbs 1 cm ³ / g or more of nitrogen at normal pressure or reduced pressure, more preferably 1000 Pa or less, more preferably 100 Pa or less. It is desirable to adsorb moisture, carbon dioxide and the like. Further, it is desirable to adsorb these at 100 ° C. or lower, more preferably at room temperature or lower. A plurality of types of gas adsorbents may be used.

  Further, the gas adsorbent can be used as a powder or a molded body, but is not particularly specified. In addition, the molded gas adsorbent can be used in the form of compression molding, tableting, pelletizing, etc., or the powder in a separate container and the powder in the container compressed Further, the gas adsorbent may be covered with another gas adsorbent.

  As for the method of using the gas adsorbent, the heat insulating body and the container containing the gas adsorbent are evacuated in a state in which the air can be vented, and then the heat insulating body is sealed to form a vacuum heat insulating space. Maintaining the degree of vacuum in the insulator with the gas adsorbent created, or evacuating the insulator to an industrially easily reachable degree, then sealing the insulator, and the remaining insulator It acts like a two-stage pressure reduction by adsorbing the gas inside with a gas adsorbent, or the gas adsorbent is sealed in a separate container and the heat insulating body is evacuated to a predetermined pressure, and then the gas adsorbent It is possible to make the gas adsorbent work like a two-stage decompression while keeping the gas adsorbent more highly active by allowing it to communicate with the heat insulation body in some way, but the usage method is particularly specified It is not a thing.

  Further, the gas adsorbing material may be arranged at one place or at a plurality of places in order to further improve the production efficiency.

  Further, it is possible to remove the gas adsorbent at the time of dismantling such as recycling. Further, the material of the jacket material is not particularly specified.

  According to a fourth aspect of the present invention, the gas barrier material according to any one of the first to third aspects is a composite material in which a resin material and a metal sheet are multilayered. The gas barrier property is markedly improved by using a composite material in which a resin material and a metal sheet are multilayered as a gas barrier material, even if the temperature of the resin material alone increases and the gas barrier property decreases. In addition, it is possible to suppress gas intrusion from the outside, improve the gas barrier property in a wide temperature range, and reduce the amount of use of the gas adsorbent.

  On the other hand, since the metal material has a high thermal conductivity, the amount of heat leak that travels through the box increases, and the heat insulation performance decreases, so that the heat leak can also be reduced by combining the metal sheet and the resin material.

  Moreover, although the kind of metal sheet is not limited, it is preferable to use Al, Fe, Cu, stainless steel, or a combination thereof from the viewpoint of cost and versatility.

  In addition, the thicker the metal sheet, the higher the gas barrier property, but the heat leak increases and the workability decreases. Conversely, when the metal sheet is thin, heat leak is reduced, but pinholes are increased and gas barrier properties are inferior. Accordingly, a thickness of 5 μm to 50 μm is preferable.

  The invention of the vacuum container according to claim 5 is characterized in that the composite material according to the invention of claim 4 is produced by insert molding, and in multi-layering, a vapor deposition method is used. In the case of the plating method, the load on the equipment and the process is increased, but if it is insert molding, it is formed into multiple layers at the same time as forming, reducing the number of steps and making it possible to form multiple layers with a simple technique.

  Molding a resin sheet in advance by forming a metal sheet with multiple layers causes the resin and metal to have different elongation and shrinkage rates, causing phenomena such as no deformation, tearing of the sheet, or wrinkling. Is difficult. In addition, the process of attaching a metal sheet to a resin molded product with an adhesive or the like has a problem of increasing the number of steps.

  Also, the molding method is not limited, but blow molding, injection molding, vacuum molding, and pressure molding are the most common and easy to mold. Any molding method may be used. In addition, blow molding has the shape of the container, injection molding has precision molding, vacuum molding and pressure molding have the advantages of low cost molding of large products, so these molding methods can be combined. I do not care.

  According to a sixth aspect of the present invention, the resin material in the fourth or fifth aspect of the invention is an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyamide 6, polyamide 11, polyamide 12, poly Butylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, polyvinylidene fluoride, polyvinylidene chloride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, polyphenylene fluoride, polyether ether ketone, polyimide, polyacrylic resin It is characterized by using at least one from the group consisting of, and by using a resin material having a high gas barrier property, the gas barrier property can be further improved.

  According to a seventh aspect of the present invention, the gas adsorbent according to any one of the first to sixth aspects comprises at least Li and a transition metal that does not form an intermetallic compound with Li. And the enthalpy of mixing of the two metals is greater than zero.

  It is a metal that does not form an intermetallic compound with each other, and a metal having an enthalpy of mixing of the two kinds of metals that is greater than 0 and that normally has no interaction, is included in the metal. It is possible to improve the activity of the metal. Accordingly, the reactivity between the metal and the gas is improved and the gas adsorption activity is increased. Therefore, it becomes a gas adsorbent capable of adsorbing inert and poorly reactive nitrogen at room temperature.

  Examples of transition metals having a mixed enthalpy with Li of greater than 0 include Fe, Cu, Ni, and W. Moreover, it is desirable that Li and at least a part of the transition metal are compatible.

  In the present invention, at least a part is compatible means a state in which at least a part cannot physically separate two kinds of substances. For example, a state in which a part of the boundary surface between two kinds of substances is mixed with each other at the atomic level is not limited to this.

  By mixing at least a part between Li and the transition metal so as to cause compatibility, the repulsive force between the metals can be further increased, and the activity of the metal contained therein can be improved. Therefore, the reactivity with the gas is improved and the gas adsorption activity is increased.

The invention of the vacuum vessel according to claim 8 is characterized in that the gas adsorbent in the invention according to any one of claims 1 to 6 has at least Li, a hardness at 25 ° C. of 5 or more, and a density. It is characterized by containing a solid substance of 4 g / cm ³ or less.

  While the hardness of Li is 0.6, a solid material having a hardness of 5 or more is allowed to coexist, and by grinding Li and the material, the Li surface can be scraped and an active surface can be born. In addition, Li can be subdivided. Therefore, nitrogen can be adsorbed at room temperature by increasing the specific surface area of Li and activating it.

Further, by using a substance having a density of 4 g / cm ³ or less, there is little increase in density even when combined with Li having a density of 0.53 g / cm ^3. For example, even when a gas adsorbent is incorporated in a product, there is no increase in weight. Few.

In the present invention, solid materials having a hardness of 5 or more and a density of 4 g / cm ³ or less include Si, B, c-C, SiO ₂ , SiC, c-BN, Al ₂ O ₃ , MgO and the like. can give. Moreover, it is desirable that Li and at least a part of the solid substance are compatible.

  Moreover, that at least a part is compatible means a state in which at least a part cannot physically separate two kinds of substances. For example, a state in which a part of the boundary surface between two kinds of substances is mixed with each other at the atomic level is not limited to this.

  The invention of the vacuum container according to claim 9 is characterized in that the gas adsorbent in the invention according to claim 7 or claim 8 is manufactured by a process including at least mechanical mixing.

  By the mechanical alloying, the above-described effect of compatibility can be effectively obtained. In addition, Li and the transition metal, or Li and the solid substance can be ground and mixed with high energy, the effect of scraping Li by the solid is increased, and the Li new surface exposure and fragmentation effects are increased. Further, since the solid substance is also cut and subdivided, it becomes more effective for subdividing Li.

  Further, it is considered that mechanical energy is accumulated in Li or the solid substance by performing mechanical mixing, and the energy possessed after mechanical mixing is increased more than the energy possessed at the starting point, resulting in higher activation. It is done.

  In addition, mechanical mixing refers to a mechanical alloying process using a ball milling method, a bulk mechanical alloying method, or the like, as long as the energy possessed after mechanical mixing is greater than the energy possessed at the starting point. The method is not limited.

  In order to produce a highly active gas adsorbent, it is preferable to perform mechanical mixing in an inert gas, for example, in a rare gas atmosphere such as Ar or He, or in a vacuum.

  The invention of the vacuum container according to claim 10 is characterized in that the gas adsorbent in the invention according to any one of claims 1 to 6 is a zeolite containing monovalent Cu ions.

  Zeolite containing monovalent Cu ions, particularly ZSM-5 type zeolite is preferred. General-purpose zeolite cannot adsorb nitrogen at room temperature and under reduced pressure, but zeolite containing monovalent Cu ions can specifically adsorb nitrogen.

  Hereinafter, embodiments of the vacuum container 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)
1 is an external perspective view of a vacuum vessel according to Embodiment 1 of the present invention, FIG. 2 is a longitudinal sectional view of the vacuum vessel according to Embodiment 1, and FIG. 3 is a box of the vacuum vessel according to Embodiment 1. It is the schematic which shows a manufacturing method.

  The configuration of the vacuum container according to the first embodiment will be described with reference to FIG.

  A vacuum vessel 1 having a structure in which hot water or water can be stored inside has a water inlet 2 for storing hot water or the like in the upper part, and an outer box 3 made of a gas barrier material on the outside, and the heat insulating space is decompressed. There are an exhaust port 4 for the purpose and an inlet 5 for enclosing the core material.

  Next, a cross-sectional configuration of the vacuum vessel in the first embodiment will be described with reference to FIG. Detailed description of components having the same configuration as in FIG. 1 is omitted.

  The vacuum vessel 1 is composed of an outer box 3 and an inner box 6 at the top, and a heat insulating space 7 exists between the outer box 3 and the inner box 6. The inside of the heat insulation space 7 is filled with a core material 8 sealed from the inlet 5, and has a gas adsorbent 9 and a moisture adsorbent 10, and the gas adsorbent 10 is installed on the inner box side. . The heat insulating space 7 is exhausted from the exhaust port 4 to become a decompressed space, and then sealed by sealing the exhaust port 4.

The gas barrier material has an air permeation rate of 10 [cm ³ · 10 μm / m ² · day · atm] or less, preferably 1 [cm ³ · 10 μm / m ² · day · atm] or less, more preferably 0.8. 1 [cm ³ · 10 μm / m ² · day · atm] or less is desirable. When the air permeation speed is greater than 10 [cm ³ · 10 μm / m ² · day · atm], the amount of air permeation from the outside increases and the long-term reliability is inferior.

  There are several methods for making a hollow double wall structure. As shown in FIG. 3A, the inner box 6 is formed by blow molding or the like, and the outer box 3 is formed by injection molding, vacuum forming, compressed air. Two outer boxes 3a and 3b are produced by molding or the like, and the inner box 6 is sandwiched and welded.

  Alternatively, as shown in FIG. 3 (b), the inner box 6 is also produced by welding two inner boxes 6a and 6b by injection molding, vacuum forming, pressure forming, etc., and welded to form a vacuum double wall structure.

  Alternatively, as shown in FIG. 3C, two hollow double-walled containers 11a and 11b are produced by blow molding and welded to each other. As shown in FIG. 3D, the hollow double-walled container 11 is formed into a hollow body by blow molding.

  There are various combinations of forming methods and welding methods, but they are not particularly limited. However, from the viewpoint of gas barrier properties and strength, the welded portion is inevitably inferior to the other portions, so it is preferable to reduce it as much as possible.

  In addition, although it is written in resin molding, heat leaks are increased even with metal materials such as stainless steel, but it can be produced by drawing, bending, welding, and has high gas barrier properties, as a vacuum heat insulating housing It is enough.

  Further, in this embodiment, there is only a notation divided into two, but even if the division is divided into three or more, the number of man-hours and welded portions are increased.

  Also, the welding method is not particularly limited, and there are differences in man-hours and equipment, but it is sufficient for joining, vibration welding, ultrasonic welding, laser welding, IRAM, DSI, welding, hot melt, electromagnetic induction, hot air Welding, impulse welding, hot air welding, near red welding, diffusion bonding, and the like are used. These may be combined.

  Moreover, since the welding part can be welded when the flange part is previously provided with the flange part, welding becomes easy.

  Next, the core material is sealed from the injection port 5 in FIG. 1, vacuuming is performed from the exhaust port 4, and after decompression, the injection port 5 and the exhaust port 4 are also welded and sealed.

  In addition, a pinch is made so that the core material does not scatter from the exhaust port when sealed. Further, when the volume of the core material is reduced by press molding, and a void that can further enclose the core material is formed, it is sealed again by pressurization until the void is not formed.

  The evaluation result of the heat insulation performance in the heat insulating body which changed the kind of gas adsorbent is shown in Example 1- Example 3. FIG.

Example 1
The core material includes a powder obtained by mixing 85.5 wt% of dry silica having an average primary particle diameter of 7 nm and 4.5 wt% of carbon black having an average particle diameter of 42 nm, and 10 wt% of glass wool having an average fiber diameter of 0.8 μm as a fiber material. Are molded.

  After mixing the powder with a cutter mill, the fiber material was further added and mixed. The core material thus produced is dried in a drying furnace at 110 ° C. for 1 hour and subjected to pressure molding.

  The box is a multilayer material made of polypropylene having a thickness of 2 mm and an ethylene-vinyl alcohol copolymer (EVOH) having a thickness of 2 μm. The polypropylene is on the inside, and molding is performed by blow molding. Polypropylene and EVOH are bonded with a bonding material (10 μm).

  The outer box is a multilayer material consisting of high density polyethylene with a thickness of 2 mm and EVOH with a thickness of 100 μm. The high density polyethylene is on the outside, and is produced by blow molding like the inner box. 10 μm). The outer box formed by blow molding is cut in half, the inner box is inserted inside, and a gas adsorbent and a moisture adsorbent are installed in the inner box.

  Moreover, it shape | molded so that it might become 10 mm between an inner box and an outer box.

  As the gas adsorbent, a powder obtained by mechanically alloying Li and Fe in an Ar atmosphere was used. After the gas adsorbent is filled in a non-woven bag having air permeability, it is sealed in a hermetically sealed bag having a weak sealing property. A sealed bag with weak sealing performance is sealed when the inside of the sealed bag is at normal pressure and the atmospheric pressure is about normal pressure to medium vacuum, that is, when the pressure difference between the inside and outside is small, When the inserted atmospheric pressure is medium vacuum to high vacuum, that is, when the pressure difference between the inside and outside becomes large, the seal part is separated and the bag has outside air and ventilation part, but the container that encloses the gas adsorbent is specified here is not. Further, calcium oxide was used as the moisture adsorbing material.

  And the outer box and the inner box were welded, and the outer box cut in half was welded at the cut portion. Thereafter, the hollow portion of the box was evacuated, and a core material prepared in advance was sealed from the injection port. After the pressure of the hollow portion of the box was reduced to 25 Pa, both the injection port and the exhaust port were sealed.

  The thermal conductivity of the vacuum container as described above was 0.0073 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0074 W / mK. There was almost no deterioration.

(Example 2)
The core material, jacket material, and moisture adsorbing material were the same as those in Example 1, and the construction method was also produced in the same manner. The gas adsorbent used was a powder obtained by mechanically alloying Li and Al ₂ O ₃ in an Ar atmosphere.

  The thermal conductivity of the vacuum container as described above was 0.0074 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0076 W / mK. There was almost no deterioration.

(Example 3)
The core material, jacket material, and moisture adsorbing material were the same as those in Example 1, and the construction method was also produced in the same manner. As the gas adsorbent, a powder obtained by mechanically alloying Li and MgO in an Ar atmosphere was used.

  The thermal conductivity of the vacuum container as described above was 0.0072 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0073 W / mK, and the performance There was almost no deterioration.

Example 4
The core material and the jacket material were the same as in Example 1, and the construction method was also produced in the same manner. As the gas adsorbent, ZSM-5 zeolite exchanged with Cu ions was used.

  The thermal conductivity of the vacuum container as described above was 0.0075 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0077 W / mK. There was almost no deterioration.

(Example 5)
The jacket material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 1, and were produced by the same method as in Example 1 until the outer box formed by blow molding was cut in half.

  The solidified core material and the inner box were inserted inside, the outer box and the inner box were welded, and the outer box cut in half was welded at the cut portion. Then, the box body hollow part was evacuated, the box body hollow part was depressurized to 25 Pa, and both the inlet and the outlet were sealed.

  A glass fiber having an average fiber diameter of 5 μm was used as the core material, and a double wall space shape was press-molded at 500 ° C. and solidified.

  The thermal conductivity of the vacuum container as described above was 0.0053 W / mK.

  In addition, 80% hot water was poured in 80% of the container, left in an atmosphere at 25 ° C for 1 day, and repeated for 60 days. The thermal conductivity was 0.0055 W / mK. There was almost no deterioration.

(Example 6)
The core material, jacket material, and moisture adsorbing material were the same as those in Example 1, and the construction method was also produced in the same manner. The gas adsorbent used was a powder obtained by mechanically alloying Li and Al ₂ O ₃ in an Ar atmosphere.

  The thermal conductivity of the vacuum container as described above was 0.0074 W / mK. This was left for 60 days in an atmosphere of 25 ° C., and then 80% of water was poured into the container at 80 ° C., and left in an atmosphere of 25 ° C. for 1 day. .0071 W / mK, almost no deterioration in performance, and improved performance due to a decrease in thermal conductivity.

(Example 7)
The core material, jacket material, and moisture adsorbing material were the same as those in Example 1, and the construction method was also produced in the same manner. The gas adsorbent used was a powder obtained by mechanically alloying Li and Al ₂ O ₃ in an Ar atmosphere. Moreover, the adsorbent was installed in the approximate center of the core.

  The thermal conductivity of the vacuum container as described above was 0.0074 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0074 W / mK. There was no deterioration and there was almost no influence of the thermal conductivity of the adsorbent.

(Embodiment 2)
FIG. 4 is a longitudinal sectional view of the vacuum vessel according to Embodiment 2 of the present invention.

  In the longitudinal cross-sectional view of FIG. 4, the vacuum vessel 12 includes an outer box 13 and an inner box 14, and a heat insulating space 7 exists between the outer box 13 and the inner box 14. A metal sheet 15 is insert-molded inside the outer box 13 and outside the inner box 14. The inside of the heat insulating space 7 is filled with a core material 16 that is pressurized and sealed from the injection port 5 to form a molded body, and has a gas adsorbing material 9 and a moisture adsorbing material 10. The gas adsorbent 9 and the moisture adsorbent 10 are installed in contact with the inner box 14. The heat insulating space 7 is exhausted from the exhaust port 4 to become a decompressed space, and then the exhaust port 4 is sealed to form a sealed space.

(Example 8)
The core material includes a powder obtained by mixing 85.5 wt% of dry silica having an average primary particle diameter of 7 nm and 4.5 wt% of carbon black having an average particle diameter of 42 nm, and 10 wt% of glass wool having an average fiber diameter of 0.8 μm as a fiber material. Are molded.

  After mixing the powder with a cutter mill, the fiber material was further added and mixed. The core material thus produced is dried in a drying furnace at 110 ° C. for 1 hour and subjected to pressure molding.

  The box is a multi-layer material having a structure in which an inner box is sandwiched between two polypropylenes having a thickness of 1 mm and an ethylene-vinyl alcohol copolymer (EVOH) having a thickness of 100 μm, and the molding is performed by blow molding. Polypropylene and EVOH are bonded with a bonding material (10 μm). A metal sheet made of a multilayer material of nylon (10 μm), aluminum sheet (20 μm) and polypropylene (7 μm) is placed on the flat surface of the inner surface of the mold at the time of blow molding and integrated into the inner box at the same time as molding. Perform insert molding. The metal sheets nylon and aluminum, and aluminum and polypropylene are bonded together by a bonding material (5 μm). Moreover, a metal sheet joins the polypropylene side with an inner box.

  The outer box is a multilayer material made of 2 mm thick high density polyethylene and 100 μm thick ethylene-vinyl alcohol copolymer (EVOH). Like the inner box, the outer box is made by blow molding, and the high density polyethylene and EVOH are bonded materials ( 10 μm). The metal sheet is a multilayer material of nylon (10 μm), aluminum sheet (20 μm), and polyethylene (7 μm), and is placed on the mold flat part during blow molding and insert molding. The metal sheets nylon and aluminum, and aluminum and polyethylene are joined together by a joining material (5 μm). Moreover, a metal sheet joins the polyethylene side with an outer case.

  The outer box formed by blow molding is cut in half, the inner box is inserted inside, and a gas adsorbent and a moisture adsorbent are installed in the inner box. Moreover, it shape | molded so that it might become 10 mm between an inner box and an outer box. The coverage with the metal sheet was 80% of the total surface area.

  As the gas adsorbent, a powder obtained by mechanically alloying Li and Fe in an Ar atmosphere was used. After the gas adsorbent is filled in a non-woven bag having air permeability, it is sealed in a hermetically sealed bag having a weak sealing property. A sealed bag with weak sealing performance is sealed when the inside of the sealed bag is at normal pressure and the atmospheric pressure is about normal pressure to medium vacuum, that is, when the pressure difference between the inside and outside is small, When the inserted atmospheric pressure is medium vacuum to high vacuum, that is, when the pressure difference between the inside and outside becomes large, the seal part is separated and the bag has outside air and ventilation part, but the container that encloses the gas adsorbent is specified here is not. Further, calcium oxide was used as the moisture adsorbing material.

  And the outer box and the inner box were welded, and the outer box cut in half was welded at the cut portion. Thereafter, the hollow portion of the box was evacuated, and a core material prepared in advance was sealed from the injection port. After the pressure of the hollow portion of the box was reduced to 24 Pa, both the injection port and the exhaust port were sealed.

  The thermal conductivity of the vacuum container as described above was 0.0069 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0069 W / mK. There was almost no deterioration.

(Embodiment 3)
FIG. 5 shows a heat storage warming device for an automobile to which a vacuum vessel according to Embodiment 3 of the present invention is applied.

  In FIG. 5, the regenerative warming device 17 is a circulation path in which the cooling water heated by the engine 19 is cooled by the radiator 20 through the cooling water circuit 18 and returns to the engine 19 again. In addition, when the cooling water at the time of starting the engine is not warmed, the thermostat 21 is fully closed, and the cooling water circulates through the bypass passage 22 without passing through the radiator 20 having a heat radiation action, and the temperature of the cooling water is increased. Speed up.

  Further, during continuous running of the automobile, the cooling water warmed in the cooling water circuit 20 flows into the vacuum vessel 26 from the switching inlet pipe 24 through the flow rate control valve 23 and is kept warm. Thereafter, when the engine is started, the flow control valve 23 is caused to flow from the switching outlet pipe 25 to the cooling water circuit and mixed with the cooling water to accelerate the temperature rise of the cooling water. Therefore, it is possible to improve the fuel efficiency of the vehicle when starting the engine.

  The vacuum vessel 26 uses the vacuum vessel of the first embodiment or the second embodiment, and since the heated cooling water is kept in the vacuum vessel, the gas barrier property of the resin material is lowered. The gas adsorbent is installed on the inner box side, the gas adsorption speed is improved, and the heat insulation performance can be maintained.

(Embodiment 4)
FIG. 6 is a longitudinal sectional view of a refrigerator to which the vacuum container according to Embodiment 4 of the present invention is applied.

  The refrigerator 27 has a vacuum heat insulating box structure, and includes an inner box 28 constituting the inside of the refrigerator and an outer box 29 constituting the outer wall, and a heat insulating layer 30 exists between the inner box 28 and the outer box 29. The outer box 29 is made of a PCM steel plate, and the inner box 28 is made of an ABS resin in which an aluminum sheet is insert-molded. The aluminum sheet is provided on the heat insulating layer side. The inside of the heat insulation layer 30 is filled with a core material 31 and has a gas adsorbent 32 and a moisture adsorbent 33. Reference numeral 34 denotes an exhaust port, 35 denotes a machine room, and 36 denotes a compressor. Isobutane is used as the refrigerant.

Example 9
The core material is made of glass fibers having an average fiber diameter of 5 μm, coated with a 3 wt% sodium silicate solution as a binder, dried in a solvent while pressing at 450 ° C. into the shape of the heat insulating layer, and solidified.

  The inner box is a multilayer material in which an aluminum sheet (20 μm) is insert-molded into a 3 mm thick ABS resin and a 20 μm thick ethylene-vinyl alcohol copolymer (EVOH). To do.

  The outer box is a 1 mm thick PCM steel plate and is formed by press molding. The core material is inserted between the outer box and the inner box, and the outer box and the inner box are joined at the contact portion.

  As the gas adsorbent, a powder obtained by mechanically alloying Li and Fe in an Ar atmosphere was used. After the gas adsorbent is filled in a non-woven bag having air permeability, it is sealed in a hermetically sealed bag having a weak sealing property. A sealed bag with weak sealing performance is sealed when the inside of the sealed bag is at normal pressure and the atmospheric pressure is about normal pressure to medium vacuum, that is, when the pressure difference between the inside and outside is small, When the inserted atmospheric pressure is medium vacuum to high vacuum, that is, when the pressure difference between the inside and outside becomes large, the seal part is separated and the bag has outside air and ventilation part, but the container that encloses the gas adsorbent is specified here is not. Further, calcium oxide was used as the moisture adsorbing material.

  The gas adsorbent was placed with emphasis on the outer wall side, which is hotter than the inside of the cabinet, particularly on the periphery of the compressor and condenser. In addition, it was also installed on the inner box side in the vicinity of the relatively high temperature around the radiant heater.

  The heat insulating layer is depressurized from the exhaust port by a vacuum pump outside the refrigerator, and seals the exhaust port portion when the degree of vacuum reaches about 30 Pa.

  When the power consumption of the refrigerator configured as described above was measured, it was reduced by 20% compared to the refrigerator without the gas adsorbent, and the heat insulating effect was confirmed.

  Next, a comparative example for the information device of the present invention is shown.

(Comparative Example 1)
The envelope material, the core material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 1, and a vacuum container having substantially the same structure and construction method was prepared. No gas adsorbent was used.

  The thermal conductivity of the vacuum container as described above was 0.0083 W / mK.

  Moreover, 80% hot water was poured in 80% of the container, left in an atmosphere at 25 ° C. for 1 day, and repeated for 60 days. The thermal conductivity was 0.0234 W / mK.

(Comparative Example 2)
The envelope material, the core material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 1, and a vacuum container having substantially the same structure and construction method was prepared. The gas adsorbent was placed in close contact with the outer box.

  The thermal conductivity of the vacuum container as described above was 0.0073 W / mK.

  In addition, 80% hot water was poured in 80% of the container, left in a 25 ° C. atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0094 W / mK.

(Comparative Example 3)
The outer casing material, the core material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 5, and a vacuum container having substantially the same configuration and construction method was manufactured. No gas adsorbent was used.

  The thermal conductivity of the vacuum container as described above was 0.0058 W / mK.

  Moreover, 80% hot water was poured in 80% of the container, left in an atmosphere at 25 ° C. for 1 day, and repeated for 60 days. The thermal conductivity was 0.0252 W / mK.

(Comparative Example 4)
The outer casing material, the core material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 5, and a vacuum container having substantially the same configuration and construction method was manufactured. The gas adsorbent was placed in close contact with the outer box.

  The thermal conductivity of the vacuum container as described above was 0.0053 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C. atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0072 W / mK.

(Comparative Example 5)
The envelope material, the core material, the gas adsorbing material, and the moisture adsorbing material were the same as those in Example 6, and a vacuum container having substantially the same structure and construction method was produced. No gas adsorbent was used.

  The thermal conductivity of the vacuum container as described above was 0.0069 W / mK.

  In addition, 80% hot water was poured into 80% of the container, left in a 25 ° C. atmosphere for 1 day, and repeated for 60 days. The thermal conductivity was 0.0105 W / mK.

  As described above, the vacuum container according to the present invention has a gas adsorbent placed in a high-temperature part so that the adsorption activity is improved, and a vacuum container excellent in heat insulation performance and reliability can be configured. It can be applied to all types of thermal insulation such as thermal storage warming devices, heat pump thermal insulation tanks, refrigerators and refrigerators, refrigerators, refrigerators, refrigerators, and other objects that want to protect against heat and cold.

External appearance perspective view of the vacuum vessel in Embodiment 1 of this invention The longitudinal cross-sectional view of the vacuum vessel in Embodiment 1 of this invention Schematic which shows the manufacturing method of the box of the vacuum vessel body in Embodiment 1 of this invention Longitudinal sectional view of a vacuum vessel in Embodiment 2 of the present invention Schematic configuration diagram of a vehicle heat storage type warming device to which a vacuum vessel according to Embodiment 3 of the present invention is applied The longitudinal cross-sectional view of the refrigerator which applied the vacuum vessel in Embodiment 4 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Vacuum container 3 Outer box 6 Inner box 7 Space 8 Core material 9 Gas adsorbent 12 Vacuum container 13 Outer box 14 Inner box 16 Core material 26 Vacuum container 27 Refrigerator 28 Inner box 29 Outer box 30 Heat insulation layer 31 Core material 32 Gas adsorption Material

Claims (10)

  A vacuum double wall comprising an outer box and an inner box made of at least a gas barrier material, a core material that is sealed under reduced pressure in a space constituted by the outer box and the inner box, and a gas adsorbing material capable of adsorbing at least nitrogen It is a vacuum container which has a structure, Comprising: The said gas adsorbent is installed in the high temperature part which becomes comparatively high temperature in the said space, The vacuum container characterized by the above-mentioned.   A vacuum double wall comprising an outer box and an inner box made of at least a gas barrier material, a core material that is sealed under reduced pressure in a space constituted by the outer box and the inner box, and a gas adsorbing material capable of adsorbing at least nitrogen It is a vacuum container which has a structure, Comprising: The said gas adsorbent is installed in the low temperature part used as the relatively low temperature in the said space, The vacuum container characterized by the above-mentioned.   A vacuum double wall comprising an outer box and an inner box made of at least a gas barrier material, a core material that is sealed under reduced pressure in a space constituted by the outer box and the inner box, and a gas adsorbing material capable of adsorbing at least nitrogen A vacuum container having a structure, wherein the gas adsorbent is installed in an intermediate temperature portion between a high temperature portion having a relatively high temperature and a low temperature portion having a relatively low temperature in the space. container.   The vacuum container according to any one of claims 1 to 3, wherein the gas barrier material is a composite material in which a resin material and a metal sheet are multilayered.   The vacuum container according to claim 4, wherein the composite material is produced by insert molding.   The resin material is ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyamide 6, polyamide 11, polyamide 12, polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, polyvinylidene fluoride, polyvinylidene chloride, ethylene-tetrafluoro. The at least one selected from the group consisting of an ethylene copolymer, polytetrafluoroethylene, polyphenylene fluoride, polyetheretherketone, polyimide, and polyacrylic resin is used. Vacuum container.   The gas adsorbent comprises at least Li and a transition metal that does not form an intermetallic compound with Li, and the enthalpy of mixing of the two metals is greater than 0. The vacuum container as described in any one of these. The said gas adsorbent contains at least Li and the solid substance whose hardness in 25 degreeC is 5 or more and whose density is 4 g / cm < ³ > or less, The any one of Claims 1-6 characterized by the above-mentioned. A vacuum container according to 1.   The vacuum container according to claim 7 or 8, wherein the gas adsorbent is manufactured by a process including at least mechanical mixing.   The vacuum container according to any one of claims 1 to 6, wherein the gas adsorbent is a zeolite containing monovalent Cu ions.

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